Chiral Signatures Research Articles

Polarization of Saturn’s moon Iapetus

Context. The surface properties of atmosphereless solar system objects can be constrained by investigating the nature of the polarized light scattered from their surfaces. Aims. We provide new and precise measurements of the phase angle and the wavelength dependence of linear polarization on the leading side of Iapetus over the maximum phase angle range accessible from Earth (∼0.5−6.0 ◦ ) and over a broad spectral range (400–800 nm), thereby identifying the polarimetric characteristics of its dark material. Moreover, we provide circular spectral polarization measurement of the same side of Iapetus at one phase angle, which was performed aiming at detection of chiral signatures on its surface. We also compare our new polarization measurements with those of the trailing hemisphere of Iapetus which were obtained in our previous work. Methods. Using the FORS2 instrument of the ESO VLT, we performed spectro-polarimetric observations of Iapetus’ leading side. Results. While the linear polarization measurements of Iapetus’ leading side show an opposite trend in phase angle dependence to that of its trailing hemisphere, the polarization values measured for the two hemispheres around similar phase angles (in the range ∼3.0−6.0 ◦ )d iffer by a factor of three. Besides this, the degree of negative linear polarization of Iapetus’ leading hemisphere shows a slight dependence on the wavelengths of observations. Furthermore, like that of its trailing hemisphere, the circular polarization measurement of Iapetus’ leading side indicates no evidence of a significant amount of optically active (chiral) molecules on its surface.

Enantioselective Demethylation of Nicotine as a Mechanism for Variable Nornicotine Composition in Tobacco Leaf

Nicotine and its N-demethylation product nornicotine are two important alkaloids in Nicotiana tabacum L. (tobacco). Both nicotine and nornicotine have two stereoisomers that differ from each other at 2'-C position on the pyrrolidine ring. (S)-Nicotine is the predominant form in the tobacco leaf, whereas the (R)-enantiomer only accounts for ∼0.2% of the total nicotine pool. Despite considerable past efforts, a comprehensive understanding of the factors responsible for generating an elevated and variable enantiomer fraction of nornicotine (EF(nnic) of 0.04 to 0.75) from the consistently low EF observed for nicotine has been lacking. The objective of this study was to determine potential roles of enantioselective demethylation in the formation of the nornicotine EF. Recombinant CYP82E4, CYP82E5v2, and CYP82E10, three known tobacco nicotine demethylases, were expressed in yeast and assayed for their enantioselectivities in vitro. Recombinant CYP82E4, CYP82E5v2, and CYP82E10 demethylated (R)-nicotine 3-, 10-, and 10-fold faster than (S)-nicotine, respectively. The combined enantioselective properties of the three nicotine demethylases can reasonably account for the nornicotine composition observed in tobacco leaves, which was confirmed in planta. Collectively, our studies suggest that an enantioselective mechanism facilitates the maintenance of a reduced (R)-nicotine pool and, depending on the relative abundances of the three nicotine demethylase enzymes, can confer a high (R)-enantiomer percentage within the nornicotine fraction of the leaf.

Chiral signature of venlafaxine as a marker of biological attenuation processes

The chiral signature of the antidepressant venlafaxine was used in this study to gain insight into biological attenuation processes and to differentiate abiotic and biotic transformation processes in water. Laboratory scale experiments revealed that sorption and phototransformation processes were not enantioselective while venlafaxine was enantioselectively biotransformed into O-desmethylvenlafaxine. The enantiomeric fraction (EF) variations of venlafaxine appeared to be proportional to its microbial fractional conversion. Enantioselective biotransformation of venlafaxine was also investigated in a eutrophic French river. Venlafaxine was found to be racemic at the output of the main wastewater treatment plant discharging into the river, independently of the sampling date during the year. An analysis of EF variations might provide evidence of biodegradation along a 30km river stretch.

Methylsulfonyl polychlorinated biphenyls in fish from an electronic waste-recycling site in South China: Levels, congener profiles, and chiral signatures

Great concerns have been raised about the fate and effects of polychlorinated biphenyls (PCBs) and other organic contaminants contained in electronic waste (e-waste) exported from industrialized countries at midlatitudes to subtropical and tropical regions. Information on the metabolites of these chemicals, for example, methylsulfonyl-PCBs (MeSO(2)-PCBs) in wildlife from the later regions is scarce. In the present study, 17 MeSO(2)-PCBs, including five chiral congeners, were detected in the muscle, liver, and brain tissues of two benthic fish species--northern snakehead and mud carp--from a small pond near an electronic waste recycling site in South China. The mean concentrations of the sum of the MeSO(2)-PCBs ranged from 80 to 340 ng/g lipid weight in the tissues, with relative higher levels in the liver than the muscle and brain tissues. These levels were one order of magnitude greater than the highest levels of MeSO(2)-PCBs previously reported in fish. The 3'-MeSO(2)-CB 87, 3'- and 4'-MeSO(2)-CB 101, 4-MeSO(2)-CB 110, and 4-MeSO(2)-CB 149 were dominant, collectively comprising more than 55% of the total MeSO(2)-PCBs. Except for 4-MeSO(2)-CB149, all of the investigated chiral MeSO(2)-PCBs displayed a clear, congener-specific enantiomeric enrichment in the tissues. No tissue-specific enantioselective retention of the enantiomers was observed in the investigated fish. This is the first report on chiral signatures of MeSO(2)-PCBs in fish tissues.

Remote sensing of chiral signatures on Mars

We describe circular polarization as a remote sensing diagnostic of chiral signatures which may be applied to Mars. The remarkable phenomenon of homochirality provides a unique biosignature which can be amenable to remote sensing through circular polarization spectroscopy. The natural tendency of microbes to congregate in close knit communities would be beneficial for such a survey. Observations of selected areas of the Mars surface could reveal chiral signatures and hence explore the possibility of extant or preserved biological material. We describe a new instrumental technique that may enable observations of this form.

Halogenated flame retardants in home-produced eggs from an electronic waste recycling region in South China: Levels, composition profiles, and human dietary exposure assessment

Three regulated halogenated flame retardants (HFRs), i.e., polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and hexabromocyclododecanes (HBCDs), and several alternative HFRs (AHFRs) including Dechlorane Plus (DP), decabromodiphenyl ethane (DBDPE), and 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), were investigated in the home-produced eggs from three recycling sites and a reference site in an electronic waste (e-waste) recycling region, South China. Mean levels of HFRs in eggs from the recycling sites ranged 2640–14100, 700–1620, 44–350, and 720–3920ng/g lipid weight for ∑PBDEs, ∑PBBs, ∑HBCDs, and ∑AHFRs, respectively, which were one to two orders of magnitude higher than those examined in the reference site. PBDEs were the predominant HFR in those eggs, with contributions >50% to the total HFRs; followed by PBBs and the AHFRs (contributing 14–22% in average). The α-HBCD was the predominant diastereoisomers of HBCDs, with preferential enrichment of the (−)-enantiomer in most of the eggs; but no significant stereoselective enrichment of the DP isomers was observed in these eggs. The average estimated daily intakes (EDIs) of PBDEs, PBBs, HBCDs, and the AHFRs via eggs from the recycling sites ranged 4200–20000, 1120–2440, 80–490, and 970–4530ng/day, respectively, which were one to two orders of magnitude higher than those reported from other parts of the world. The potential adverse effects of these HFRs to human health in the e-waste sites should be further investigated. This is the first report on the isomer compositions of DP and the chiral signatures of HBCDs in hen eggs.

Levels, isomer profiles and chiral signatures of particle-bound hexabromocyclododecanes in ambient air around Shanghai, China

Hexabromocyclododecanes (HBCDs) have been considered candidate persistent organic pollutants, however, environmental data on their presence in China, a major world market, are limited. In this study, airborne particle-bound HBCDs in Shanghai, China were quantified with liquid chromatography–tandem mass spectrometry, and their total concentrations varied from 3.21 to 123 pg/m3. The industrial area showed about three times higher HBCD levels than the urban areas. Gamma-HBCD dominated in particle-associated HBCDs in the industrial area, while α-HBCD was the major diastereomer of the urban areas, which is quite different from the pattern of technical products. Besides α-, β- and γ-HBCDs, δ-HBCD was also detected in all samples (0.09–6.31 pg/m3), while no ɛ-HBCD was found. Airborne β- and γ-HBCDs were racemic in most studied areas due to their chiral signatures showing no significant difference from commercial mixture. Fractions of (+)-α-HBCD (0.417–0.467), however, suggested the enrichment of (−)-α-HBCD and the involvement of enantioselective bioprocesses.

Chiral induction in thioester and oxoester liquid crystals by dispersed carbon nanotubes

Multi-walled carbon nanotubes were dispersed at low concentrations into various achiral liquid crystals having either a thioester or oxoester linkage group in the core. The presence of the carbon nanotubes resulted in chiral signatures being observed in the liquid crystals, including an electroclinic effect (a rotation of the liquid crystal director perpendicular to, and linear in, an applied electric field) in both the nematic and smectic A phases, and a macroscopic helical twist of the liquid crystal director in the nematic phase. For both experiments the chiral signatures for the thioester liquid crystals were found to be an order of magnitude larger than those of the oxoesters. We speculate that the much larger strength of the thioester's chiral properties is a result of stronger non-covalent interactions between the liquid crystal molecule and carbon nanotube.

2,2′,3,3′,6,6′-Hexachlorobiphenyl (PCB 136) Is Enantioselectively Oxidized to Hydroxylated Metabolites by Rat Liver Microsomes

Developmental exposure to multiple ortho-substituted polychlorinated biphenyls (PCBs) causes adverse neurodevelopmental outcomes in laboratory animals and humans by mechanisms involving the sensitization of Ryanodine receptors (RyRs). In the case of PCB 136, the sensitization of RyR is enantiospecific, with only (-)-PCB 136 being active. However, the role of enantioselective metabolism in the developmental neurotoxicity of PCB 136 is poorly understood. The present study employed hepatic microsomes from phenobarbital (PB)-, dexamethasone (DEX)- and corn oil (VEH)-treated male Sprague-Dawley rats to investigate the hypothesis that PCB 136 atropisomers are enantioselectively metabolized by P450 enzymes to potentially neurotoxic, hydroxylated PCB 136 metabolites. The results demonstrated the time- and isoform-dependent formation of three metabolites, with 5-OH-PCB 136 (2,2',3,3',6,6'-hexachlorobiphenyl-5-ol) being the major metabolite. The formation of 5-OH-PCB 136 increased with the activity of P450 2B enzymes in the microsomal preparation, which is consistent with PCB 136 metabolism by rat P450 2B1. The minor metabolite 4-OH-PCB 136 (2,2',3,3',6,6'-hexachlorobiphenyl-4-ol) was produced by a currently unidentified P450 enzyme. An enantiomeric enrichment of (-)-PCB 136 was observed in microsomal incubations due to the preferential metabolism of (+)-PCB 136 to the corresponding 5-OH-PCB 136 atropisomer. 4-OH-PCB 136 displayed an enrichment of the atropisomer formed from (-)-PCB 136; however, the enrichment of this metabolite atropisomer did not affect the enantiomeric enrichment of the parent PCB because 4-OH-PCB 136 is only a minor metabolite. Although the formation of 5- and 4-OH-PCB 136 atropisomers increased with time, the enantioselective formation of the OH-PCB metabolites resulted in constant enantiomeric enrichment, especially at later incubation times. These observations not only demonstrate that the chiral signatures of PCBs and their metabolites in wildlife and humans are due to metabolism by P450 enzymes but also suggest that the enantioselective formation of neurotoxic PCB 136 metabolites, such as 4-OH-PCB 136, may play a role in the developmental neurotoxicity of PCBs.

Chiral Signatures Show Volatilization from Soil Contributes to Polychlorinated Biphenyls in Grass

Enantiomer fractions (EFs) of PCB 95 and concentrations of PCBs 28/31, 52, 101, 118, 138, 153, and 180 were determined in air. Samples were taken at ~14 day intervals on a vertical gradient at an urban background site in Birmingham U.K. in summer 2009 (114 days) and spring 2010 (84 days). EFs in air at 3 cm height were nonracemic (average 0.453 (2009) and 0.468 (2010)) and differed significantly (p < 0.05) from the racemic EFs in air at 10, 40, 90, and 130 cm. EFs in soil (average 0.452 (2009) and 0.447 (2010)) closely matched those in air at 3 cm, while those in grass (average 0.468 (2009) and 0.484 (2010)) were intermediate between those in soil and the racemic EFs in air at ≥ 10 cm. This implies that at the study site, PCBs volatilize from soil to an extent discernible only at the soil:air interface, and that PCBs in grass arise due to foliar uptake of volatile emissions from soil. Atmospheric concentrations of ΣPCBs increased significantly (p < 0.05) with increasing height. Combined with the chiral signature data, this suggests the influence of PCB emissions from soil on airborne concentrations decreases with altitude, while that of emissions from the built environment increases.

Chiral Sum Frequency Generation Spectroscopy for Characterizing Protein Secondary Structures at Interfaces

In situ and real-time characterization of protein secondary structures at interfaces is important in biological and bioengineering sciences, yet remains technically challenging. In this study, we used chiral sum frequency generation (SFG) spectroscopy to establish a set of vibrational optical markers for characterizing protein secondary structures at interfaces. We discovered that the N-H stretches along the peptide backbones of α-helices can be detected in chiral SFG spectra. We further observed that the chiral vibrational signatures of the N-H stretch together with the peptide amide I are unique to α-helix, β-sheet, and random coil at interfaces. Using these chiral vibrational signatures, we studied the aggregation of human islet amyloid polypeptide (hIAPP), which is implicated in type II diabetes. We observed in situ and in real time the misfolding of hIAPP from random coils to α-helices and then β-sheets upon interaction with a lipid-water interface. Our findings show that chiral SFG spectroscopy is a powerful tool to follow changes in protein conformations at interfaces and identify interfacial protein secondary structures that elude conventional techniques.

SIGNATURES OF CHIRALITY IN THE CORE-PARTICLE-HOLE SYSTEMS

An odd-odd nucleus is treated as the core-particle-hole system. The core is described by the Bohr Hamiltonian. Different collective potentials of the core are investigated. The odd particle and hole are assumed to be in the symmetric [Formula: see text] configuration. Signatures of chirality in the odd-odd nucleus spectra are observed. The sufficient condition for the appearance of signatures of chirality in the core-particle-hole system is the α-symmetry of the core provided the particle-hole configuration of the odd valence particles is symmetric.

Residues and chiral signatures of organochlorine pesticides in sediments from Xiangshan Bay, East China Sea

Residual levels and enantiomeric signatures of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs) in surface sediments from Xiangshan Bay, East China Sea were investigated. The concentrations of ∑HCHs (sums of α-, β-, γ-, and δ-HCH) and ∑DDTs (sums of p, p′-DDT, p, p′-DDD,p, p′-DDE, o, p′-DDT, and o, p′-DDD) ranged from 0.14 to 0.67 ng g−1 and 0.61 to 22.38 ng g−1, respectively. A slight potential health risk to the organism was then indicated for the residual levels of DDTs according to the ERL/ERM guidelines. Moreover, the predominant β-HCH implied that the technical HCH contamination was mainly due to the historical usage. But the high ratio of DDT/∑DDTs depicted a cocktail input pattern of fresh and weathered DDTs. The enantiomeric fractions (EFs) of α-HCH, o, p′-DDT, and o, p′-DDD were also determined. The degradation of α-HCH was enantioselective in all sediments samples, resulting in an enrichment of (–)-enantiomers. However, the racemic residues of o, p′-DDT and o, p′-DDD were observed in all sediments samples.

Temporal trend (1988–2008) of hexabromocyclododecane enantiomers in herring gull eggs from the german coastal region

Levels of α-, β-, and γ-hexabromocyclododecane (HBCD) were determined in pooled eggs from herring gulls ( Larus argentatus) sampled on three bird sanctuaries near the German North Sea coast between 1988 and 2008 (Mellum and Trischen) and the German Baltic Sea coast between 1998 and 2008 (Heuwiese) and archived by the German Environmental Specimen Bank. Pressurized fluid extraction, gel permeation chromatography, and LC–MS/MS using 13C 12-labelled isotope standards and a chiral column were applied. α-HBCD was the dominating diastereomer and ranged between 3.7 and 107 ng g −1 lw while β- and γ-HBCD were throughout close to LOQ. The highest α-HBCD concentration was found in eggs from Mellum sampled in the year 2000. Interestingly, HBCD in eggs from the three islands displayed similar time courses with levels increasing to a peak contamination around 2000 and decreasing levels ever since. Chiral signatures of α-HBCD in eggs differed among the islands but indicated a preferential enrichment of the first eluting enantiomer (−)-α-HBCD.

Coherence in electron transfer pathways

Central to the view of electron-transfer reactions is the idea that nuclear motion generates a transition state geometry at which the electron/hole amplitude propagates coherently from the electron donor to the electron acceptor. In the weakly coupled or nonadiabatic regime, the electron amplitude tunnels through an electronic barrier between the donor and acceptor. The structure of the barrier is determined by the covalent and noncovalent interactions of the bridge. Because the tunneling barrier depends on the nuclear coordinates of the reactants (and on the surrounding medium), the tunneling barrier is highly anisotropic, and it is useful to identify particular routes, or pathways, along which the transmission amplitude propagates. Moreover, when more than one such pathway exists, and the paths give rise to comparable transmission amplitude magnitudes, one may expect to observe quantum interferences among pathways if the propagation remains coherent. Given that the effective tunneling barrier height and width are affected by the nuclear positions, the modulation of the nuclear coordinates will lead to a modulation of the tunneling barrier and hence of the electron flow. For long distance electron transfer in biological and biomimetic systems, nuclear fluctuations, arising from flexible protein moieties and mobile water bridges, can become quite significant. We discuss experimental and theoretical results that explore the quantum interferences among coupling pathways in electron-transfer kinetics; we emphasize recent data and theories associated with the signatures of chirality and inelastic processes, which are manifested in the tunneling pathway coherence (or absence of coherence).

Mechanically Generated Surface Chirality at the Nanoscale

A substrate coated with an achiral polyimide alignment layer was scribed bidirectionally with the stylus of an atomic force microscope to create an easy axis for liquid crystal orientation. The resulting noncentrosymmetric topography resulted in a chiral surface that manifests itself at the molecular level. To show this unambiguously, a planar-aligned negative dielectric aniostropy achiral nematic liquid crystal was placed in contact with the surface and subjected to an electric field E. The nematic director was found to undergo an azimuthal rotation approximately linear in E. This so-called "surface electroclinic effect" is a signature of surface chirality and was not observed when the polyimide was treated for a centrosymmetric topography, and therefore was nonchiral.

Absolute Probe of Surface Chirality Based on Focused Circularly Polarized Light

We present a new nonlinear optical technique to probe chirality, i.e., lack of reflection symmetry, of surfaces and thin molecular films. The technique is based on second-harmonic generation and focusing of circularly polarized light at normal incidence on the sample. Because of the high symmetry of the experimental arrangement, the technique provides an unambiguous probe of chirality in the sense that it avoids false chiral signatures arising from possible in-plane anisotropy of the sample. The technique is verified by using two Langmuir−Blodgett thin films, one chiral and anisotropic, the other achiral and anisotropic, where the latter acted as a reference. Due to the focusing condition, the technique is also naturally applicable to nonlinear chiral microscopy of surfaces and interfaces.

Novel deoxycholic acid alkylamide-phenylurea-derived organogelators

Three monomeric and three dimeric deoxycholic acid (DCA) alkylamido-phenylurea derivatives are designed based on known gelators and are synthesized and characterized by 1H and 13C NMR spectroscopy, ESI-TOF mass spectrometry, and elemental analyses. Among them, a monomeric derivative forms supramolecular gels in CHCl 3 and chlorobenzene, whereas a dimeric derivative gels THF and higher 1-alkanols containing 7–10 carbons. The morphologies of their xerogels are studied by scanning electron microscopy (SEM). No signature of macroscopic chirality of the gels is visible.

Current-Use Brominated Flame Retardants in Water, Sediment, and Fish from English Lakes

Concentrations are reported of hexabromocyclododecanes (HBCDs) and tetrabromobisphenol-A (TBBP-A) in water (n = 27), sediment (n = 9), and fish samples (n = 30) from nine English lakes. Seasonal variation in concentrations in water is minimal. Concentrations of TBBP-A range from 140 to 3200 pg L(-1) (water), 330 to 3800 pg g(-1) dry weight (sediment), and <0.29 to 1.7 ng g(-1) lipid weight (fish). Those of SigmaHBCDs range between 80 and 270 pg L(-1) (water), 880 and 4800 pg g(-1) dry weight (sediment), and 14 and 290 ng g(-1) lipid weight (fish). Aqueous concentrations of SigmaHBCDs and TBBP-A are significantly positively correlated, indicating a common source. Average +/-sigma(n) "freely-dissolved" phase proportions are 47 +/- 4.7% (SigmaHBCDs) and 61 +/- 2.9% (TBBP-A). Average field-derived bioaccumulation factors are 5900, 1300, 810, and 2100 for alpha-, beta-, gamma-, and SigmaHBCDs, respectively. Tetrabromocyclododecadienes are detected in all sediments, with pentabromocyclododecenes present in some. This suggests HBCD degrades via sequential loss of HBr. The delta-HBCD meso form was quantified in 43% of fish samples (1.0-11% SigmaHBCDs). Its absence from temporally and spatially consistent water and sediment samples suggests it is formed via bioisomerization. While HBCD chiral signatures are racemic in water and sediment, our data reveal enantiomeric enrichment of (-)alpha-HBCD and (+)gamma-HBCD in fish.

DNA on Stage: Showcasing Oligonucleotides at Surfaces and Interfaces with Second Harmonic and Vibrational Sum Frequency Generation

The field of nonlinear optics continues to expand and surprise. The ability to study DNA with nonlinear optics has opened the door to understand, on a molecular level and without the use of external labels, the physical and chemical properties of DNA single and double strands at surfaces and interfaces. In this Perspective, we survey how nonlinear optical probes access the electronic, vibrational, electrostatic, and chiral signatures of interfacial DNA in its native state. We also show how this exciting new field is directly applicable to tracking and understanding molecular recognition in DNA oligonucleotides and aptamers.