Amino Acid Racemization Research Articles

Capillary electrophoresis and molecular modeling of the chiral separation of aromatic amino acids using α/β-cyclodextrin and 18-crown-6.

In this work, chiral separation of enantiomers of three amino acids was achieved using capillary electrophoresis technique with α-cyclodextrin (αCD) as a running buffer additive. Only tryptophan has exhibited baseline separation in the presence of αCD, while the enantiomers of the other two amino acids, phenylalanine and tyrosine, were only partially separated. The addition of 18-crown-6 (18C6) as a second additive imparted only slight improvement to the separation of all enantiomers. On the other hand, all three racemic amino acid mixtures demonstrated no indication of separation when the larger cavity cyclodextrin members, β- and γCD, are used as running buffer chiral additives. However, remarkable improvements in the separation of the enantiomers of phenylalanine and tyrosine were obtained when 18C6 is used together with βCD as a running buffer additive. Surprisingly, tryptophan enantiomers were not separated by the dual additive system of cyclodextrin and crown ether. Using electrospray ionization mass spectrometry (ESI-MS), all amino acids were found to form stable binary complexes with individual hosts as well as ternary compounds involving the crown ether and the cyclodextrin. Furthermore, we used molecular dynamics (MD) simulations to build a clear picture about the interaction between the guest and the hosts. Most of these complexes remained stable throughout the simulation times, and the molecular dynamics study allowed better understanding of these supramolecular assemblies.

Last interglacial (MIS 5e) sea-level proxies in southeastern South America

Abstract. Coastal southeast South America is one of the classic locations where there are robust, spatially extensive records of past high sea level. Sea-level proxies interpreted as last interglacial (Marine Isotope Stage 5e, MIS 5e) exist along the length of the Uruguayan and Argentinian coast with exceptional preservation especially in Patagonia. Many coastal deposits are correlated to MIS 5e solely because they form the next-highest terrace level above the Holocene highstand; however, dating control exists for some landforms from amino acid racemization, U∕Th (on molluscs), electron spin resonance (ESR), optically stimulated luminescence (OSL), infrared stimulated luminescence (IRSL), and radiocarbon dating (which provides minimum ages). As part of the World Atlas of Last Interglacial Shorelines (WALIS) database, we have compiled a total of 60 MIS 5 proxies attributed, with various degrees of precision, to MIS 5e. Of these, 48 are sea-level indicators, 11 are marine-limiting indicators (sea level above the elevation of the indicator), and 1 is terrestrial limiting (sea level below the elevation of the indicator). Limitations on the precision and accuracy of chronological controls and elevation measurements mean that most of these indicators are considered to be low quality. The database is available at https://doi.org/10.5281/zenodo.3991596 (Gowan et al., 2020).

Stereorandomization as a Method to Probe Peptide Bioactivity

Solid-phase peptide synthesis (SPPS) is usually performed with optically pure building blocks to prepare peptides as single enantiomers. Herein we report that SPPS using racemic amino acids provides stereorandomized (sr) peptides, containing up to billions of different stereoisomers, as well-defined single HPLC peaks, single mass products with high yield, which can be used to investigate peptide bioactivity. To exemplify our method, we show that stereorandomization abolishes the membrane-disruptive effect of α-helical amphiphilic antimicrobial peptides but preserves their antibiofilm effect, implying different mechanisms involving folded versus disordered conformations. For antimicrobial peptide dendrimers by contrast, stereorandomization preserves antibacterial, membrane-disruptive, and antibiofilm effects but reduces hemolysis and cytotoxicity, thereby increasing their therapeutic index. Finally, we identify partially stereorandomized analogues of the last resort cyclic peptide antibiotic polymyxin B with preserved antibacterial activity but lacking membrane-disruptive and lipopolysaccharide-neutralizing activity, pointing to the existence of additional targets.

Enantioselective extraction of unprotected amino acids coupled with racemization

Scalable and economical methods for the production of optically pure amino acids, both natural and unnatural, are essential for their use as synthetic building blocks. Currently, enzymatic dynamic kinetic resolution (DKR) underpins some of the most effective processes. Here we report the development of enantioselective extraction coupled with racemization (EECR) for the chirality conversion of underivatized amino acids. In this process, the catalytic racemization of amino acids in a basic aqueous solution is coupled with the selective extraction of one enantiomer into an organic layer. Back-extraction from the organic layer to an acidic aqueous solution then completes the deracemization of the amino acid. The automation of the EECR process in a recycling flow reactor is also demonstrated. Continuous EECR is made possible by the sterically hindered chiral ketone extractant 5, which prevents the coextraction of the copper racemization catalyst because of its nonplanar geometry. Furthermore, the extractant 5 unexpectedly forms imines with amino acids faster and with greater enantioselectivity than less bulky derivatives, even though 5 cannot participate in intramolecular resonance-assisted hydrogen bonding. These features may allow EECR to challenge the preponderance of enzymatic DKR in the production of enantiomerically enriched amino acids.

Dental age estimation using incremental lines of cementum

Forensic odontology is a specialty of dentistry which in the interest of justice deals with the examination of dental evidence for evaluation and presentation of the dental findings. An important aspect of forensic odontology is the identification of age, sex and race of an individual based on their dental characteristics. Various methods utilizing the dentin translucency, cemental annulations, attrition, pulp-tooth ratio, amino acid racemization among others are available for dental age estimation. The aim of the present study was to evaluate the efficiency of incremental lines of cementum in age estimation. Ten freshly extracted teeth were histologically observed using light microscope and image analysis software for assessment of incremental lines of cementum. The incremental lines were counted, and the age was estimated using a prescribed formula. The estimated age was then compared with the actual age of the individual to determine its efficiency. The preliminary study results indicated a positive correlation between estimated age and the actual age in 70% of the samples. Thus, it can be concluded that cemental annulations could serve as an important factor in age determination. Further analysis with larger sample size and advanced techniques will help in improving the accuracy of this method. Keywords: Dental age estimation, Incremental lines of cementum, Forensic odontology.

Ancestral L-amino acid oxidases for deracemization and stereoinversion of amino acids

L-amino acid oxidases (LAAOs) can be applied to convert racemic amino acids to D-isomers, which are potential precursors of pharmaceuticals. However, this application is hampered by the lack of available stable and structure-determined LAAOs. In this study, we attempt to address this limitation by utilizing two ancestral LAAOs: AncLAAO-N4 and AncLAAO-N5. AncLAAO-N4 has the highest thermal and temporal stabilities among the designed LAAOs that can be used for deracemization and stereoinversion. AncLAAO-N5 can provide X-ray crystal structures, which are helpful to reveal substrate recognition and reaction mechanisms of LAAOs at the molecular level. Next, we attempted to improve activity of AncLAAO-N4 toward L-Val through a semi-rational protein engineering method. Three variants with enhanced activity toward L-Val were obtained. Taken together, we believe that the activity and substrate selectivity of AncLAAOs give them the potential to be key enzymes in various chemoenzymatic reactions.

First sequencing of ancient coral skeletal proteins

Here we report the first recovery, sequencing, and identification of fossil biomineral proteins from a Pleistocene fossil invertebrate, the stony coral Orbicella annularis. This fossil retains total hydrolysable amino acids of a roughly similar composition to extracts from modern O. annularis skeletons, with the amino acid data rich in Asx (Asp + Asn) and Glx (Glu + Gln) typical of invertebrate skeletal proteins. It also retains several proteins, including a highly acidic protein, also known from modern coral skeletal proteomes that we sequenced by LC–MS/MS over multiple trials in the best-preserved fossil coral specimen. A combination of degradation or amino acid racemization inhibition of trypsin digestion appears to limit greater recovery. Nevertheless, our workflow determines optimal samples for effective sequencing of fossil coral proteins, allowing comparison of modern and fossil invertebrate protein sequences, and will likely lead to further improvements of the methods. Sequencing of endogenous organic molecules in fossil invertebrate biominerals provides an ancient record of composition, potentially clarifying evolutionary changes and biotic responses to paleoenvironments.

Modulation of physical properties of organic cocrystals by amino acid chirality

Amino acid chirality plays an important role in conveying directionality and specificity to their supramolecular organization. However, the impact of enantiopure and racemic amino acids on the favorable packing and macroscopic properties of organic cocrystals with nonchiral coformers is poorly understood. Herein, we performed a systematic study of the effect of chirality on the macroscopic properties of acetylated alanine (AcA) single crystals and cocrystals with a nonchiral photo-sensitive bipyridine derivative (BPE). Cocrystallization with BPE produced a marked morphology transition that improved the supramolecular chirality, thermal stability and mechanical strength of AcA crystals. The distinct supramolecular packing modes were analyzed by X-ray crystallography. The highest rigidity was observed for BPE/dl-AcA, while BPE/d-AcA and BPE/l-AcA crystals exhibited higher efficiency of photo-induced emission for fluorescent imprinting, as well as significantly higher piezoelectricity. This work provides a striking illustration that subtle differences in amino acid stereochemistry translate into tunable macroscopic properties of organic cocrystals for future applications in rigid solids, fluorescent imprinting, and energy harvesting.

Organocatalytic Asymmetric Tandem Cyclization/Michael Addition via Oxazol-5(2H)-One Formation: Access to Perfluoroalkyl-Containing N,O-Acetal Derivatives.

Herein, we report a convenient organocatalytic asymmetric tandem cyclization/Michael addition protocol for the synthesis of diastereomerically pure and highly enantioenriched perfluoroalkyl-containing N,O-acetal derivatives starting from racemic N-perfluoroacyl amino acids under mild conditions. This efficient atom economic reaction leads to highly enantioselective and diastereoselective construction of N,O-acetal derivatives containing oxazolone and perfluoroalkyl moieties containing vicinal quaternary and tertiary stereocenters (up to 97% yield, up to 96% ee, and up to >20:1 dr).

Abstract 5998: In vitro and in vivo anticancer effects of D/L-alpha-metyrosine (SM-88), a novel metabolism-based therapy

Abstract Introduction: D/L-alpha-metyrosine (SM-88, racemetyrosine) is a clinical stage chemically modified racemic amino acid therapy with broad anticancer activity in patients across 15 different indications. While amino acid metabolism has been leveraged in oncology imaging for decades, SM-88 offers a novel therapeutic approach to selectively disrupt cancer cells. This study explored phenotypic and mechanistic effects of exposing cancer cells to D/L-alpha-metyrosine as well as potential immunomodulation of the in vivo tumor microenvironment related to tyrosine hydroxylase inhibition and catecholamine depletion. Methods: In vitro experiments were conducted in a range of human and mouse cancer cell lines, including MCF-7, 4T1, HCT116, CAPAN2, PAN02, PANC01. The effect of SM-88 methyl-ester (SM-88 ME) alone on viability, apoptosis, migration/invasion, protein synthesis inhibition, autophagy, cell cycle arrest, and ROS generation was assessed. In vivo experiments included xenograph studies of HCT116 with monotherapy consisting of either IP injections up to 200 mg/kg/day of SM-88 ME, or orally administered SM-88 up to 324 mg/kg/day. Orthotopic xenographs of 4T1 and PAN02 models using monotherapy doses up to 200 mg/kg/day are ongoing. Ongoing immunohistochemistry and flow cytometry is focused on correlation with LAT1 expression and efficacy, alteration in macrophage polarization (M1/M2 ratio), Tregs, and various T cell populations in the tumor microenvironment. Results: Exposure to SM-88 ME exhibited a dose dependent increase in ROS, as well as decreases in caspase 3/7 activation. An increase in ROS following exposure to SM-88 ME was also observed in PAN02 cells. Similar decreases in caspase 3/7 activation were observed in CAPAN2, HCT116, and MCF7 cells. Interestingly, across a variety of cell lines including PAN02, PANC1, and 4T1 cell morphology changes suggested the formation of autophagic vacuoles. Viability across all cell lines was reduced in a dose and time dependent manner. In a mouse HCT116 SC xenograft model, mice receiving 324 mg/kg/day SM-88 ME showed significantly reduced tumor size compared to control mice. Additional in vitro and in vivo experiments are ongoing. Conclusions: The importance of amino acid metabolism in cancer has gained greater awareness over the past decade, however potential therapeutic approaches in this area remain limited. SM-88 has been dosed in over 180 cancer patients with encouraging efficacy and safety findings to date. Early data suggest increases in ROS generation and decreases in apoptosis may occur in certain cancer types (PAN02 pancreatic cancer), suggesting a shift away from apoptosis and towards autophagy. Potential immune modulatory effects of SM-88, including alterations in macrophage polarization related to tyrosine hydroxylase inhibition and subsequent reductions in catecholamine production are being examined. Citation Format: Alexander Vandell, Jonathan Eckard, Steve Hoffman, Giuseppe Del Priore, Martin Fernandez-Zapico. In vitro and in vivo anticancer effects of D/L-alpha-metyrosine (SM-88), a novel metabolism-based therapy [abstract]. In: Proceedings of the Annual Meeting of the American Association for Cancer Research 2020; 2020 Apr 27-28 and Jun 22-24. Philadelphia (PA): AACR; Cancer Res 2020;80(16 Suppl):Abstract nr 5998.

An efficient method for the determination of enantiomeric purity of racemic amino acids using micellar chromatography, a green approach.

A simple, sensitive and green micellar liquid chromatographic method (RP-HPLC) was developed for enantioseparation of four racemic amino acids, namely, (RS)-selenomethionine, (RS)-methionine, (RS)-cysteine and (RS)-penicillamine. An aqueous solution of sodium dodecyl sulfate and Brij-35 was prepared and used as mobile phase for HPLC analysis. Activated esters of (S)-ibuprofen, (S)-ketoprofen and (S)-levofloxacin were synthesized by reacting them with N-hydroxybenzotriazole. These esters were characterized by UV, IR, 1 HNMR, HRMS and elemental analysis. These chiral reagents (activated esters) were used for the synthesis of diastereomeric derivatives of the chosen amino acids. The diastereomeric derivatives were separated on a C18 column by micellar liquid chromatography. Chromatographic conditions were optimized by varying concentration of surfactant in aqueous solution, and by varying the concentration and pH of the buffer. The green assessment score was calculated for the developed method (78, an excellent green method score). In addition, density functional theory calculations were performed, using Gaussian 09 rev. A.02 and hybrid density functional B3LYP with a 6-31G* basis set program, in order to develop lowest energy optimized structures of diastereomeric derivatives. The method was validated according to International Conference on Harmonization guidelines and the retention factor (k), selectivity factor (α), resolution factor (RS ) and limit of detection (0.295 ng ml-1 ) and limit of quantification (0.896 ng ml-1 ) were calculated.

Seismic stratigraphic framework of the continental shelf offshore Delmarva, U.S.A.: Implications for Mid-Atlantic Bight Evolution since the Pliocene

Understanding how past coastal systems have evolved is critical to predicting future coastal change. Using over 12,000 trackline kilometers of recently collected, co-located multi-channel boomer, sparker and chirp seismic reflection profile data integrated with previously collected borehole and vibracore data, we define the upper (< 115 m below mean lower low water) seismic stratigraphic framework offshore of the Delmarva Peninsula, USA. Twelve seismic units and 11 regionally extensive unconformities (U1-U11) were mapped over 5900 km2 of North America's Mid-Atlantic continental shelf. We interpret U3, U7, U9, U11 as transgressive ravinement surfaces, while U1,2,4,5,6,8,10 are subaerial unconformities illustrating distinct periods of lower sea-level. Based on areal distribution, stratigraphic relationships and dating results (Carbon 14 and amino acid racemization estimates) from earlier vibracore and borehole studies, we interpret the infilled channels as late Neogene and Quaternary courses of the Susquehanna, Potomac, Rappahannock, York, James rivers and tributaries, and a broad flood plain. These findings indicate that the region's geologic framework is more complex than previously thought and that Pleistocene paleochannels are abundant in the Mid-Atlantic. This study synthesizes and correlates the findings of other Atlantic Margin studies and establishes a large-scale Quaternary framework that enables more detailed stratigraphic analysis in the future. Such work has implications for inner continental shelf systems tract evolution, the relationship between antecedent geology and modern coastal systems, assessments of eustacy, glacial isostatic adjustment, and other processes and forcings that play a role in passive margin evolution.

The utility of single foraminifera amino acid racemization analysis for the relative dating of Quaternary beach barriers and identification of reworked sediment

Abstract The identification and correlation of a sequence of Pleistocene beach barriers located within the northern Coorong Coastal Plain, South Australia, is made difficult by long-term subsidence and extensive reworking. Associated shell beds, to all but the last interglacial barrier, are subsurface and not readily accessible. The whole-rock amino acid racemization method was found to be unsuitable for distinguishing age differences of the individual barriers due to the low calcium carbonate content of the sediments, concerns for the leaching or contamination as a result of the comminuted nature of the shelly component, and the potentially high content of reworked sediment. These difficulties prompted an investigation into the applicability of AAR analysis of single foraminifera tests to ascertain whether the relative age of beach barriers could be determined and whether sediment contribution from antecedent barriers could be identified. Foraminifera tests of multiple genera (including Cibicides corticatus and Rosalina bradyi) from numerous modern depositional environments were analyzed to establish aminozones of aspartic acid and glutamic acid D/L values representative of modern/Holocene foraminifera and to assess natural variability of Holocene D/L values between depositional settings. Tests of Lamellodiscorbis dimidiatus, common in the Pleistocene barriers, were analyzed from MIS 5 and MIS 7 sediments and aminozones identified, allowing correlation of non-contiguous barrier features and the identification of reworked foraminifera. Rejection criteria removed, on average, between 25 and 30% of analytical results. The Holocene aminozone for every genus analyzed falls within the same general constraint: D/L values less than 0.40 for aspartic acid and less than 0.20 for glutamic acid. The D/L values of approximately 15% of foraminifera from the modern sediments exceed the Holocene aminozone constraint and the tests are considered reworked. The range of D/L values representative of each interglacial aminozone decreases with age, reflecting the slowing rate of amino acid racemization with time. Pleistocene sediments are found to have a higher percentage of reworked tests. Thermoluminescence dating of the Pleistocene successions was used to evaluate the AAR results. This work illustrates that foraminifera tests are surprisingly robust and can survive potentially multiple phases of deposition and reworking.

Mimicking the effects of anthropogenic heating on amino acid racemisation dating of gastropod shells

Abstract Pre- or post-depositional heating of fossil biominerals will impact resulting amino acid dates, but the study on the effects on their amino acids of dry artificial heating of molluscs has not yet been fully tested. Here we report a study on three mollusc species to show how amino acid content can potentially be used to identify archaeological samples that have been subjected to artificial heating. The identification of markers of exposure to high temperature could be useful to reject compromised samples for amino acid racemisation dating. In order to identify markers of heat exposure, we artificially heated modern shell samples belonging to three marine molluscs found in abundance at archaeological sites, namely Patella vulgata, Phorcus lineatus and Littorina littorea. The markers found were compared with data from an archaeological dataset for these three species. Our results indicate that there is unlikely to be a single marker indicating artificial heating of a sample, especially for archaeological samples, which have been exposed to a wide variety of complex conditions that cannot be simulated in an isothermal experiment. However in general, we observed changes in shell composition which were indicative of heating: higher %Glx and %Ala and lower %Asx and %Ser for a given Asx D/L value. Moreover, samples heated at high temperatures showed higher than expected Glx and Ala D/L values for a given Asx D/L value. Likewise, the amino acid content of the shells decreased with heating time and temperature. Furthermore, shells artificially heated at > 300 °C had additional compounds evident in the chromatogram, and a poor baseline, thus causing a loss of resolution of late eluting amino acids. Of note, samples heated at 500 °C (5 min) and 400 °C (10–20 min) preserved negligible amino acid content. Archaeological samples that deviated from the expected unheated trend were therefore identified as having been heated.

The Pleistocene and Holocene records of the Mazarrón Basin (SE Spain)

Here we reconstructed the evolution of the Mazarrón Basin during the Pleistocene and Holocene. In this regard, we studied 9 cores with the aim to: 1) define a chronological framework; 2) obtain data on the palaeoenvironment; and 3) establish the relationship with recent tectonics. A total of 158 samples were recovered for amino acid racemization (AAR) dating, 4 for radiocarbon dating (14C), and 332 for sedimentological and palaeontological determination, and 110 for determination of the mineralogical content. These approaches allowed us to elucidate the evolutionary phases of the palaeo-landscape of the Mazarrón Basin, a fault-controlled graben affected by diverse faults, mainly those of Las Moreras and Rella. The ages of the records and the facies correlation indicate that Las Moreras Fault controlled sedimentation during Marine Isotope Stage (MIS) 7, whereas the Rella Fault was strongly active during the Middle Holocene. During MIS7, a brackish lagoon developed in the western area, overlying alluvial fan deposits. Later, the area was uplifted, thereby becoming exposed to erosion. The activity of the Rella Fault allowed sedimentation in the western part of the Mazarrón Basin during the Middle Holocene, while in the Upper Holocene sedimentation occurred in the eastern part. The Holocene transgression was reflected in a temporarily floodable marsh in the hinterland, with changing salinity conditions, from brackish to euhaline waters. Along the sea front, the marine influence was evident but not dominant. Thus, the Mazarrón Basin during the Holocene was brackish to highly euhaline, with variable biological diversity linked to a narrow and probably discontinuous communication with the sea, with restricted circulation and long flushing times, which was reflected by the significant presence of halite. The record ended with recent alluvial/anthropic sediments.

Acceleration of amino acid racemization by isovaline: possible implications for homochirality and biosignature search

AbstractIn nature, abiotically formed amino acids are usually racemic. However, this is not true for the α,α-dialkyl amino acid isovaline (Iva), which has an L-enantiomeric excess in some specimens of carbonaceous meteorites. On the early Earth and Mars, such meteorites were sources of amino acids, including Iva. Therefore, a connection may exist between the possible chiral influence of non-racemic Iva and the origin of biological homochirality. On the surface of a young terrestrial planet, amino acids can be chemically altered in many ways. For example, high temperatures from geothermal heating can lead to racemization. Four billion years ago, active volcanism and volcanic islands provided suitable conditions for such reactions and perhaps even for early microbial life on Earth. In the current study, we investigated the influence of D- and L-Iva on the thermal racemization of L-alanine (L-Ala) and L-2-aminobutyric acid (L-Abu) in a simulated hot volcanic environment. The amino acids were intercalated in the clay mineral calcium montmorillonite (SAz-1). While Iva was resistant to racemization, partial racemization was observed for Ala and Abu after 8 weeks at 150°C. The experimental results – for example, accelerated racemization in the presence of Iva and different influences of the Iva enantiomers – suggest that the amino acid molecules interacted with each other, possibly in hydrogen-bonded dimers. Accelerated racemization of amino acids could have been an obstacle to the development of homochirality. Besides, it is also detrimental to the use of homochirality as a biosignature, for example, in the search for microbial life on Mars.

On the mechanism of solid-state phase transitions in molecular crystals - the role of cooperative motion in (quasi)racemic linear amino acids.

During single-crystal-to-single-crystal (SCSC) phase transitions, a polymorph of a compound can transform to a more stable form while remaining in the solid state. By understanding the mechanism of these transitions, strategies can be developed to control this phenomenon. This is particularly important in the pharmaceutical industry, but also relevant for other industries such as the food and agrochemical industries. Although extensive literature exists on SCSC phase transitions in inorganic crystals, it is unclear whether their classications and mechanisms translate to molecular crystals, with weaker interactions and more steric hindrance. A comparitive study of SCSC phase transitions in aliphatic linear-chain amino acid crystals, both racemates and quasi-racemates, is presented. A total of 34 transitions are considered and most are classified according to their structural change during the transition. Transitions without torsional changes show very different characteristics, such as transition temperature, enthalpy and free energy, compared with transitions that involve torsional changes. These differences can be rationalized using classical nucleation theory and in terms of a difference in mechanism; torsional changes occur in a molecule-by-molecule fashion, whereas transitions without torsional changes involve cooperative motion with multiple molecules at the same time.

Sub‐seafloor biogeochemical processes and microbial life in the Baltic Sea

The post-glacial Baltic Sea has experienced extreme changes that are archived today in the deep sediments. IODP Expedition 347 retrieved cores down to 100 m depth and studied the climate history and the deep biosphere. We here review the biogeochemical and microbiological highlights and integrate these with other studies from the Baltic seabed. Cell numbers, endospore abundance and organic matter mineralization rates are extremely high. A 100-fold drop in cell numbers with depth results from a small difference between growth and mortality in the ageing sediment. Evidence for growth derives from a D:L amino acid racemization model, while evidence for mortality derives from the abundance and potential activity of lytic viruses. The deep communities assemble at the bottom of the bioturbated zone from the founding surface community by selection of organisms suited for life under deep sediment conditions. The mean catabolic per-cell rate of microorganisms drops steeply with depth to a life in slow-motion, typical for the deep biosphere. The subsurface life under extreme energy limitation is facilitated by exploitation of recalcitrant substrates, by biochemical protection of nucleic acids and proteins and by repair mechanisms for random mismatches in DNA or damaged amino acids in proteins.

Enantiomorphic Microvortex‐Enabled Supramolecular Sensing of Racemic Amino Acids by Using Achiral Building Blocks

AbstractChiral analysis of bioactive molecules is of increasing significance in chemical and life sciences. However, the quantitative detection of a racemic mixture of enantiomers is a challenging task, which relies on complicated and time‐consuming multiple steps of chiral derivatization, chiral separation, and spectroscopic measurement. Herein, we show that, without the use of chiral molecules or pretreatment steps, the co‐assembly of amino acids with achiral TPPS4 monomers controlled by enantiomorphic microvortices allows quantitative detection of racemic or enantiomeric amino acids, through analysis of the sign and magnitude of supramolecular chirality in different outlets of a microfluidic platform. A model demonstrates that chiral microvortices can induce an initial chiral bias by bending the sheet structure, resulting in supramolecular self‐assembly of TPPS4 and amino acids of compatible chirality by the self‐sorting. This sensing system may find versatile applications in chiral sensing.

Enantiomorphic Microvortex-Enabled Supramolecular Sensing of Racemic Amino Acids by Using Achiral Building Blocks.

Chiral analysis of bioactive molecules is of increasing significance in chemical and life sciences. However, the quantitative detection of a racemic mixture of enantiomers is a challenging task, which relies on complicated and time-consuming multiple steps of chiral derivatization, chiral separation, and spectroscopic measurement. Herein, we show that, without the use of chiral molecules or pretreatment steps, the co-assembly of amino acids with achiral TPPS4 monomers controlled by enantiomorphic microvortices allows quantitative detection of racemic or enantiomeric amino acids, through analysis of the sign and magnitude of supramolecular chirality in different outlets of a microfluidic platform. A model demonstrates that chiral microvortices can induce an initial chiral bias by bending the sheet structure, resulting in supramolecular self-assembly of TPPS4 and amino acids of compatible chirality by the self-sorting. This sensing system may find versatile applications in chiral sensing.