WorldWideScience

Sample records for achiral

  1. Chiral heteropoly blues and controllable switching of achiral polyoxometalate clusters.

    Science.gov (United States)

    Wang, Yizhan; Li, Haolong; Wu, Che; Yang, Yang; Shi, Lei; Wu, Lixin

    2013-04-22

    Managing the blues: Chiral heteropoly blues of achiral polyoxometalate clusters were created through an intermolecular interaction with a chiral organic compound. Controllable chiroptical switching of the cluster complexes was possible through reversible photochromism of the polyoxometalates (see picture).

  2. Helical Nanostructure of Achiral Silver p-Tolylacetylide Molecules

    OpenAIRE

    Ken Judai; Yoshikiyo Hatakeyama; Junichi Nishijo

    2013-01-01

    Silver p-tolylacetylide is an achiral molecule; however, its nanostructure has been found to consist of twisted nanoribbons. The twisted ribbon is a helicoid that combines translation and perpendicular rotation along the ribbon axis. A helix, a typical chiral structure, can be created by the aggregation of achiral molecules, and the recrystallization conditions control the twist of the nanoribbons. Therefore, the recrystallization controls the chirality.

  3. Chiroptical activity in colloidal quantum dots coated with achiral ligands.

    Science.gov (United States)

    Melnikau, Dzmitry; Savateeva, Diana; Gaponik, Nikolai; Govorov, Alexander O; Rakovich, Yury P

    2016-01-25

    We studied the chiroptical properties of colloidal solution of CdSe and CdSe/ZnS quantum dots (QDs) with a cubic lattice structure which were initially prepared without use of any chiral molecules and coated with achiral ligands. We demonstrate circular dichroism (CD) activity around first and second excitonic transition of these CdSe based nanocrystals. We consider that this chiroptical activity is caused by imbalance in racemic mixtures of QDs between the left and right handed nanoparticles, which appears as a result of the formation of various defects or incorporation of impurities into crystallographic structure during their synthesis. We demonstrate that optical activity of colloidal solution of CdSe QDs with achiral ligands weakly depends on the QDs size and number of ZnS monolayers, but does not depend on the nature of achiral ligands or polarity of the solution. PMID:26832599

  4. Ferroelectric Smectic Phase Formed by Achiral Straight Core Mesogens

    Science.gov (United States)

    Stannarius, Ralf; Li, Jianjun; Weissflog, Wolfgang

    2003-01-01

    We report electro-optic experiments in liquid crystalline freestanding films of achiral hockey stick shaped mesogens with a straight aromatic core. The material forms two smectic mesophases. In the higher temperature phase, a spontaneous polarization exists in the smectic layer plane and the films show polar switching in electric fields. It is the first example of a ferroelectric phase formed by nearly rodlike achiral mesogens. Mirror symmetry of the phase is spontaneously broken. We propose a molecular configuration similar to a synclinic ferroelectric (CSPF) high temperature phase and an anticlinic, probably antiferroelectric (CAPA) low temperature phase.

  5. Can enantiomers be separated in achiral chromatographic systems?

    Science.gov (United States)

    Davankov, V. A.

    2016-10-01

    Consideration of chromatography of a nonracemic mixture on an achiral sorbent from a stereochemical point of view allows the claim that partial separation of the excess enantiomer zone from the racemate zone is possible only with analytes capable of self-associating under the conditions of the chromatographic column. It is from these positions that features of this process can be explained and conditions for its maximal proceeding formulated.

  6. Heparin-induced circular dichroism of an achiral, bicyclic species.

    Science.gov (United States)

    Stanley, Floyd E; Warner, Andrew M; McWilliams, Kayla M; Stalcup, Apryll M

    2011-01-01

    Antimalarial drugs have shown potential in suppressing the role of glycosaminoglycans (GAGs) in the pathology of prion protein conformational disorders (e.g. "Mad Cow" disease) by competing for sites of electrostatic interaction. In this study, circular dichroism (CD) and UV/Visible (UV/Vis) absorption spectroscopy techniques were used to investigate the interactions between N-methyl-N'-(7-chloro-4-quinolyl)-1,3-diaminopropane (QD), an achiral, bicyclic compound similar to previously investigated antimalarial drugs, and heparin, a complex GAG that is frequently used as a clinical anticoagulant. Relatively intense heparin-induced CD features were observed for QD and were noted to be radically different from previous studies using related chiral drugs, underscoring the importance of the Pfieffer effect on this and similar heparin research. Additionally, the induced CD for QD was observed to be highly dependent upon drug concentration, heparin concentration, system pH, equilibration time, and ionic strength. These results, in connection with recent work, provide new insight into the nature of the association between GAGs and antimalarial species. PMID:21125690

  7. Phonon and thermal properties of achiral single wall carbon nanotubes

    Indian Academy of Sciences (India)

    Prapti Saxena; Sankar P Sanyal

    2006-08-01

    A detailed theoretical study of the phonon and thermal properties of achiral single wall carbon nanotubes has been carried out using force constant model considering up to third nearest-neighbor interactions. We have calculated the phonon dispersions, density of states, radial breathing modes (RBM) and the specific heats for various zigzag and armchair nanotubes, with radii ranging from 2.8 Å to 11.0 Å. A comparative study of phonon spectrum with measured Raman data reveals that the number of Raman active modes for a tube does not depend on the number of atoms present in the unit cell but on its chirality. Calculated phonon modes at the zone center more or less accurately predicted the Raman active modes. The radial breathing mode is of particular interest as for a specific radius of a nanotube it is found to be independent of its chirality. We have also calculated the variation of RBM and G-band modes for tubes of different radii. RBM shows an inverse dependence on the radius of the tube. Finally, the values of specific heat are calculated for various nanotubes at room temperature and it was found that the specific heat shows an exponential dependence on the diameter of the tube.

  8. Generation of Absolute Controlled Crystal Chirality by the Removal of Crystal Water from Achiral Crystal of Nucleobase Cytosine

    OpenAIRE

    Kawasaki, Tsuneomi; Hakoda, Yuko; Mineki, Hiroko; Suzuki, Kenta; Soai, Kenso

    2010-01-01

    The enantioselective formation of chiral crystal of achiral nucleobase cytosine was achieved mediated by the crystal direction selective dehydration of crystal water in the achiral crystal of cytosine monohydrate (P21/c). Heat transfer from the enantiotopic face of the single crystal of cytosine monohydrate afforded the enantiomorphous crystal of anhydrous cytosine.

  9. Chiral and achiral helical coordination polymers of zinc and cadmium from achiral 2,6-bis(imidazol-1-yl)pyridine: Solvent effect and spontaneous resolution

    Indian Academy of Sciences (India)

    Sarita Tripathi; Renganathan Srirambalaji; Namita Singh; Ganapathi Anantharaman

    2014-09-01

    Four 2D helical coordination polymers (CPs) (1-4) were synthesized using achiral 2,6-bis (imidazol-1-yl)pyridine (pyim2) ligand with metal nitrates (metal = zinc and cadmium), which showed that variation in the solvent condition leads to difference in geometry around the central metal ion and results in chiral/achiral behaviour of these CPs. By using (pyim2), [trans-Zn(pyim2)2(NO3)2] (1) was obtained by unary solvent (MeOH), while [trans-Cd(pyim2)2(NO3)2] (2) was formed under binary solvent mixtures (DMF/MeOH). On the other hand, in ternary solvent mixture (DMF/MeOH/H2O) it resulted into an achiral {[trans-Zn(pyim2)2(H2O)2]·(NO3)2} (3) and homochiral {[cis-Cd(pyim2)2(H2O)2]·(NO3)2} (4) coordination polymer, respectively. The homochiral behaviour of the coordination polymer (4) was further studied by solid state CD spectra and also its optical behaviour was analyzed by polarimetry.

  10. Asymmetric Michael Reaction of Malononitrile Catalyzed by Chiral Ru(Ⅱ) Complex and Achiral Base

    Institute of Scientific and Technical Information of China (English)

    MA Ya-Ping; XING Zhi-Kui; ZHU Jin; CUI Xin; CUN Lin-Feng; DENG Jin-Gen

    2003-01-01

    @@ Michael addition reactions represent one of the most important carbon-carbon bond forming reactions in modern synthetic organic chemistry. [1 ~3] We achieved catalytic enantioselective Michael addition reactions of malononitrile with chiral vicinal diamine-Ru(Ⅱ) complex in the presence of achiral base. High yields and moderate ee were observed.

  11. A new achiral reagent for the incorporation of multiple amino groups into oligonucleotides

    DEFF Research Database (Denmark)

    Behrens, Carsten; Petersen, Kenneth H.; Egholm, Michael;

    1995-01-01

    The synthesis of a new functionalized achiral linker reagent (10) for the incorporation of multiple primary amino groups into oligonucleotides is described. The linker reagent is compatible with conventional DNA-synthesis following the phosphoramidite methodology, and the linker can be incorporat...

  12. Crystallization of an achiral cyclohexanone ethylene ketal in enantiomorphs and determination of the absolute structure.

    Science.gov (United States)

    Graus, Sara; Tejedor, Rosa M; Uriel, Santiago; Serrano, José Luis; Alkorta, Ibon; Elguero, José

    2010-06-16

    The achiral 4-methoxy-4-(p-methoxyphenyl)-cyclohexanone ethylene ketal (1) resolves spontaneously. The crystal structure is solved in chiral spatial group P2(1). Because compound 1 is composed of only light atoms (C, H, O) it is not possible to determine its absolute structure configuration. An efficient procedure for the absolute structure configuration determination of flexible molecules containing only light atoms is proposed, based on the combination of X-ray diffraction, solid-state VCD, and DFT calculations.

  13. The achiral tetrapeptide Z-Aib-Aib-Aib-Gly-OtBu.

    Science.gov (United States)

    Gessmann, Renate; Brückner, Hans; Petratos, Kyriacos

    2014-11-01

    The title achiral peptide N-benzyloxycarbonyl-α-aminoisobutyryl-α-aminoisobutyryl-α-aminoisobutyrylglycine tert-butyl ester or Z-Aib-Aib-Aib-Gly-OtBu (Aib is α-aminoisobutyric acid, Z is benzyloxycarbonyl, Gly is glycine and OtBu indicates the tert-butyl ester), C26H40N4O7, is partly hydrated (0.075H2O) and has two different conformations which together constitute the asymmetric unit. Both molecules form incipient 310-helices. They differ in the relative orientation of the N-terminal protection group and at the C-terminus. There are two 4→1 intramolecular hydrogen bonds.

  14. Layer thinning transition in an achiral four-ring hockey stick shaped liquid crystal

    Science.gov (United States)

    Paul, Manoj Kr.; Nath, Rahul K.; Moths, Brian; Pan, LiDong; Wang, Shun; Deb, Rajdeep; Shen, Yongqiang; Rao, Nandiraju V. S.; Huang, C. C.

    2012-12-01

    Depolarized reflected light microscopy and high resolution optical reflectivity measurements have been conducted on free-standing films of an achiral four-ring hockey stick shaped liquid crystal exhibiting SmA-B2-SmX* transition sequence. A layer thinning transition above the bulk isotropic-SmA phase transition has been observed. This behaviour was highly irreproducible, indicating an irregular layer thinning transition. From optical reflectivity data, both thickness of the free-standing films and the smectic interlayer spacing were determined. This is the first report of the layer thinning transition in a hockey stick shaped liquid crystal.

  15. Right handed chiral superstructures from achiral molecules: self-assembly with a twist.

    Science.gov (United States)

    Anuradha; La, Duong Duc; Al Kobaisi, Mohammad; Bhosale, Sheshanath V

    2015-01-01

    The induction and development of chiral supramolecular structures from hierarchical self-assembly of achiral compounds is closely related to the evolution of life and the chiral amplification found in nature. Here we show that the combination of achiral tetraphenylethene (TPE) an AIE-active luminophore bearing four long alkyl chains via amide linkage allows the entire process of induction and control of supramolecular chirality into well-defined uniform right-handed twisted superstructures via solvent composition and polarity, i.e. solvophobic effect. We showed that the degree of twist and the pitch of the ribbons can be controlled to one-handed helical structure via solvophobic effects. The twisted superstructure assembly was visualised by scanning electron microscope (SEM) and transmission electron microscopy (TEM), furthermore, circular dichroism (CD) confirms used to determine controlled right-handed assembly. This controlled assembly of an AIE-active molecule can be of practical value; for example, as templates for helical crystallisation, catalysis and a chiral mechanochromic luminescent superstructure formation. PMID:26493294

  16. Tuning of giant 2D-chiroptical response using achiral metasurface integrated with graphene.

    Science.gov (United States)

    Cao, Tun; Wei, Chen-Wei; Mao, Li-Bang; Wang, Shuai

    2015-07-13

    Tuning the chiroptical response of a molecule is crucial for detecting the material's chirality. Here, we demonstrate a pronounced circular conversion dichroism (CCD) by using an achiral metasurface (AMS) which is composed of a rectangular reflectarray of Au squares separated from a continuous Au film by a dielectric interlayer. This extrinsically 2D chirality originates from the mutual orientation between the AMS and oblique incident wave. The AMS is further incorporated with graphene to tune the CCD spectra in the mid-infrared (MIR) region by electrically modulating the graphene's Fermi level. This approach offers a high fabrication tolerance and will be a promising candidate for controlling electromagnetic (EM) waves in the MIR region from 1500 to 3000 nm. PMID:26191920

  17. Chiral assembly of achiral pseudoisocyanine with D-and L-phenylalanine

    Institute of Scientific and Technical Information of China (English)

    ZENG LiXi; HE Yujian; DAI ZhiFeng; WANG Jian; WANG CaiQi; YANG YongGang

    2009-01-01

    Supramolecular chirality and molecular self-assembly are important and interesting phenomena in living and non-living systems.In this work,supramolecular chirality of achiral pseudoisocyanine (PIC) J-aggregates was successfully induced by D-,L-phenylalanine (Phe) and other amino acids in NaCI solution.The chiral J-aggregates showed a characteristic,induced circular dichroism (ICD) in the visible region of J-band chromophore which depends on the absolute configuration,concentration and side groups of a-amino acids,as well as temperature.The atomic force microscopy images indicated that the J-aggregates exist in large bundles of entangled nanof ibers,and the observed ICD might result from the macroscopic helical arrangement of the assemblies.

  18. Chiral assembly of achiral pseudoisocyanine with D-and L-phenylalanine

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Supramolecular chirality and molecular self-assembly are important and interesting phenomena in living and non-living systems.In this work,supramolecular chirality of achiral pseudoisocyanine(PIC) J-aggregates was successfully induced by D-,L-phenylalanine(Phe) and other amino acids in NaCl solution.The chiral J-aggregates showed a characteristic,induced circular dichroism(ICD) in the visible region of J-band chromophore which depends on the absolute configuration,concentration and side groups of α-amino acids,as well as temperature.The atomic force microscopy images indicated that the J-aggregates exist in large bundles of entangled nanofibers,and the observed ICD might result from the macroscopic helical arrangement of the assemblies.

  19. Circularly polarized laser emission induced in isotropic and achiral dye systems

    Science.gov (United States)

    Cerdán, Luis; García-Moreno, Sara; Costela, Angel; García-Moreno, Inmaculada; de la Moya, Santiago

    2016-01-01

    The production of efficient, tunable, and switchable circularly polarized laser emission would have far reaching implications in optical communications or biophotonics. In this work, it is demonstrated the direct generation of circularly polarized (CP) laser emission in achiral and isotropic dye laser systems without the use of extracavity polarizing elements, and without resorting to chiral dyes, chiral liquid crystal matrices, or interferometric methods. The origin of this ellipticity arises from the dynamic birefringence induced by the strong and polarized laser pumping and the subsequent orientation anisotropy of the excited molecular dipoles. A complete polarimetric characterization of the polarization state of conventional dye laser oscillators as a function of different experimental parameters is performed and it is shown that the generated light always possesses a certain level of circularity that changes in a distinctive way with pump energy and polarization. These results demonstrate that it is possible to generate and modulate CP laser light from efficient and photostable conventional laser dyes. PMID:27350073

  20. Circularly polarized laser emission induced in isotropic and achiral dye systems

    Science.gov (United States)

    Cerdán, Luis; García-Moreno, Sara; Costela, Angel; García-Moreno, Inmaculada; de La Moya, Santiago

    2016-06-01

    The production of efficient, tunable, and switchable circularly polarized laser emission would have far reaching implications in optical communications or biophotonics. In this work, it is demonstrated the direct generation of circularly polarized (CP) laser emission in achiral and isotropic dye laser systems without the use of extracavity polarizing elements, and without resorting to chiral dyes, chiral liquid crystal matrices, or interferometric methods. The origin of this ellipticity arises from the dynamic birefringence induced by the strong and polarized laser pumping and the subsequent orientation anisotropy of the excited molecular dipoles. A complete polarimetric characterization of the polarization state of conventional dye laser oscillators as a function of different experimental parameters is performed and it is shown that the generated light always possesses a certain level of circularity that changes in a distinctive way with pump energy and polarization. These results demonstrate that it is possible to generate and modulate CP laser light from efficient and photostable conventional laser dyes.

  1. Generation of Supramolecular Chirality around Twofold Rotational or Helical Axes in Crystalline Assemblies of Achiral Components

    Directory of Open Access Journals (Sweden)

    Mikiji Miyata

    2015-10-01

    Full Text Available A multi-point approximation method clarifies supramolecular chirality of twofold rotational or helical assemblies as well as bundles of the one-dimensional (1D assemblies. While one-point approximation of materials claims no chirality generation of such assemblies, multi-point approximations do claim possible generation in the 1D assemblies of bars and plates. Such chirality derives from deformations toward three-axial directions around the helical axes. The chiral columns are bundled in chiral ways through symmetry operations. The preferable right- or left-handed columns are bundled together to yield chiral crystals with right- or left-handedness, respectively, indicating that twofold helix symmetry operations cause chiral crystals composed of achiral components via a three-stepwise and three-directional process.

  2. Sequential rhodium/palladium catalysis: enantioselective formation of dihydroquinolinones in the presence of achiral and chiral ligands.

    Science.gov (United States)

    Zhang, Lei; Qureshi, Zafar; Sonaglia, Lorenzo; Lautens, Mark

    2014-12-01

    Compatible combinations of achiral and chiral ligands can be used in rhodium/palladium catalysis to achieve highly enantioselective domino reactions. The difference in rates of catalysis and minimal effects of ligand interference confer control in the domino sequence. The "all-in-one" 1,4-conjugate arylation and C-N cross-coupling through sequential Rh/Pd catalysis provides access to enantioenriched dihydroquinolinone building blocks.

  3. Interfacial organization of achiral porphyrins via unidirectional compression: a general method for chiroptical porphyrin assemblies of selected chirality.

    Science.gov (United States)

    Zhang, Xiao; Wang, Yanping; Chen, Penglei; Rong, Yunlong; Liu, Minghua

    2016-05-18

    Porphyrins are considered to be important scaffolds bridging supramolecular chemistry and chiral chemistry, where chirality selection via physical effects such as directional stirring and spin-coating has aroused particular interest. Nevertheless, these protocols could only work on a limited number of achiral porphyrins. It still remains a formidable challenge to pave a general avenue for the construction of chiral assemblies using achiral porphyrins. By means of a unique Langmuir-Schaefer (LS) technique of a unidirectional compression configuration, we herein have demonstrated that a series of achiral porphyrins could be facilely organized to form chiral interfacial assemblies of controlled supramolecular chirality. It has been disclosed that such a fascinating chirality selection scenario is intimately related to the direction of the compression-generated vortex-like flow, while the compression speed, one of the most significant parameters of the Langmuir technique, contributes less to this issue. With regard to a surface-pressure-dependent chirality selection phenomenon, it is suggested that the directional vortex-like flow generated by lateral compression might play a role in promoting the preferential growth of chiral assemblies showing an enhanced yet controlled CD signal. Our protocol might be, to some extent, a general method for achieving chiral porphyrin assemblies of controlled chirality.

  4. Chiral and Achiral Nanodumbbell Dimers: The Effect of Geometry on Plasmonic Properties.

    Science.gov (United States)

    Smith, Kyle W; Zhao, Hangqi; Zhang, Hui; Sánchez-Iglesias, Ana; Grzelczak, Marek; Wang, Yumin; Chang, Wei-Shun; Nordlander, Peter; Liz-Marzán, Luis M; Link, Stephan

    2016-06-28

    Metal nanoparticles with a dumbbell-like geometry have plasmonic properties similar to those of their nanorod counterparts, but the unique steric constraints induced by their enlarged tips result in distinct geometries when self-assembled. Here, we investigate gold dumbbells that are assembled into dimers within polymeric micelles. A single-particle approach with correlated scanning electron microscopy and dark-field scattering spectroscopy reveals the effects of dimer geometry variation on the scattering properties. The dimers are prepared using exclusively achiral reagents, and the resulting dimer solution produces no detectable ensemble circular dichroism response. However, single-particle circular differential scattering measurements uncover that this dimer sample is a racemic mixture of individual nanostructures with significant positive and negative chiroptical signals. These measurements are complemented with detailed simulations that confirm the influence of various symmetry elements on the overall peak resonance energy, spectral line shape, and circular differential scattering response. This work expands the current understanding of the influence self-assembled geometries have on plasmonic properties, particularly with regard to chiral and/or racemic samples which may have significant optical activity that may be overlooked when using exclusively ensemble characterization techniques.

  5. Instrumental Idiosyncrasies Affecting the Performance of Ultrafast Chiral and Achiral Sub/Supercritical Fluid Chromatography.

    Science.gov (United States)

    Barhate, Chandan L; Wahab, M Farooq; Tognarelli, D J; Berger, Terry A; Armstrong, Daniel W

    2016-09-01

    It is widely accepted that column technology is ahead of existing chromatographic instruments. The chromatographic output may not reflect the true picture of the peak profile inside the column. The instrumental optimization parameters become far more important when peaks elute in a few seconds. In this work, the low viscosity advantage of the supercritical/subcritical CO2 is coupled with the high efficiency of narrow particle size distribution silica. Using short efficient columns and high flow rates (up to 19 mL/min), separations on the order of a few seconds are demonstrated. In the domain of ultrafast supercritical fluid chromatography (SFC), unexpected results are seen which are absent in ultrafast liquid chromatography. These effects arise due to the compressible nature of the mobile phase and detector idiosyncrasies to eliminate back-pressure regulator noise. We demonstrate unusual connection tubing effects with 50, 75, 127, 254, and 500 μm tubings and show the complex relation of dead time, retention time, efficiency, and optimum velocity with the tubing diameter (via column outlet pressure). Fourier analysis at different back-pressure regulator (BPR) settings shows that some instruments have very specific noise frequencies originating from the BPR, and those specific frequencies vanish under certain conditions. The performance of embedded digital filters, namely, moving average, numerically simulated low pass RC, and Gaussian kernels, is compared. This work also demonstrates, using a simple derivative test, that some instruments employ interpolation techniques while sampling at "true" low frequencies to avoid picking up high frequency noise. Researchers engaged in ultrafast chromatography need to be aware of the instrumental nuances and optimization procedures for achieving ultrafast chiral or achiral separations in SFC mode. PMID:27500473

  6. Synthesis and mesomorphic behaviour of achiral four-ring unsymmetrical bent-core liquid crystals: Nematic phases

    Science.gov (United States)

    Paul, Manoj Kumar; Kalita, Gayatri; Laskar, Atiqur Rahman; Debnath, Somen; Gude, Venkatesh; Sarkar, Dipika Debnath; Mohiuddin, Golam; Varshney, Sanjay Kumar; Nandiraju Rao, V. S.

    2013-10-01

    Achiral four ring unsymmetrical bent-core liquid crystals derived from 3-amino-2-methylbenzoic acid have been designed and synthesized with an imine, ester and photochromic azo linking moieties. These hockey-stick shape resembling bent molecules possess an alkoxy chain at one end of the molecule and methyl or methoxy group at the other end. The synthesis, phase transition temperatures and characterization of phase behaviour are discussed. The molecular structure characterization is consistent with data from elemental and spectroscopic analysis. The materials thermal behaviour and phase characterization have been investigated by differential scanning calorimetry and polarizing optical microscopy. All these compounds exhibit enantiotropic nematic phase over wide temperature range. Stable supercooling of nematic phase has been observed in methoxy homologues. The density functional theory (DFT) calculations were performed to obtain the stable molecular conformation, polarizability, dipole moment, Highest occupied molecular orbital (HOMO), Lowest unoccupied molecular orbital (LUMO) energies and bending angle of the compound.

  7. Separation mechanism of chiral impurities, ephedrine and pseudoephedrine, found in amphetamine-type substances using achiral modifiers in the gas phase.

    Science.gov (United States)

    Holness, Howard K; Jamal, Adeel; Mebel, Alexander; Almirall, José R

    2012-11-01

    A new mechanism is proposed that describes the gas-phase separation of chiral molecules found in amphetamine-type substances (ATS) by the use of high-resolution ion mobility spectrometry (IMS). Straight-chain achiral alcohols of increasing carbon chain length, from methanol to n-octanol, are used as drift gas modifiers in IMS to highlight the mechanism proposed for gas-phase separations of these chiral molecules. The results suggest the possibility of using these achiral modifiers to separate the chiral molecules (R,S) and (S,R)-ephedrine and (S,S) and (R,R)-pseudoephedrine which contain an internal hydroxyl group at the first chiral center and an amino group at the other chiral center. Ionization was achieved with an electrospray source, the ions were introduced into an IMS with a resolving power of 80, and the resulting ion clusters were characterized with a coupled quadrupole mass spectrometer detector. A complementary computational study conducted at the density functional B3LYP/6-31g level of theory for the electronic structure of the analyte-modifier clusters was also performed, and showed either "bridged" or "independent" binding. The combined experimental and simulation data support the proposed mechanism for gas-phase chiral separations using achiral modifiers in the gas phase, thus enhancing the potential to conduct fast chiral separations with relative ease and efficiency.

  8. Validation of a method using an achiral liquid chromatography sorbent and a circular dichroism detector. Analysis of the efaroxan enantiomers.

    Science.gov (United States)

    Lorin, Marie; Delépée, Raphaël; Ribet, Jean-Paul; Morin, Philippe

    2007-02-01

    The known HPLC method using an achiral C8 silica sorbent and a circular dichroism (CD) detector for the determination of efaroxan enantiomeric excess has been validated. After optimization of the mobile phase, the enantiomers were detected at 278 nm offering maximum ellipticity between two optically active forms. The calibration curve of the anisotropy factor (g) versus the enantiomeric excess was linear with a correlation coefficient (r2) of 0.9985. The accuracy of the method was assessed by comparing the enantiomeric excess obtained by measuring the g factor (C8 column, CD and UV detections) with those determined by enantioselective HPLC (Chiralpak AD-H column, UV detection). Statistical tests (level of confidence of 95%) were assessed to compare the two orthogonal methods. The straight line gave a correlation coefficient of 0.9995, an intercept not significantly different from zero (0.0549) and a slope of 1.026. The precision evaluated on retention time (RSDmethod has the advantages of being fast and precise without using expensive chiral column. Non-enantioselective HPLC-CD was suitable for the simultaneous determination of the optical and chemical purity of efaroxan.

  9. Pinwheel clusters of achiral rod-like molecules formed on achiral surface%非手性的棒状分子在非手性表面形成的风车团簇

    Institute of Scientific and Technical Information of China (English)

    邵婷娜; 兰梦; 谢佳乐; 孙凯; 蔡田田; 王俊忠

    2012-01-01

    利用低温STM研究了非手性的棒状并五苯分子在Bi(111)表面形成的手性风车团簇.在团簇内部,并五苯分子分别沿Bi(111)的3个对称轴方向平行排列,形成6个不同的分子带.在每个分子带中,相邻分子之间有一个滑移错位.当平行排列的分子数多于4时,滑移错位发生反向,形成弯曲的风车扇叶.我们认为,分子的滑移错位来自于分子之间的π-π相互作用;而滑移错位的反向是团簇内部的吸引力导致的密堆积的结果.这两种作用的竞争是形成手性风车团簇的微观机制.%The molecular arrangement and chirality of the self-assembly of pentacene on Bi(lll) were investigated using scanning tunneling microscopy (STM). Upon adsorption on Bi(111), this achiral molecule spontaneously forms two types of chiral pinwheel clusters with opposite chirality. Within the clusters, each pentacene molecule is aligned in the symmetric axis of Bi(111), resulting the formation of six molecular rows. In each row, the adjacent pentacene molecule is shifted along the long molecular axis. When the molecule number exceeding four, the shifting directions is reversed, lead to the formation of bent flabellum. The formation mechanism is attributed to the competition between it-it interaction and the net attractive interaction among the pentacene molecules.

  10. Colloidal chirality in wormlike micellar systems exclusively originated from achiral species: Role of secondary assembly and stimulus responsivity.

    Science.gov (United States)

    Zhao, Wenrong; Hao, Jingcheng

    2016-09-15

    Colloidal chirality in wormlike micellar systems exclusively originated from achiral species and discussion of the role of secondary assembly of fiber-like aggregates in chirality generation were presented in this paper. Herein, formation of colloidal wormlike micelles for the first time incorporated chirality and redox-responsiveness into one design via noncovalent interaction. A dual-stimuli-responsive gel of wormlike micelles which were designed by employing a dual-responsive cationic surfactant (FTMA) and a strong gelator (AzoNa4) and regulated by redox reaction and host-guest inclusion is presented. Both the redox and host-guest interaction play an important role in regulating the viscosity and supramolecular chirality of gels of the wormlike micelles. The supramolecular chirality and viscosity of the wormlike micelle gels were switched reversibly by exerting chemical redox onto the ferrocenyl groups. For the amphiphile FTMA containing redox-active ferrocenyl group, reversible control of the oxidation state of ferrocenyl groups leads to the charge and hydrophobicity changes of FTMA, therefore change its self-assembly behavior. Of equal interest, β-CD successfully detached the wormlike micelles via the recognition-inclusion behavior with FTMA and invalidate the H-bond and hydrophobic interaction between FTMA and AzoH4. This designed system provides a new strategy to tune the supramolecular chirality of colloidal aggregates and explore the specific packing mode detail within the micelles or the secondary assembly of the inter-micelles. We anticipate this dual-responsive H-bond-directed chiral gel switch could propose a new strategy when researchers designing new, multi-responsive functional gel materials. PMID:27314643

  11. NON-RACEMIC AMINO ACID PRODUCTION BY ULTRAVIOLET IRRADIATION OF ACHIRAL INTERSTELLAR ICE ANALOGS WITH CIRCULARLY POLARIZED LIGHT

    International Nuclear Information System (INIS)

    The delivery of organic matter to the primitive Earth via comets and meteorites has long been hypothesized to be an important source for prebiotic compounds such as amino acids or their chemical precursors that contributed to the development of prebiotic chemistry leading, on Earth, to the emergence of life. Photochemistry of inter/circumstellar ices around protostellar objects is a potential process leading to complex organic species, although difficult to establish from limited infrared observations only. Here we report the first abiotic cosmic ice simulation experiments that produce species with enantiomeric excesses (e.e.'s). Circularly polarized ultraviolet light (UV-CPL) from a synchrotron source induces asymmetric photochemistry on initially achiral inter/circumstellar ice analogs. Enantioselective multidimensional gas chromatography measurements show significant e.e.'s of up to 1.34% for (13C)-alanine, for which the signs and absolute values are related to the helicity and number of CPL photons per deposited molecule. This result, directly comparable with some L excesses measured in meteorites, supports a scenario in which exogenous delivery of organics displaying a slight L excess, produced in an extraterrestrial environment by an asymmetric astrophysical process, is at the origin of biomolecular asymmetry on Earth. As a consequence, a fraction of the meteoritic organic material consisting of non-racemic compounds may well have been formed outside the solar system. Finally, following this hypothesis, we support the idea that the protosolar nebula has indeed been formed in a region of massive star formation, regions where UV-CPL of the same helicity is actually observed over large spatial areas.

  12. On the balance between syn- and anticlinicity in smectic phases formed by achiral hockey-stick mesogens with and without chiral dopants

    OpenAIRE

    Enz, Eva; Findeisen-Tandel, Sonja; Dabrowski, Roman; Giesselmann, Frank; Weissflog, Wolfgang; Baumeister, Ute; Lagerwall, Jan

    2009-01-01

    A series of achiral hockey-stick-shaped mesogens forming tilted smectic liquid crystal phases of synclinic SmC- as well as anticlinic SmCa-type was prepared and characterized. While all homologues exhibit both phases, the balance shifts from anticlinic to synclinic order upon elongation of the terminal chain at the meta-position, defining the hockey-stick shape. The elongation also leads to an increased kinetic hindrance of the transition between syn- and anticlinic phases and a decreased tra...

  13. A new approach to determine the stereospecificity in lipase catalysed hydrolysis using circular dichroism (CD): lipases produce optically active diglycerides from achiral triglycerides.

    Science.gov (United States)

    Uzawa, H; Nishida, Y; Ohrui, H; Meguro, H

    1990-04-30

    We describe a sensitive CD method for determining the stereospecificity in lipase (E.C.3.1.1.3) catalysed hydrolysis of triacyl glycerols into diacyl glycerols. The diglycerols were converted to chiral tert-butyldimethylsilylated 1,2- or 2,3-di-O-benzoyl-sn-glycerol (5 or 5'), and their CD was measured. This approach showed for the first time that lipases produce optically active diacyl glycerides from achiral tripalmitin and tribenzoyl glyceride with a variable extent of enantioselectivity depending on the acyl groups and the enzymes.

  14. Left-handed helical preference in an achiral peptide chain is induced by an L-amino acid in an N-terminal type II β-turn.

    Science.gov (United States)

    De Poli, Matteo; De Zotti, Marta; Raftery, James; Aguilar, Juan A; Morris, Gareth A; Clayden, Jonathan

    2013-03-15

    Oligomers of the achiral amino acid Aib adopt helical conformations in which the screw-sense may be controlled by a single N-terminal residue. Using crystallographic and NMR techniques, we show that the left- or right-handed sense of helical induction arises from the nature of the β-turn at the N terminus: the tertiary amino acid L-Val induces a left-handed type II β-turn in both the solid state and in solution, while the corresponding quaternary amino acid L-α-methylvaline induces a right-handed type III β-turn.

  15. Relationship between chromatographic resolution and amide structure of chiral 2-hydroxy acids as O-(-)-menthoxycarbonylated diastereomeric derivatives for enantiomeric separation on achiral gas chromatography.

    Science.gov (United States)

    Cha, Eunju; Kim, Sohee; Lee, Kang Mi; Kim, Ho Jun; Kim, Ki Hun; Kwon, Oh-Seung; Park, Ki Duk; Lee, Jaeick

    2016-02-15

    The relationship between chromatographic resolution and amide structure of chiral 2-hydroxy acids as O-(-)-menthoxycarbonylated diastereomeric derivatives on achiral gas chromatography was investigated to elucidate the best diastereomeric conformation for enantiomeric separation of chiral 2-hydroxy acids. Thirteen chiral 2-hydroxy acids were converted into nine different diastereomeric O-(-)-menthoxycarbonylated amide derivatives using the primary, secondary and cyclic amines to achieve complete enantiomeric separation through an achiral column. Each enantiomeric pair of 2-hydroxy acids as O-(-)-menthoxycarbonylated tert-butylamide derivatives was resolved on both the DB-5 and DB-17 columns with resolution factors ranging from 1.7 to 4.8 and 1.7 to 3.4, respectively. The results revealed that the structure of the amide moiety is shown to significantly affect chromatographic resolution. In addition, O-(-)-menthoxycarbonylated tert-butylamide derivatives were shown to be the best diastereomeric conformations for enantiomeric separation of 2-hydroxy acids. When comparing with our previous O-trifluoroacetylated(-)-menthyl ester derivatization method, the present results suggested that size differences between groups attached to the chiral center and conformational rigidity can have stronger effects on resolution than the distance between chiral centers. The elution of R- and S-stereoisomers was affected by the class of amine; i.e., primary, secondary, or cyclic, regardless of the substituents on the amine group, the structure of the 2-hydroxy acid, and the polarity of the column. PMID:26800225

  16. Efficient resolution of (±)-rans-2,3-diphenylpiperazine using (1)-(+)-10-camphorsulfonic acid and enrichment of enantiomeric purity of non-racemic 2,3-diphenylpiperazine using different achiral acids

    Indian Academy of Sciences (India)

    Pothiappan Vairaprakash; Mariappan Periasamy

    2008-01-01

    Enantiomerically pure (,)-(+)-2,3-diphenylpiperazine with 98% was obtained by resolution of the corresponding racemic mixture using (1)-(+)-10-camphorsulfonic acid. The partially resolved enriched sample of (,)-(-)-2,3-diphenylpiperazine with 73% ee was purified to obtain samples of 97% ee using different achiral acids via the preparation of either homochiral or heterochiral hydrogen bonded aggregates.

  17. Synthesis of racemic and chiral BEDT-TTF derivatives possessing hydroxy groups and their achiral and chiral charge transfer complexes

    Directory of Open Access Journals (Sweden)

    Sara J. Krivickas

    2015-09-01

    Full Text Available Chiral molecular crystals built up by chiral molecules without inversion centers have attracted much interest owing to their versatile functionalities related to optical, magnetic, and electrical properties. However, there is a difficulty in chiral crystal growth due to the lack of symmetry. Therefore, we made the molecular design to introduce intermolecular hydrogen bonds in chiral crystals. Racemic and enantiopure bis(ethylenedithiotetrathiafulvalene (BEDT-TTF derivatives possessing hydroxymethyl groups as the source of hydrogen bonds were designed. The novel racemic trans-vic-(hydroxymethyl(methyl-BEDT-TTF 1, and racemic and enantiopure trans-vic-bis(hydroxymethyl-BEDT-TTF 2 were synthesized. Moreover, the preparations, crystal structure analyses, and electrical resistivity measurements of the novel achiral charge transfer salt θ21-[(S,S-2]3[(R,R-2]3(ClO42 and the chiral salt α’-[(R,R-2]ClO4(H2O were carried out. In the former θ21-[(S,S-2]3[(R,R-2]3(ClO42, there are two sets of three crystallographically independent donor molecules [(S,S-2]2[(R,R-2] in a unit cell, where the two sets are related by an inversion center. The latter α’-[(R,R-2]ClO4(H2O is the chiral salt with included solvent H2O, which is not isostructural with the reported chiral salt α’-[(S,S-2]ClO4 without H2O, but has a similar donor arrangement. According to the molecular design by introduction of hydroxy groups and a ClO4− anion, many intermediate-strength intermolecular hydrogen bonds (2.6–3.0 Å were observed in these crystals between electron donor molecules, anions, and included H2O solvent, which improve the crystallinity and facilitate the extraction of physical properties. Both salts are semiconductors with relatively low resistivities at room temperature and activation energies of 1.2 ohm cm with Ea = 86 meV for θ21-[(S,S-2]3[(R,R-2]3(ClO42 and 0.6 ohm cm with Ea = 140 meV for α'-[(R,R-2]2ClO4(H2O, respectively. The variety of donor arrangements

  18. Sequence of Four Orthogonal Smectic Phases in an Achiral Bent-Core Liquid Crystal: Evidence for the SmAPα Phase

    Science.gov (United States)

    Panarin, Y. P.; Nagaraj, M.; Sreenilayam, S.; Vij, J. K.; Lehmann, A.; Tschierske, C.

    2011-12-01

    The mesomorphic properties of an achiral bent-core liquid crystal derived from 4-cyanoresorcinol are studied by polarizing optical microscopy, x-ray diffraction, and second harmonic electro-optic response. It shows a novel sequence of four nontilted or orthogonal smectic phases on cooling: SmA-SmAPR-SmAPX-SmAPA. Here SmAPX is the new orthogonal polar uniaxial smectic phase. The electric-field-induced transformations in the SmAPX phase give rise to two biaxial states separated by a uniaxial one. The second harmonic electro-optic response in this phase is interpreted in terms of the polar interaction with the electric field. A comparison of the experimental results with the next-nearest-neighbor model for the structure of the SmAPX phase shows it to be an SmAPα phase.

  19. Effects of the dynamic modification of stationary phases by sorbates in gas chromatography: The possibility of separating enantiomers in achiral systems

    Science.gov (United States)

    Zenkevich, I. G.; Pavlovskii, A. A.

    2016-10-01

    It is shown that the gas chromatographic separation of enantiomers on columns with achiral nonpolar stationary phases is principally possible as a result of the dynamic modification of stationary phases by sorbates under analysis. It is found that a number of key characteristic features is intrinsic to such separation: it can be only partial, it does not occur for all chromatographic columns, and it is observed only for some compounds and only within narrow ranges of quantities of sorbates that are close to the limits of mass overload of chromatographic systems. These characteristic features are illustrated by the examples of separating (1 R,5 R)-(+)- and (1 S,5 S)-(-)-α-pinenes on a WCOT column with an RTX-5 phase. The main characteristic feature of the separation of enantiomers as a result of the dynamic modification of stationary phases is the nonconformity of peaks in chromatograms with two individual enantiomers, compared to other ways and means for their separation; the first eluting peak belongs to the enantiomer that predominates in a mixture irrespective of its configuration, while the second peak corresponds to the racemic mixture of enantiomers; i.e., the ratio of peak areas in chromatograms does not correspond to the actual ratio of enantiomers in samples under analysis and is strongly distorted as a result of their incomplete separation. It is concluded that the separation of racemic mixtures in achiral systems is fundamentally impossible under any conditions, and this is one of the key criteria of the validity of the considered concept as a whole.

  20. Achiral pyrazinone-based inhibitors of the hepatitis C virus NS3 protease and drug-resistant variants with elongated substituents directed toward the S2 pocket.

    Science.gov (United States)

    Gising, Johan; Belfrage, Anna Karin; Alogheli, Hiba; Ehrenberg, Angelica; Åkerblom, Eva; Svensson, Richard; Artursson, Per; Karlén, Anders; Danielson, U Helena; Larhed, Mats; Sandström, Anja

    2014-03-13

    Herein we describe the design, synthesis, inhibitory potency, and pharmacokinetic properties of a novel class of achiral peptidomimetic HCV NS3 protease inhibitors. The compounds are based on a dipeptidomimetic pyrazinone glycine P3P2 building block in combination with an aromatic acyl sulfonamide in the P1P1' position. Structure-activity relationship data and molecular modeling support occupancy of the S2 pocket from elongated R(6) substituents on the 2(1H)-pyrazinone core and several inhibitors with improved inhibitory potency down to Ki = 0.11 μM were identified. A major goal with the design was to produce inhibitors structurally dissimilar to the di- and tripeptide-based HCV protease inhibitors in advanced stages of development for which cross-resistance might be an issue. Therefore, the retained and improved inhibitory potency against the drug-resistant variants A156T, D168V, and R155K further strengthen the potential of this class of inhibitors. A number of the inhibitors were tested in in vitro preclinical profiling assays to evaluate their apparent pharmacokinetic properties. The various R(6) substituents were found to have a major influence on solubility, metabolic stability, and cell permeability. PMID:23517538

  1. "Heart-cut" bidimensional achiral-chiral liquid chromatography applied to the evaluation of stereoselective metabolism, in vivo biological activity and brain response to chiral drug candidates targeting the central nervous system.

    Science.gov (United States)

    Battisti, Umberto M; Citti, Cinzia; Larini, Martina; Ciccarella, Giuseppe; Stasiak, Natalia; Troisi, Luigino; Braghiroli, Daniela; Parenti, Carlo; Zoli, Michele; Cannazza, Giuseppe

    2016-04-22

    A "heart-cut" two-dimensional achiral-chiral liquid chromatography triple-quadrupole mass spectrometry method (LC-LC-MS/MS) was developed and coupled to in vivo cerebral microdialysis to evaluate the brain response to the chiral compound (±)-7-chloro-5-(3-furanyl)-3-methyl-3,4-dihydro-2H-1,2,4-benzothiadiazine-1,1-dioxide ((±)-1), a potent positive allosteric modulator (PAM) of AMPA receptor. The method was successfully employed to evaluate also its stereoselective metabolism and in vitro biological activity. In particular, the LC achiral method developed, employs a pentafluorinated silica based column (Discovery HS-F5) to separate dopamine, acetylcholine, serotonin, (±)-1 and its two hepatic metabolites. In the "heart-cut" two-dimension achiral-chiral configuration, (±)-1 and (±)-1-d4 eluted from the achiral column (1st dimension), were transferred to a polysaccharide-based chiral column (2nd dimension, Chiralcel OD-RH) by using an automatic six-port valve. Single enantiomers of (±)-1 were separated and detected using electrospray positive ionization mode and quantified in selected reaction monitoring mode. The method was validated and showed good performance in terms of linearity, accuracy and precision. The new method employed showed several possible applications in the evaluation of: (a) brain response to neuroactive compounds by measuring variations in the brain extracellular levels of selected neurotransmitters and other biomarkers; (b) blood brain barrier penetration of drug candidates by measuring the free concentration of the drug in selected brain areas; (c) the presence of drug metabolites in the brain extracellular fluid that could prove very useful during drug discovery; (d) a possible stereoselective metabolization or blood brain barrier stereoselective crossing of chiral drugs. Finally, compared to the methods reported in the literature, this technique avoids the necessity of euthanizing an animal at each time point to measure drug

  2. TPPS和Gemini表面活性剂的复合膜及其手性的研究%Supramolecular Assembly and Chirality of a Complex Film between Achiral TPPS and a Gemini Surfactant at the Air/water Interface

    Institute of Scientific and Technical Information of China (English)

    张莉; 王金本; 刘鸣华

    2004-01-01

    研究了一种新的gemini表面活性剂(C 12H24-α,ω-(C12H25N+(CH3)2Br-)2,(简写为C12-C12-C12)和TPPS在气液界面上形成的复合膜及其手性.实验发现,单独C12-C12-C12不能在纯水表面形成稳定的单分子膜,但当亚相中存在TPPS时,可形成稳定的单分子膜.通过水平提拉法将复合膜转移到固体基板上,发现在适当的pH值条件下,TPPS可在复合膜中形成J-聚集体,并且发现,尽管Gemini表面活性剂和TPPS都是非手性的,TPPS的J-聚集体表现出强烈的Cotton效应.另外,gemini表面活性剂的两个正电荷中心对TPPS的J-聚集体的手性并不能表现出协同效应.%Supramolecular assembly and chirality between a novel gemini surfactant (C12H24-α, ω-(C12H25N + (CH3)2Br-)2,(abbreviated as C12-C12-C12) and TPPS (tetrakis(4-sulfonatophenyl) porphine) at the air/water interface were investigated. It was found that although the gemini surfactant itself could not form a stable monolayer at the air/water interface, when there existed TPPS in the subphase, a stable complex monolayer could be formed. The complex monolayer could be transferred onto solid substrate by a horizontal lifting method. At a certain pH value of the subphase, TPPS could form a J-aggregate. It was further found that the J-aggregate of TPPS showed a strong split Cotton effect in the transferred film although both the gemini surfactant and TPPS are achiral. Further investigation through AFM measurements revealed that the nanothread formed in the transferred film was responsible for the chirality of the multilayer film. In addition, the two positive charge center of the gemini surfactant did not necessarily play the cooperative role in inducing the chirality of TPPS J-aggregate.

  3. Optical Activity of Planar Achiral Metamaterials

    CERN Document Server

    Plum, E; Zheludev, N I

    2008-01-01

    We report that the classical phenomena of optical activity and circular dichroism, which are traditionally associated with chirality (helicity) of organic molecules, proteins and inorganic structures, can be observed in non-chiral artificial media. Intriguingly, our metamaterial structure yields exceptionally strong resonant optical activity, which also leads to the appearance of a backward wave, a characteristic sign of negative-index media.

  4. From achiral to chiral analysis of citalopram

    OpenAIRE

    Carlsson, Björn

    2003-01-01

    Within the field of depression the “monoamine hypothesis” has been the leading theory to explain the biological basis of depression. This theory proposes that the biological basis of depression is due to a deficiency in one or more of three key neurotransmitter systems, namely noradrenaline, dopamine and serotonin which are thought to mediate the therapeutic actions of virtually every known antidepressant agent. Citalopram is a selective serotonin-reuptake inhibitor (SSRI) used for the treatm...

  5. Highly tunable optical activity in planar achiral terahertz metamaterials

    CERN Document Server

    Singh, Ranjan; Zhang, Weili; Zheludev, Nikolay I

    2010-01-01

    Using terahertz time domain spectroscopy we demonstrate tunable polarization rotation and circular dichroism in intrinsically nonchiral planar terahertz metamaterials without twofold rotational symmetry. The observed effect is due to extrinsic chirality arising from the mutual orientation of the metamaterial plane and the propagation direction of the incident terahertz wave.

  6. Microsecond linear optical response in the unusual nematic phase of achiral bimesogens

    Science.gov (United States)

    Panov, V. P.; Balachandran, R.; Nagaraj, M.; Vij, J. K.; Tamba, M. G.; Kohlmeier, A.; Mehl, G. H.

    2011-12-01

    Some hydrocarbon linked mesogenic dimers are known to exhibit an additional nematic phase (Nx) below a conventional uniaxial nematic (Nu) phase. Although composed of non-chiral molecules, the Nx phase is found to exhibit linear (polar) switching under applied electric field. This switching has remarkably low response time of the order of a few microseconds. Two chiral domains with opposite handedness and consequently opposite responses are found in planar cells. Uniformly lying helix, electroclinic, and flexoelectric effects are given as possible causes for this intriguing phenomenon.

  7. Giant Nonlinear Optical Activity of Achiral Origin in Planar Metasurfaces with Quadratic and Cubic Nonlinearities.

    Science.gov (United States)

    Chen, Shumei; Zeuner, Franziska; Weismann, Martin; Reineke, Bernhard; Li, Guixin; Valev, Ventsislav Kolev; Cheah, Kok Wai; Panoiu, Nicolae Coriolan; Zentgraf, Thomas; Zhang, Shuang

    2016-04-20

    3D chirality is shown to be unnecessary for introducing strong circular dichroism for harmonic generations. Specifically, near-unity circular dichroism for both second-harmonic generation and third-harmonic generations is demonstrated on suitably designed ultrathin plasmonic metasurfaces with only 2D planar chirality. The study opens up new routes for designing chip-type biosensing platform, which may allow for highly sensitive detection of bio- and chemical molecules with weak chirality.

  8. On the stereoselective synthesis of (+)-pinoresinol in Forsythia suspensa from its achiral precursor, coniferyl alcohol.

    Science.gov (United States)

    Davin, L B; Bedgar, D L; Katayama, T; Lewis, N G

    1992-11-01

    The residue from Forsythia suspensa stems, upon removal of soluble enzymes, has provided the first evidence for a stereoselective coupling enzyme in lignan biosynthesis. This preparation catalyses the preferred formation (ca 65%) of (+)-[8,8'-14C]pinoresinol from [8-14C]coniferyl alcohol in the absence of exogenously provided cofactors; addition of H2O2 had little effect on enantiomeric composition. However, when NAD and malate were supplied, the stereoselectivity of the coupling reaction was significantly enhanced and pinoresinol consisting of ca 80% of the (+)-antipode was obtained. Clearly, the insoluble residue contains a specific coupling enzyme which catalyses (+)-pinoresinol formation from coniferyl alcohol. By contrast, when [8-14C]sinapyl alcohol was employed as substrate, only racemic syringaresinols were formed: this non-stereoselective peroxidase-catalysed coupling reaction presumably accounts for the low levels of (-)-pinoresinol encountered in this system when coniferyl alcohol is used as a substrate.

  9. Dexamethasone decreases plasma levels of the prochiral fenbendazole and its chiral and achiral metabolites in sheep.

    Science.gov (United States)

    Sánchez, S; Small, J; Jones, D G; McKellar, Q A

    2003-07-01

    1. The effect of co-administration of either short- or long-acting formulations of DXM on hepatic function and the plasma pharmacokinetic behaviour of prochiral fenbendazole (FBZ) and its metabolites was evaluated in sheep. 2. Neither DXM treatment markedly affected any of the biochemical markers of hepatic function tested. In contrast, both formulations significantly modified the plasma pharmacokinetic behaviour of FBZ and its metabolites. 3. Plasma FBZ concentrations and the associated area under the time-concentration curves were significantly lower, although the plasma detection period was longer (72 versus 48 h) in the DXM pretreated animals compared with those given FBZ alone. 4. DXM also appeared to alter the pattern of FBZ absorption, possibly through effects on abomasal pH. The shape of the plasma concentration-time curves for oxfendazole (OFZ) and fenbendazole sulphone (FBZSO(2)) were similar to FBZ, raising the possibility that DXM treatment may have altered the liver biotransformation of the parent drug. 5. The concentrations of the (+) chiral metabolite of OFZ were significantly lower in DXM pretreated animals compared with those given FBZ alone. The trend was similar for the (-) antipode, although the differences between DXM pretreated and non-pretreated animals were not statistically significant.

  10. Spontaneous emergence of chirality in achiral lyotropic chromonic liquid crystals confined to cylinders.

    Science.gov (United States)

    Nayani, Karthik; Chang, Rui; Fu, Jinxin; Ellis, Perry W; Fernandez-Nieves, Alberto; Park, Jung Ok; Srinivasarao, Mohan

    2015-01-01

    The presumed ground state of a nematic fluid confined in a cylindrical geometry with planar anchoring corresponds to that of an axial configuration, wherein the director, free of deformations, is along the long axis of the cylinder. However, upon confinement of lyotropic chromonic liquid crystals in cylindrical geometries, here we uncover a surprising ground state corresponding to a doubly twisted director configuration. The stability of this ground state, which involves significant director deformations, can be rationalized by the saddle-splay contribution to the free energy. We show that sufficient anisotropy in the elastic constants drives the transition from a deformation-free ground state to a doubly twisted structure, and results in spontaneous symmetry breaking with equal probability for either handedness. Enabled by the twist angle measurements of the spontaneous twist, we determine the saddle-splay elastic constant for chromonic liquid crystals for the first time. PMID:26287517

  11. Mirror Symmetry Breaking by Chirality Synchronisation in Liquids and Liquid Crystals of Achiral Molecules.

    Science.gov (United States)

    Tschierske, Carsten; Ungar, Goran

    2016-01-01

    Spontaneous mirror symmetry breaking is an efficient way to obtain homogeneously chiral agents, pharmaceutical ingredients and materials. It is also in the focus of the discussion around the emergence of uniform chirality in biological systems. Tremendous progress has been made by symmetry breaking during crystallisation from supercooled melts or supersaturates solutions and by self-assembly on solid surfaces and in other highly ordered structures. However, recent observations of spontaneous mirror symmetry breaking in liquids and liquid crystals indicate that it is not limited to the well-ordered solid state. Herein, progress in the understanding of a new dynamic mode of symmetry breaking, based on chirality synchronisation of transiently chiral molecules in isotropic liquids and in bicontinuous cubic, columnar, smectic and nematic liquid crystalline phases is discussed. This process leads to spontaneous deracemisation in the liquid state under thermodynamic control, giving rise to long-term stable symmetry-broken fluids, even at high temperatures. These fluids form conglomerates that are capable of extraordinary strong chirality amplification, eventually leading to homochirality and providing a new view on the discussion of emergence of uniform chirality in prebiotic systems. PMID:26416335

  12. Large-scale fabrication of achiral plasmonic metamaterials with giant chiroptical response.

    Science.gov (United States)

    Slyngborg, Morten; Tsao, Yao-Chung; Fojan, Peter

    2016-01-01

    A variety of extrinsic chiral metamaterials were fabricated by a combination of self-ordering anodic oxidation of aluminum foil, nanoimprint lithography and glancing angle deposition. All of these techniques are scalable and pose a significant improvement to standard metamaterial fabrication techniques. Different interpore distances and glancing angle depositions enable the plasmonic resonance wavelength to be tunable in the range from UVA to IR. These extrinsic chiral metamaterials only exhibit significant chiroptical response at non-normal angles of incidence. This intrinsic property enables the probing of both enantoimeric structures on the same sample, by inverting the tilt of the sample relative to the normal angle. In biosensor applications this allows for more precise, cheap and commercialized devices. As a proof of concept two different molecules were used to probe the sensitivity of the metamaterials. These proved the applicability to sense proteins through non-specific adsorption on the metamaterial surface or through functionalized surfaces to increase the sensing sensitivity. Besides increasing the sensing sensitivity, these metamaterials may also be commercialized and find applications in surface-enhanced IR spectroscopy, terahertz generation and terahertz circular dichroism spectroscopy.

  13. Asymmetric Aldol Reaction Catalyzed by L-Proline and Achiral Thiourea Fluoroboric Acid Salt

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Eun; Lee, Haney; Kim, Taek Hyeon [Chonnam National University, Gwangju (Korea, Republic of)

    2015-01-15

    Considering its ready availability and low cost, L-proline would be the first choice catalyst for preparing aldol adducts with high diastereo- and enantioselectivity. However, proline presents some major drawbacks, including poor performance in direct aldol reactions with aromatic aldehydes, limited solubility, and reactivity in nonpolar organic solvents, and side reactions that make using high catalyst loadings necessary to reach satisfactory conversions. Therefore, numerous proline-modified organo catalysts such as prolinamides, proline thioamides, sulfonamides, chiral amines, and organic salts have been designed for direct aldol reactions. An alternative is to add a readily available additive to the reactions containing proline. This last approach is clearly advantageous in avoiding tedious chemical syntheses of organo catalysts and would ultimately allow the construction of libraries of catalyst protocols by simply changing the additive. Acid additives can influence the outcome of enamine mediated reactions; however, only a few screening studies of acid additions to thiourea organo catalysts are available in the literature. The reaction between cyclohexanone and 4-nitrobenzaldehyde was selected as a standard model reaction for screening of more effective acid additives to thiourea.

  14. A New Achiral Linker Reagent for the Incorporation of Multiple Amino Groups Into Oligonucleotides

    DEFF Research Database (Denmark)

    1997-01-01

    with the linker in conventional phosphoamidite or H-phosphonate DNA syntheses. Directly, or via a post modification step, an oligonucleotide is labelled with one or more reporter moieties, e.g. dansyl (5-dimethylamino)-1-naphthalenesulfonyl), biotin, digoxigenin, DOXYL (N-oxyl-4,4-dimethyloxazolidine), PROXYL (N......, to a method for preparing a labelled oligonucleotide, and to the use of the labelled oligonucleotide as hybridisation probe, in polymerase chain reactions (PCR), in nucleic acid sequencing, in cloning recombinant DNA and $i(in vitro) mutagenesis....

  15. Alternating twist structures formed by electroconvection in the nematic phase of an achiral bent-core molecule.

    Science.gov (United States)

    Tanaka, Shingo; Dhara, Surajit; Sadashiva, B K; Shimbo, Yoshio; Takanishi, Yoichi; Araoka, Fumito; Ishikawa, Ken; Takezoe, Hideo

    2008-04-01

    We report an unusual electroconvection in the nematic phase of a bent-core liquid crystal. In a voltage-frequency diagram, two frequency regions exhibiting prewavy stripe patterns were found, as reported by Wiant We found that these stripes never show extinction dark when cells were rotated under crossed polarizers. Based on the color interchange in between neighboring stripes by the rotation of the cells or an analyzer, twisted molecular orientation is suggested; i.e., the directors are alternately twisted from the top to the bottom surfaces with a pretilt angle in adjacent stripes, which is an analogue of the twisted (splayed) structure observed in surface-stabilized ferroelectric liquid crystal cells. The transmittance spectra calculated using the 4x4 matrix method from the model structure are consistent with the experimental observation.

  16. Understanding the role of surface plasmon polaritons in two-dimensional achiral nanohole arrays for polarization conversion

    CERN Document Server

    Cao, Z L; Zhang, Z Q; Chan, C T; Ong, H C

    2016-01-01

    We have studied the dependence of the rotation angle and ellipticity on the sample orientation and incident polarization from metallic nanohole arrays. The arrays have four-fold symmetry and thus do not possess any intrinsic chirality. We elucidate the role of surface plasmon polaritons (SPPs) in determining the extrinsic chirality and we verify the results by using finite-difference time-domain simulation. Our results have indicated the outgoing reflection arises from the interference between the nonresonant background, which preserves the input polarization, and the SPP radiation damping, which is linearly polarized but carries a different polarization defined by the vectorial field of SPPs. More importantly, the interference manifests various polarization states ranging from linear to elliptical across the SPP resonance. We analytically formulate the outgoing waves based on temporal coupled mode theory (CMT) and the results agree well with the experiment and simulation. From CMT, we find the polarization c...

  17. Discovery-Oriented Approach To Organic Synthesis: Tandem Aldol Condensation-Michael Addition Reactions. Identifying Diastereotopic Hydrogens in an Achiral Molecule by NMR Spectroscopy

    Science.gov (United States)

    Wachter-Jurcsak, Nanette; Reddin, Kendra

    2001-09-01

    We have found a beautiful example of anisochrony of diastereotopic acyclic methylene hydrogens in a symmetric diketone, synthesized by techniques traditionally performed in an introductory organic laboratory course. Synthesis of the diketone is high-yielding and easy to carry out, and the products can be directly isolated with a good degree of purity with no need of further manipulation. The reaction can be accomplished in a single laboratory session.

  18. 4-Oxocyclo-hexa-neacetic acid: catemeric hydrogen bonding and spontaneous resolution of a single conformational enanti-omer in an achiral ∊-keto acid.

    Science.gov (United States)

    Barcon, Alan; Brunskill, Andrew P J; Lalancette, Roger A; Thompson, Hugh W

    2010-01-01

    The asymmetric unit of the title compound, C(8)H(12)O(3), consists of a single conformational enanti-omer, which aggregates in the catemeric acid-to-ketone hydrogen-bonding mode [O⋯O = 2.682 (4) Å and O-H⋯O = 172 (6)°]. Four hydrogen-bonding chains of translationally related mol-ecules pass through the cell orthogonal to the 4(3) screw axis along c, alternating in the 110 and the 10 direction, with alignment with respect to this axis of + + - -. Successive chains are rotated by 90° around the c axis. One C-H⋯O=C close contact, involving the carboxyl group, exists. PMID:21587559

  19. 4-Oxocyclohexaneacetic acid: catemeric hydrogen bonding and spontaneous resolution of a single conformational enantiomer in an achiral ∊-keto acid

    Directory of Open Access Journals (Sweden)

    Hugh W. Thompson

    2010-10-01

    Full Text Available The asymmetric unit of the title compound, C8H12O3, consists of a single conformational enantiomer, which aggregates in the catemeric acid-to-ketone hydrogen-bonding mode [O...O = 2.682 (4 Å and O—H...O = 172 (6°]. Four hydrogen-bonding chains of translationally related molecules pass through the cell orthogonal to the 43 screw axis along c, alternating in the 110 and the overline{1}10 direction, with alignment with respect to this axis of + + − −. Successive chains are rotated by 90° around the c axis. One C—H...O=C close contact, involving the carboxyl group, exists.

  20. Association of two single-isomer anionic CD in NACE for the chiral and achiral separation of fenbendazole, its sulphoxide and sulphone metabolites: application to their determination after in vitro metabolism.

    Science.gov (United States)

    Rousseau, Anne; Gillotin, Florian; Chiap, Patrice; Crommen, Jacques; Fillet, Marianne; Servais, Anne-Catherine

    2010-05-01

    A NACE method was developed for the separation of fenbendazole (FBZ), a prochiral drug giving rise to chiral (oxfendazole or OFZ) and nonchiral (FBZ sulphone or FBZSO(2)) metabolites. First, the effect of the nature and the concentration of CD as well as that of the acidic BGE on the enantiomeric separation of OFZ were studied. OFZ enantiomers were completely resolved using a BGE made up of 10 mM ammonium formate and 0.5 M TFA in methanol containing 10 mM heptakis(2,3-di-O-acetyl-6-O-sulfo)-beta-CD and 10 mM heptakis(2,3-di-O-methyl-6-O-sulfo)-beta-CD. Moreover, the NACE method was found to be particularly well suited to the simultaneous determination of FBZ, OFZ enantiomers, and FBZSO(2). Thiabendazole was selected as an internal standard. The CD-NACE potential was then evaluated for in vitro metabolism studies using FBZ as a model case. The OFZ enantiomers and FBZSO(2) could be detected after incubation of FBZ in the phenobarbital-induced male rat liver microsomes systems.

  1. 4-Oxocyclo­hexa­neacetic acid: catemeric hydrogen bonding and spontaneous resolution of a single conformational enanti­omer in an achiral ∊-keto acid

    Science.gov (United States)

    Barcon, Alan; Brunskill, Andrew P. J.; Lalancette, Roger A.; Thompson, Hugh W.

    2010-01-01

    The asymmetric unit of the title compound, C8H12O3, consists of a single conformational enanti­omer, which aggregates in the catemeric acid-to-ketone hydrogen-bonding mode [O⋯O = 2.682 (4) Å and O—H⋯O = 172 (6)°]. Four hydrogen-bonding chains of translationally related mol­ecules pass through the cell orthogonal to the 43 screw axis along c, alternating in the 110 and the 10 direction, with alignment with respect to this axis of + + − −. Successive chains are rotated by 90° around the c axis. One C—H⋯O=C close contact, involving the carboxyl group, exists. PMID:21587559

  2. Interplay of metalloligand and organic ligand to tune micropores within isostructural mixed-metal organic frameworks (M'MOFs) for their highly selective separation of chiral and achiral small molecules

    NARCIS (Netherlands)

    M. C. Das; Q. Guo; Y. He; J. Kim; C.-G. Zhao; K. Hong; S. Xiang; Z. Zhang; K. M. Thomas; R. Krishna; B. Chen

    2012-01-01

    Four porous isostructural mixed-metal-organic frameworks (M′MOFs) have been synthesized and structurally characterized. The pores within these M′MOFs are systematically tuned by the interplay of both the metalloligands and organic ligands which have enabled us not only to direct their highly selecti

  3. Synthesis and characterization of mixed ligand chiral nanoclusters

    OpenAIRE

    Güven, Zekiye Pelin; Guven, Zekiye Pelin; Üstbaş, Burçin; Ustbas, Burcin; Harkness, Kellen M.; Coşkun, Hikmet; Coskun, Hikmet; Joshi, Chakra P.; Besong, Tabot M. D.; Stellacci, Francesco; Bakr, Osman M.; Akbulut, Özge; Akbulut, Ozge

    2015-01-01

    Chiral mixed ligand silver nanoclusters were synthesized in the presence of a chiral and an achiral ligand. The ratio of the ligands was changed to track the formation of these clusters. While the chiral ligand lead to nanoparticles, Presence of the achiral ligand induced the formation of nanoclusters with chiral properties.

  4. Synthesis and characterization of mixed ligand chiral nanoclusters

    KAUST Repository

    Guven, Zekiye P.

    2016-06-22

    Chiral mixed ligand silver nanoclusters were synthesized in the presence of a chiral and an achiral ligand. While the chiral ligand led mostly to the formation of nanoparticles, the presence of the achiral ligand drastically increased the yield of nanoclusters with enhanced chiral properties. © 2016 The Royal Society of Chemistry.

  5. Asymmetric autocatalysis induced by meteoritic amino acids with hydrogen isotope chirality† †This article is part of a ChemComm ‘Catalysis in Organic Synthesis’ web-theme issue showcasing high quality research in organic chemistry. Please see our website (http://www.rsc.org/chemcomm/organicwebtheme2009) to access the other papers in this issue. ‡ ‡Electronic supplementary information (ESI) available: Procedures for the asymmetric autocatalysis in the presence of 1 and 2, the preparation of enantiomers of 1 and 2, and the determination of the enantiomeric purity of 1 and 2. See DOI: 10.1039/b908754k Click here for additional data file.

    Science.gov (United States)

    Kawasaki, Tsuneomi; Shimizu, Masako; Nishiyama, Daisuke; Ito, Masateru; Ozawa, Hitomi

    2009-01-01

    Achiral meteoritic amino acids, glycine and α-methylalanine, with hydrogen isotope (D/H) chirality, acted as the source of chirality in asymmetric autocatalysis with amplification of ee to afford highly enantioenriched 5-pyrimidyl alkanols. PMID:19597604

  6. Catalytic Enantioselective Olefin Metathesis in Natural Product Synthesis. Chiral Metal-Based Complexes that Deliver High Enantioselectivity and More

    Science.gov (United States)

    Malcolmson, Steven J.; Meek, Simon J.; Zhugralin, Adil R.

    2012-01-01

    Chiral olefin metathesis catalysts enable chemists to access enantiomerically enriched small molecules with high efficiency; synthesis schemes involving such complexes can be substantially more concise than those that would involve enantiomerically pure substrates and achiral Mo alkylidenes or Ru-based carbenes. The scope of research towards design and development of chiral catalysts is not limited to discovery of complexes that are merely the chiral versions of the related achiral variants. A chiral olefin metathesis catalyst, in addition to furnishing products of high enantiomeric purity, can offer levels of efficiency, product selectivity and/or olefin stereoselectivity that are unavailable through the achiral variants. Such positive attributes of chiral catalysts (whether utilized in racemic or enantiomerically enriched form) should be considered as general, applicable to other classes of transformations. PMID:19967680

  7. Symmetry Breaking in Chiral Ionic Liquids Evidenced by Vibrational Optical Activity.

    Science.gov (United States)

    Oulevey, Patric; Luber, Sandra; Varnholt, Birte; Bürgi, Thomas

    2016-09-19

    Ionic liquids (ILs) are receiving increasing interest for their use in synthetic laboratories and industry. Being composed of charged entities, they show a complex and widely unexplored dynamic behavior. Chiral ionic liquids (CILs) have a high potential as solvents for use in asymmetric synthesis. Chiroptical methods, owing to their sensitivity towards molecular conformation, offer unique possibilities to study the structure of these chiral ionic liquids. Raman optical activity proved particularly useful to study ionic liquids composed of amino acids and the achiral 1-ethyl-3-methylimidazolium counterion. We could substantiate, supported by selected theoretical methods, that the achiral counterion adopts an overall chiral conformation in the presence of chiral amino acid ions. These findings suggest that in the design of chiral ionic liquids for asymmetric synthesis, the structure of the achiral counter ion also has to be carefully considered.

  8. Dual-band polarization conversion based on non-twisted Q-shaped metasurface

    Science.gov (United States)

    Cao, Hailin; Liang, Jianshuo; Wu, Xiaodong; Pi, Yuwei; Xu, Hang; Liu, Junjie; Meng, Zhenya; Zhang, Yongliang

    2016-07-01

    In this paper, we theoretically and experimentally report an achiral dual-band metasurface with linear birefringence. The unit cell of the achiral metasurface consists of non-twisted Q-shape metallic ring resonators with a stub breaking the rotational symmetry. Moreover, due to the presence of the stub, we find the proposed metasurface emits dual-band circularly polarized wave with low transmission loss and high polarization extinction for a normal incident y-direction linearly polarized wave. We also systematically investigate the dependence of the electromagnetic response of the proposed structure on the geometric parameters. It is hoped that the proposed simple, easily fabricated model of achiral metasurface can be used in further polarization control applications

  9. Dinucleating Ligand Platforms Supporting Indium and Zinc Catalysts for Cyclic Ester Polymerization.

    Science.gov (United States)

    Kremer, Alexandre B; Osten, Kimberly M; Yu, Insun; Ebrahimi, Tannaz; Aluthge, Dinesh C; Mehrkhodavandi, Parisa

    2016-06-01

    The synthesis of the first alkoxide-bridged indium complex supported by a chiral dinucleating ligand platform (1), along with its zinc analogue (2), is reported. Both complexes are synthesized in a one-pot reaction starting from a chiral dinucleating bis(diamino)phenolate ligand platform, sodium ethoxide, and respective metal salts. The dinucleating indium analogue (7) based on an achiral ligand backbone is also reported. Indium complexes bearing either the chiral or achiral ligand catalyze the ring-opening polymerization of racemic lactide (rac-LA) to afford highly heterotactic poly(lactic acid) (PLA; Pr > 0.85). The indium complex bearing an achiral ligand affords essentially atactic PLA from meso-LA. The role of the dinucleating ligand structure in catalyst synthesis and polymerization activity is discussed. PMID:27187767

  10. Principles of self-assembly of helical pores from dendritic dipeptides

    OpenAIRE

    Percec, Virgil; Dulcey, Andrés E.; Peterca, Mihai; Ilies, Monica; Nummelin, Sami; Sienkowska, Monika J.; Heiney, Paul A.

    2006-01-01

    The self-assembly of the dendritic dipeptides (4-3,4-3,5)nG2-CH2-Boc-l-Tyr-l-Ala-OMe and their achiral dendritic alcohol (4-3,4-3,5)nG2-CH2OH precursors, both with n = 1–16, where n represents the number of methylenic units in the alkyl groups of the dendron, are reported. All chiral dendritic dipeptides and achiral dendritic alcohols self-assemble into helical porous columns that are stable in both solution and solid state. The pore diameter (Dpore) of the columns self-assembled from dendrit...

  11. Organocatalytic cascade aza-Michael/hemiacetal reaction between disubstituted hydrazines and α,β-unsaturated aldehydes: Highly diastereo- and enantioselective synthesis of pyrazolidine derivatives

    Directory of Open Access Journals (Sweden)

    Zhi-Cong Geng

    2012-10-01

    Full Text Available The catalytic synthesis of nitrogen-containing heterocycles is of great importance to medicinal and synthetic chemists, and also a challenge for modern chemical methodology. In this paper, we report the synthesis of pyrazolidine derivatives through a domino aza-Michael/hemiacetal sequence with chiral or achiral secondary amines as organocatalysts. Thus, a series of achiral pyrazolidine derivatives were obtained with good yields (up to 90% and high diastereoselectivities (>20:1 with pyrrolidine as an organocatalyst, and enantioenriched pyrazolidines are also achieved with good results (up to 86% yield, >10/1 regioselectivity, >20:1 dr, 99% ee in the presence of (S-diphenylprolinol trimethylsilyl ether catalyst.

  12. Understanding complex chiral plasmonics

    Science.gov (United States)

    Duan, Xiaoyang; Yue, Song; Liu, Na

    2015-10-01

    Chiral nanoplasmonics exhibits great potential for novel nanooptical devices due to the generation of a strong chiroptical response within nanoscale metallic structures. Recently, a number of different approaches have been utilized to create chiral nanoplasmonic structures. However, particularly for tailoring nanooptical chiral sensing devices, the understanding of the resulting chiroptical response when coupling chiral and achiral structures together is crucial and has not been completely understood to date. Here, we present a thorough and step-by-step experimental study to understand the intriguing chiral-achiral coupling scheme. We set up a hybrid plasmonic system, which bears resemblance to the `host-guest' system in supramolecular chemistry to analyze and explain the complex chiral response both at the chiral and achiral plasmonic resonances. We also provide an elegant and simple analytical model, which can describe, predict, and comprehend the chiroptical spectra in detail. Our study will shed light on designing well-controlled chiral-achiral coupling platforms for reliable chiral sensing.Chiral nanoplasmonics exhibits great potential for novel nanooptical devices due to the generation of a strong chiroptical response within nanoscale metallic structures. Recently, a number of different approaches have been utilized to create chiral nanoplasmonic structures. However, particularly for tailoring nanooptical chiral sensing devices, the understanding of the resulting chiroptical response when coupling chiral and achiral structures together is crucial and has not been completely understood to date. Here, we present a thorough and step-by-step experimental study to understand the intriguing chiral-achiral coupling scheme. We set up a hybrid plasmonic system, which bears resemblance to the `host-guest' system in supramolecular chemistry to analyze and explain the complex chiral response both at the chiral and achiral plasmonic resonances. We also provide an elegant

  13. Supramolecular Chemistry: Induced Circular Dichroism to Study Host-Guest Geometry

    Science.gov (United States)

    Mendicuti, Francisco; Gonzalez-Alvarez, Maria Jose

    2010-01-01

    In this laboratory experiment, students obtain information about the structure of a host-guest complex from the interpretation of circular dichroism measurements. The value and sign of the induced circular dichroism (ICD) on an achiral chromophore guest when it complexes with a cyclodextrin can be related to the guest penetration and its…

  14. Rapid procedure for the resolution of racemic gossypol

    OpenAIRE

    Sampath, DS; Balaram, P

    1986-01-01

    Racemic gossypol [(±)-I] was resolved rapidly and efficiently by high-performance liq. chromatog. sepn. of the diastereoisomeric adducts of (±)-I with L-phenylalaninol on an achiral, reversed-phase, C18 column. The sepd. adducts were hydrolyzed by 2M HCl to give (+)- and (-)-I with 50-60% recovery.

  15. Synthesis and complexation characteristics of phenanthroline and bipyridine diols

    NARCIS (Netherlands)

    Koning, B.; Boer, J.W. de; Meetsma, A.; Kellogg, R.M.

    2004-01-01

    Neocuproine (2,9-dimethyl-1,10-phenanthroline) 1 was converted to achiral and chiral tetradentate phenanthroline diols 3a-c by addition to benzophenone, adamantanone and camphor, respectively. Analogously 6,6'-dimethyl-2,2'-bipyridine 2 was converted to diol 7a on base-induced addition to benzopheno

  16. A different approach to enantioselective organic synthesis

    DEFF Research Database (Denmark)

    Lennartson, Anders; Olsson, Susanne; Sundberg, Jonas;

    2009-01-01

    Voilà, optical activity: Both enantiomers of 1-chloroindene have been synthesized in high selectivity from solely achiral starting materials, and without using optically active catalysts (see scheme). These symmetry-breaking syntheses provide a proof-of-concept for a new approach to asymmetric sy...... synthesis. NCS=N-chlorosuccinimide....

  17. Synthesis and Resolution of the Atropisomeric 1,1'-Bi-2-Naphthol: An Experiment in Organic Synthesis and 2-D NMR Spectroscopy

    Science.gov (United States)

    Mak, Kendrew K. W.

    2004-01-01

    NMR spectroscopy is presented. It is seen that the experiment regarding the synthesis and resolution of 1,1'-Bi-2-naphtol presents a good experiment for teaching organic synthesis and NMR spectroscopy and provides a strategy for obtaining enantiopure compounds from achiral starting materials.

  18. Metabolic reprogramming of periwinkle plant culture

    OpenAIRE

    Runguphan, Weerawat; O’Connor, Sarah E.

    2009-01-01

    We transformed an alkaloid biosynthetic gene with reengineered substrate specificity into Catharanthus roseus. The resulting transgenic plant cell culture produced a variety of unnatural alkaloid compounds when cocultured with simple, achiral, commercially available precursors that the reengineered enzyme was designed to accept. This work demonstrates the power of genetic engineering to retailor the structures of complex alkaloid natural products in plant culture.

  19. One-Pot Catalysis Using a Chiral Iridium Complex/Brønsted Base: Catalytic Asymmetric Synthesis of Catalponol.

    Science.gov (United States)

    Suzuki, Takeyuki; Ismiyarto; Ishizaka, Yuka; Zhou, Da-Yang; Asano, Kaori; Sasai, Hiroaki

    2015-11-01

    Tandem asymmetric hydrogen transfer oxidation/aldol condensation under relay catalysis of a chiral iridium complex/achiral Brønsted base binary system is described for the synthesis of α-benzylidene-γ-hydroxytetralones with high ee's. A two-step synthesis of catalponol was achieved using this sequential methodology together with regio- and stereoselective hydroboration. PMID:26496409

  20. Smectic C chevrons in nanocylinders

    Energy Technology Data Exchange (ETDEWEB)

    Lefort, R., E-mail: ronan.lefort@univ-rennes1.fr; Morineau, D. [Institut de Physique de Rennes, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes cedex (France); Jean, F. [Institut de Physique de Rennes, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes cedex (France); Institut NEEL, CNRS and Université Joseph Fourier, 38042 Grenoble (France); Noirez, L. [Laboratoire Léon Brillouin (CEA-CNRS) CE Saclay, 91191 Gif-sur-Yvette (France); Ndao, M. [Institut de Physique de Rennes, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes cedex (France); Institut de Chimie de Clermont-Ferrand (ICCF)—UMR-CNRS 6296, Université Blaise Pascal, Campus des Cézeaux, 63171 Aubiere cedex (France); Cerclier, C. V. [Institut de Physique de Rennes, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes cedex (France); Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2 rue de la Houssiniere BP32229, 44322 Nantes cedex 3 (France)

    2014-11-17

    The structure of an achiral smectic-C liquid crystal confined in nanocylinders with a planar surface anchoring is studied by small angle neutron scattering. We observe an invariant alignment of the nematic director with the pore axis, that promotes an original chevron structure with revolution symmetry.

  1. Controlled chiral electrochromism of polyoxometalates incorporated in supramolecular complexes.

    Science.gov (United States)

    Zhang, Bin; Guan, Weiming; Zhang, Simin; Li, Bao; Wu, Lixin

    2016-04-01

    A three-component supramolecular system was constructed by combining host-guest recognition and electrostatic interaction for realization of induced circular dichroism of achiral polyanionic clusters in aqueous solution, while the induced chiral heteropoly blue was built and switched off by controlling the redox of the inorganic component via electrochemistry. PMID:27002653

  2. A General Approach to the Basiliolide/Transtaganolide Natural Products: Total Syntheses of Basiliolide B, epi-8-Basiliolide B, Transtaganolide C, and Transtaganolide D

    KAUST Repository

    Nelson, Hosea M.

    2011-03-25

    (Figure Presented) In a flash: The total synthesis of transtaganolide and basiliolide natural products is achieved in three steps from achiral, monocyclic esters (see scheme). Featured in the syntheses are an Ireland-Claisen/Diels- Alder cascade and a novel methoxyacetylide coupling/cyclization sequence. © 2011 Wiley-VCH Verlag GmbH & Co. KGaA.

  3. Enantioselective Evans-Tishchenko Reduction of b-Hydroxyketone Catalyzed by Lithium Binaphtholate

    Directory of Open Access Journals (Sweden)

    Makoto Nakajima

    2011-06-01

    Full Text Available Lithium diphenylbinaphtholate catalyzed the enantioselective Evans-Tishchenko reduction of achiral b-hydroxyketones to afford monoacyl-protected 1,3-diols with high stereoselectivities. In the reaction of racemic b-hydroxyketones, kinetic optical resolution occurred in a highly stereoselective manner.

  4. Chiral light intrinsically couples to extrinsic/pseudo-chiral metasurfaces made of tilted gold nanowires

    Science.gov (United States)

    Belardini, Alessandro; Centini, Marco; Leahu, Grigore; Hooper, David C.; Li Voti, Roberto; Fazio, Eugenio; Haus, Joseph W.; Sarangan, Andrew; Valev, Ventsislav K.; Sibilia, Concita

    2016-08-01

    Extrinsic or pseudo-chiral (meta)surfaces have an achiral structure, yet they can give rise to circular dichroism when the experiment itself becomes chiral. Although these surfaces are known to yield differences in reflected and transmitted circularly polarized light, the exact mechanism of the interaction has never been directly demonstrated. Here we present a comprehensive linear and nonlinear optical investigation of a metasurface composed of tilted gold nanowires. In the linear regime, we directly demonstrate the selective absorption of circularly polarised light depending on the orientation of the metasurface. In the nonlinear regime, we demonstrate for the first time how second harmonic generation circular dichroism in such extrinsic/pseudo-chiral materials can be understood in terms of effective nonlinear susceptibility tensor elements that switch sign depending on the orientation of the metasurface. By providing fundamental understanding of the chiroptical interactions in achiral metasurfaces, our work opens up new perspectives for the optimisation of their properties.

  5. Anisotropic and dispersive wave propagation within strain-gradient framework

    CERN Document Server

    Rosi, Giuseppe

    2016-01-01

    In this paper anisotropic and dispersive wave propagation within linear strain-gradient elasticity is investigated. This analysis reveals significant features of this extended theory of continuum elasticity. First, and contrarily to classical elasticity, wave propagation in hexagonal (chiral or achiral) lattices becomes anisotropic as the frequency increases. Second, since strain-gradient elasticity is dispersive, group and energy velocities have to be treated as different quantities. These points are first theoretically derived, and then numerically experienced on hexagonal chiral and achiral lattices. The use of a continuum model for the description of the high frequency behavior of these microstructured materials can be of great interest in engineering applications, allowing problems with complex geometries to be more easily treated.

  6. Multicomponent synthesis of unsymmetrical unsaturated N-heterocyclic carbene precursors and their related transition-metal complexes

    KAUST Repository

    Queval, Pierre

    2013-12-04

    A low-cost, modular, and easily scalable multicomponent procedure affording access in good yields and excellent selectivity (up to 93 %) to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl-imidazolium salts is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron donor ability, high steric discrimination, and modular steric demand. A low-cost, modular, and easily scalable multicomponent procedure, affording access to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl- imidazolium salts in good yields and excellent selectivities, is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron-donor ability, high steric discrimination, and modular steric demand. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Low symmetry tetrahedral nematic liquid crystal phases: Ambidextrous chirality and ambidextrous helicity.

    Science.gov (United States)

    Pleiner, Harald; Brand, Helmut R

    2014-02-01

    We discuss the symmetry properties as well as the dynamic behavior of various non-polar nematic liquid crystal phases with tetrahedral order. We concentrate on systems that show biaxial nematic order coexisting with octupolar (tetrahedral) order. Non-polar examples are phases with D2 and S4 symmetries, which can be characterized as biaxial nematics lacking inversion symmetry. It is this combination that allows for new features in the statics and dynamics of these phases. The D2-symmetric phase is chiral, even for achiral molecules, and shows ambidextrous chirality in all three preferred directions. The achiral S4-symmetric phase allows for ambidextrous helicity, similar to the higher-symmetric D2d-symmetric phase. Such phases are candidates for nematic phases made from banana-shaped molecules.

  8. Mechanically generated surface chirality at the nanoscale.

    Science.gov (United States)

    Ferjani, Sameh; Choi, Yoonseuk; Pendery, Joel; Petschek, Rolfe G; Rosenblatt, Charles

    2010-06-25

    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. PMID:20867414

  9. Emergence of Chirality from Isotropic Interactions of Three Length Scales

    Science.gov (United States)

    Mkhonta, S. K.; Elder, K. R.; Huang, Zhi-Feng

    2016-05-01

    Chirality is known to play a pivotal role in determining material properties and functionalities. However, it remains a great challenge to understand and control the emergence of chirality and the related enantioselective process particularly when the building components of the system are achiral. Here we explore the generic mechanisms driving the formation of two-dimensional chiral structures in systems characterized by isotropic interactions and three competing length scales. We demonstrate that starting from isotropic and rotationally invariant interactions, a variety of chiral ordered patterns and superlattices with anisotropic but achiral units can self-assemble. The mechanisms for selecting specific states are related to the length-scale coupling and the selection of resonant density wave vectors. Sample phase diagrams and chiral elastic properties are identified. These findings provide a viable route for predicting chiral phases and selecting the desired handedness.

  10. A Helical Polyphenylacetylene Having Amino Alcohol Moieties Without Chiral Side Groups as a Chiral Ligand for the Asymmetric Addition of Diethylzinc to Benzaldehyde.

    Science.gov (United States)

    Liu, Lijia; Long, Qing; Aoki, Toshiki; Zhang, Geng; Kaneko, Takashi; Teraguchi, Masahiro; Zhang, Chunhong; Wang, Yudan

    2015-08-01

    One-handed helical polyphenylacetylenes having achiral amino alcohol moieties, but no chiral side groups, were synthesized by the helix-sense-selective copolymerization of an achiral phenylacetylene having an amino alcohol side group with a phenylacetylene having two hydroxyl groups. Since the resulting helical copolymers were successfully utilized as chiral ligands for the enantioselective alkylation of benzaldehyde with diethylzinc, we can conclude that the main-chain chirality based on the one-handed helical conformation is useful for the chiral catalysis of an asymmetric reaction for the first time. The enantioselectivities of the reaction were controlled by the optical purities of the helical polymer ligands. In addition, the polymer ligands could be easily recovered by precipitation after the reaction.

  11. Explanation for the Emergence of a Single Chiral Solid State during Attrition-Enhanced Ostwald Ripening: Survival of the Fittest

    OpenAIRE

    Noorduin, Wim L.; Meekes, Hugo; Bode, Arno A.C.; Enckevort, Willem J.P. van; Kaptein, Bernard; Kellogg, Richard M.; Vlieg, Elias

    2008-01-01

    The overabundant occurrence of single-handed chiral molecules in living systems has inspired scientists for well more than a century. A route to the evolution of a single chiral solid phase, using abrasive grinding of the crystals in contact with a saturated solution, has been demonstrated for the achiral compound NaClO3 crystallizing in a chiral space group and, recently, for an intrinsically chiral amino acid derivative. In order to obtain insight in the complex processes involved in these ...

  12. Synthesizing skyrmion bound pairs in Fe-Gd thin films

    Science.gov (United States)

    Lee, J. C. T.; Chess, J. J.; Montoya, S. A.; Shi, X.; Tamura, N.; Mishra, S. K.; Fischer, P.; McMorran, B. J.; Sinha, S. K.; Fullerton, E. E.; Kevan, S. D.; Roy, S.

    2016-07-01

    We show that properly engineered amorphous Fe-Gd alloy thin films with perpendicular magnetic anisotropy exhibit bound pairs of like-polarity, opposite helicity skyrmions at room temperature. Magnetic mirror symmetry planes present in the stripe phase, instead of chiral exchange, determine the internal skyrmion structure and the net achirality of the skyrmion phase. Our study shows that stripe domain engineering in amorphous alloy thin films may enable the creation of skyrmion phases with technologically desirable properties.

  13. Asymmetric Synthesis of β, γ-β-Hydroxyl-γ-butyrolactones

    Institute of Scientific and Technical Information of China (English)

    WANG Jin-Xin; ZHANG Chao-Xin; LI Ying

    2003-01-01

    @@ Chiral β-hydroxyl-γ-butyrolactones have attracted substantial interest in recent years due to their presence inmany strongly active natural products having antitumor, fungicidal, anti-inflammatory activity, and their use as important precursors in natural product synthesis. [1] In the course of the total synthesis of the natural product Tuxpano lide ,[2] we found a concise and efficient strategy on the stereocontrolled synthesis of β-hydroxyl-γ-butyrolactonederivatives from cheap and achiral starting material.

  14. Synthesis, Chiroptical Behavior, and Sensing of Carboxylic Acid Functionalized.Poly(phenylene ethynylene-alt-bithiophene)s

    OpenAIRE

    Vandeleene, Steven; Verswyvel, Michiel; Verbiest, Thierry; Koeckelberghs, Guy

    2010-01-01

    Several poly(phenylene ethynylene-alt-bithiophene)s with (chiral) nonfunctionalized substituents were synthesized with a variable phenylene ethynylene (PE) spacer length (up to 4 repeating units). The chiroptical behavior was evaluated with UV vis and circular dichroism (CD) spectroscopy, revealing a highly solvent-sensitive aggregate formation. Based on this high sensitivity, both chiral and achiral carboxylic acid functionalized analogues were prepared, of which the length of the spacer con...

  15. A Simple Method for the Determination of Enantiomeric Excess and Identity of Chiral Carboxylic Acids

    OpenAIRE

    Joyce, Leo A.; Maynor, Marc S.; Dragna, Justin M.; da Cruz, Gabriella M.; Lynch, Vincent M.; Canary, James W.; Eric V. Anslyn

    2011-01-01

    The association between an achiral copper(II) host (1) and chiral carboxylate guests was studied using exciton-coupled circular dichroism (ECCD). Enantiomeric complexes were created upon binding of the enantiomers of the carboxylate guests to the host, and the sign of the resultant CD signal allowed for determination of the configuration of the studied guest. The difference in magnitudes and shapes of the CD signals, in conjunction with linear discriminant analysis (LDA), allowed for the iden...

  16. Probing the "additive effect" in the proline and proline hydroxamic acid catalyzed asymmetric addition of nitroalkanes to cyclic enones.

    Science.gov (United States)

    Hanessian, Stephen; Govindan, Subramaniyan; Warrier, Jayakumar S

    2005-11-01

    The effect of chirality and steric bulk of 2,5-disubstituted piperazines as additives in the conjugate addition of 2-nitropropane to cyclohexenone, catalyzed by l-proline, was investigated. Neither chirality nor steric bulk affects the enantioselectivity of addition, which gives 86-93% ee in the presence of achiral and chiral nonracemic 2,5-disubstituted piperazines. Proline hydroxamic acid is shown for the first time to be an effective organocatalyst in the same Michael reaction. PMID:16189834

  17. On tame embeddings of solenoids into 3-space

    OpenAIRE

    Jiang, Boju; Wang, Shicheng; Zheng, Hao; Zhou, Qing

    2006-01-01

    Solenoids are ``inverse limits'' of the circle, and the classical knot theory is the theory of tame embeddings of the circle into the 3-space. We give some general study, including certain classification results, of tame embeddings of solenoids into the 3-space as the ``inverse limits'' of the tame embeddings of the circle. Some applications are discussed. In particular, there are ``tamely'' embedded solenoids $\\Sigma\\subset \\R^3$ which are strictly achiral. Since solenoids are non-planar, th...

  18. An epistemological note on chirality

    International Nuclear Information System (INIS)

    The terms ''chiral'' and ''achiral'' are sharply defined when applied to geometric figures or models. The same terms are also commonly used to refer to the real systems to which these models have been adjoined. e.g., molecules, solvents, or reagents. Here, the terms are not sharply defined but depend upon conditions or measurement. The contrast between the geometric and operational usages is discussed in detail

  19. Design and Stereoselective Preparation of a New Class of Chiral Olefin Metathesis Catalysts and Application to Enantioselective Synthesis of Quebrachamine: Catalyst Development Inspired by Natural Product Synthesis

    Science.gov (United States)

    Sattely, Elizabeth S.; Meek, Simon J.; Malcolmson, Steven J.; Schrock, Richard R.; Hoveyda, Amir H.

    2010-01-01

    A total synthesis of the Aspidosperma alkaloid quebrachamine in racemic form is first described. A key catalytic ring-closing metathesis of an achiral triene is used to establish the all-carbon quaternary stereogenic center and the tetracyclic structure of the natural product; the catalytic transformation proceeds with reasonable efficiency through the use of existing achiral Ru or Mo catalysts. Ru- or Mo-based chiral olefin metathesis catalysts have proven to be inefficient and entirely nonselective in cases where the desired product is observed. In the present study, the synthesis route thus serves as a platform for the discovery of new olefin metathesis catalysts that allow for efficient completion of an enantioselective synthesis of quebrachamine. Accordingly, on the basis of mechanistic principles, stereogenic-at-Mo complexes bearing only monodentate ligands have been designed. The new catalysts provide significantly higher levels of activity than observed with the previously reported Ru- or Mo-based complexes. Enantiomerically enriched chiral alkylidenes are generated through diastereoselective reactions involving achiral Mo-based bispyrrolides and enantiomerically pure silyl-protected binaphthols. Such chiral catalysts initiate the key enantioselective ring-closing metathesis step in the total synthesis of quebrachamine efficiently (1 mol % loading, 22 °C, 1 h, >98% conversion, 84% yield) and with high selectivity (98:2 er, 96% ee). PMID:19113867

  20. Symmetrically tetrasubstituted [2.2]paracyclophanes: their systematization and regioselective synthesis of several types of bis-bifunctional derivatives by double electrophilic substitution.

    Science.gov (United States)

    Vorontsova, Natalia V; Rozenberg, Valeria I; Sergeeva, Elena V; Vorontsov, Evgenii V; Starikova, Zoya A; Lyssenko, Konstantin A; Hopf, Henning

    2008-01-01

    The possible number of chiral and achiral tetrasubstituted [2.2]paracyclophanes possessing different types of symmetry (C(2), C(i), C(s), C(2v), C(2h)) is evaluated and a unified independent trivial naming descriptor system is introduced. The reactivity and regioselectivity of the electrophilic substitution of the chiral pseudo-meta- and achiral pseudo-para-disubstituted [2.2]paracyclophanes are investigated in an approach suggested to be general for the synthesis of bis-bifunctional [2.2]paracyclophanes. The mono- and diacylation of chiral pseudo-meta-dihydroxy[2.2]paracyclophane 14 with acetylchloride occur ortho-regioselectively to produce tri- 22, 23 and symmetrically 21 tetrasubstituted acyl derivatives. The same reaction with benzoylchloride is neither regio-, nor chemoselective, and gives rise to a mixture of ortho-/para-, mono-/diacylated compounds 27-31. The double acylation of pseudo-meta-dimethoxy[2.2]paracyclophane 18 is completely para-regioselective. Electrophilic substitution of pseudo-meta-bis(methoxycarbonyl)[2.2]paracyclophane 20 regioselectively generates the pseudo-gem-substitution pattern. Formylation of this substrate produces the monocarbonyl derivatives 35 only, whereas the Fe-catalyzed bromination may be directed towards mono- 36 or disubstitution 37 products chemoselectively by varying the reactions conditions. The diacylation and dibromination reactions of the respective achiral diphenol 12 and bis(methoxycarbonyl) 40 derivatives of the pseudo-para-structure retain regioselectivities which are characteristic for their pseudo-meta-regioisomers. Imino ligands 26, 25, and 39, which were obtained from monoacyl- 22 and diacyldihydroxy[2.2]paracyclophanes 21, 38, are tested as chiral ligands in stereoselective Et(2)Zn addition to benzaldehyde producing 1-phenylpropanol with ee values up to 76 %.

  1. Impact of Chiral Bioanalytical Methods on the Bioequivalence of Ibuprofen Products Containing Ibuprofen Lysinate and Ibuprofen Base.

    Science.gov (United States)

    García-Arieta, Alfredo; Ferrero-Cafiero, Juan Manuel; Puntes, Montse; Gich, Ignasi; Morales-Alcelay, Susana; Tarré, Maite; Font, Xavier; Antonijoan, Rosa Maria

    2016-05-01

    The purpose was to assess the impact of the use of a chiral bioanalytical method on the conclusions of a bioequivalence study that compared two ibuprofen suspensions with different rates of absorption. A comparison of the conclusion of bioequivalence between a chiral method and an achiral approach was made. Plasma concentrations of R-ibuprofen and S-ibuprofen were determined using a chiral bioanalytical method; bioequivalence was tested for R-ibuprofen and for S-ibuprofen separately and for the sum of both enantiomers as an approach for an achiral bioanalytical method. The 90% confidence interval (90% CI) that would have been obtained with an achiral bioanalytical method (90% CI: Cmax: 117.69-134.46; AUC0 (t) : 104.75-114.45) would have precluded the conclusion of bioequivalence. This conclusion cannot be generalized to the active enantiomer (90% CI: Cmax : 103.36-118.38; AUC0 (t) : 96.52-103.12), for which bioequivalence can be concluded, and/or the distomer (90% CI: Cmax : 132.97-151.33; AUC0 (t) : 115.91-135.77) for which a larger difference was observed. Chiral bioanalytical methods should be required when 1) the enantiomers exhibit different pharmacodynamics and 2) the exposure (AUC or Cmax ) ratio of enantiomers is modified by a difference in the rate of absorption. Furthermore, the bioequivalence conclusion should be based on all enantiomers, since the distomer(s) might not be completely inert, in contrast to what is required in the current regulatory guidelines. In those cases where it is unknown if the ratio between enantiomers is modified by changing the rate of absorption, chiral bioanalytical methods should be employed unless enantiomers exhibit the same pharmacodynamics. Chirality 28:429-433, 2016. © 2016 Wiley Periodicals, Inc. PMID:27094918

  2. Field-induced transformations in the biaxial order of non-tilted phases in a bent-core smectic liquid crystal

    Science.gov (United States)

    Panarin, Y. P.; Nagaraj, Mamatha; Vij, J. K.; Keith, C.; Tschierske, C.

    2010-10-01

    The structural and electro-optic investigations of an achiral bent-core molecule in SmAPA phase, in which the polar directors in the neighboring layers are arranged anti-ferroelectrically, show that it undergoes transformation from one biaxial to another biaxial structure via a quasi-stable uniaxial structure on the application of the electric field. The non-continuous change in biaxiality is explained by an intermediate state in which the secondary directors in the neighboring layers are perpendicular to each other.

  3. The lowest optical phonon mode of small single-walled carbon nanotubes

    Directory of Open Access Journals (Sweden)

    CHEN Yan

    2015-08-01

    Full Text Available We demonstrate that the lowest optical phonon mode (LOM of the single-walled carbon nanotubes (SWCNTs is not always a E2g mode for achiral tube or E2 mode for chiral tube.For some small SWCNTs of which the periodic unit length along tube axis is larger than its circumference,the LOM is the standing wave along the tube axis.By the present numerical calculation based on empirical potential,we confirm that the energy of such an optical phonon mode is inversely proportional to the tube radius.

  4. A Multidisciplinary Approach Toward the Rapid and Preparative-Scale Biocatalytic Synthesis of Chiral Amino Alcohols: A Concise Transketolase-/omega-Transaminase-Mediated Synthesis of (2S,3S)-2-Aminopentane-1,3-diol

    DEFF Research Database (Denmark)

    Smith, M.E.B; Chen, B.H.; Hibbert, E.G;

    2010-01-01

    establishment of biocatalytic routes to chiral aminodiols taking the original synthesis of (2S,3S)-2-aminopentane-1,3-diol as a specific example. An engineered variant of Escherichi coli transketolase (D469T) was used for the initial asymmetric ynthesis of (3S)-1,3-dihydroxypentan-2-one from the achiral...... substrates propanal and hydroxypyruvate. A bioinformatics led strategy was then used to identify and clone an ω-transaminase from Chromobacterium violaceum (DSM30191) capable of converting the product of the transketolase-catalysed step to the required (2S,3S)-2-aminopentane-1,3-diol using isopropylamine...

  5. Inorganic positive uniaxial films fabricated by serial bideposition.

    Science.gov (United States)

    Hodgkinson, Ian; Wu, Qi Hong; De Silva, Lakshman; Arnold, Matthew

    2004-08-01

    The physical vapor deposition process of serial bideposition is adapted to the fabrication of uniaxial optical coatings. During the coating process the vapor impinges at an angle of incidence of about 70 on to the substrate, and a stepwise axial rotation with 90 increments causes a columnar structure to grow normal to the substrate. Symmetry considerations that follow from the choice of 90 for the stepwise increment ensure that the film is achiral and has negligible in-plane linear birefringence. Optical characterization techniques confirm that films of tantalum oxide, titanium oxide and zirconium oxide are positive uniaxial with ne -no in the range 0.10 to 0.14. PMID:19483917

  6. Question 1: Peptide Nucleic Acids and the Origin and Homochirality of Life

    Science.gov (United States)

    Nielsen, Peter E.

    2007-10-01

    The possibilities of pseudo peptide DNA mimics like PNA (peptide nucleic acid) having a role for the prebiotic origin of life prior to an RNA world is discussed. In particular a scenario is proposed in which protocells with an achiral genetic material through several generations stepwise is converted into a chiral genetic material, e.g., by incorporation of RNA units. Provided that a sufficiently large sequence space is occupied, a selection process based on catalytic function in which a single cell (first common ancestor) has a definite evolutionary advantage, selection of this cell would by contingency also lock it into homochirality.

  7. Question 1: Peptide nucleic acids and the origin and homochirality of life.

    Science.gov (United States)

    Nielsen, Peter E

    2007-10-01

    The possibilities of pseudo peptide DNA mimics like PNA (peptide nucleic acid) having a role for the prebiotic origin of life prior to an RNA world is discussed. In particular a scenario is proposed in which protocells with an achiral genetic material through several generations stepwise is converted into a chiral genetic material, e.g., by incorporation of RNA units. Provided that a sufficiently large sequence space is occupied, a selection process based on catalytic function in which a single cell (first common ancestor) has a definite evolutionary advantage, selection of this cell would by contingency also lock it into homochirality.

  8. Molecular chirality and the orbital angular momentum of light

    CERN Document Server

    Andrews, D L; Babiker, M; Andrews, David L.; Romero, Luciana C. Davila; Babiker, Mohamed

    2003-01-01

    Optical beams with a new and distinctive type of helicity have become the subject of much recent interest. While circularly polarised light comprises photons with spin angular momentum, these optically engineered 'twisted beams' (optical vortices) are endowed with orbital angular momentum. Here, the wave- front surface of the electromagnetic fields assumes helical form. To date, optical vortices have generally been studied only in their interactions with achiral matter. This study assesses what new features, if any, can be expected when such beams are used to interrogate a chiral system.

  9. A new family of four-ring bent-core nematic liquid crystals with highly polar transverse and end groups

    Directory of Open Access Journals (Sweden)

    Kalpana Upadhyaya

    2013-01-01

    Full Text Available Non-symmetrically substituted four-ring achiral bent-core compounds with polar substituents, i.e.., chloro in the bent or transverse direction in the central core and cyano in the lateral direction at one terminal end of the molecule, are designed and synthesized. These molecules possess an alkoxy chain attached at only one end of the bent-core molecule. The molecular structure characterization is consistent with data from elemental and spectroscopic analysis. The materials thermal behaviour and phase characterization have been investigated by differential scanning calorimetry and polarizing microscopy. All the compounds exhibit a wide-ranging monotropic nematic phase.

  10. Stereoselective cyclotetramerization of a 3-(Hydroxymethyl)salicylaldehyde

    Science.gov (United States)

    Butler; Brown; Boger; Ferfolia; Fitzgibbons; Jongeling; Kelleher; Malec; Malerich; Weltner

    2000-12-28

    Both 3-(hydroxymethyl)-5-methylsalicylaldehyde and its acetonide condense in the presence of hydrogen chloride in ether to form macrocyclic S(4)-symmetric tetraacetal 2. The reaction is completely oligo- and stereoselective, forming only the tetramer and only the achiral (R,S,R,S)-stereoisomer. Acid-catalyzed equilibration studies and molecular mechanics calculations indicate that the stereoselectivity is thermodynamic in origin. In the crystal the saddle-shaped molecules of 2 form coaxial stacks reminiscent of the packing of Pringles potato chips. PMID:11150180

  11. Wave Polarization Scattering and Transmission Property in Randomly Distributed Chiral Spheroids

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In this paper, the scattering amplitude functions of a spatially-oriented chiral spheroid are derived. Po larization scattering from a layer of randomly distributed chiral spheroids in the Mueller matrix solution is obtained. Co-polarized and de-polarized backscattering and polarization degree for any polarized incidence are numerically calcu lated. Transmissions of coherent waves with four Stokes parameters through the layer are also discussed. Comparisons of polarization scattering from the chiral and achiral particulate media demonstrate the chirality effect on wave scattering and transmission.

  12. Landau Theory and the Emergence of Chirality in Viral Capsids

    CERN Document Server

    Dharmavaram, Sanjay; Klug, William; Rudnick, Joseph; Bruinsma, Robijn

    2016-01-01

    We present a generalized Landau-Brazovskii theory for the solidification of chiral molecules on a spherical surface. With increasing sphere radius one encounters first intervals where robust achiral density modulations appear with icosahedral symmetry via first-order transitions. Next, one en- counters intervals where fragile but stable icosahedral structures still can be constructed but only by superposition of multiple irreducible representations. Chiral icoshedral structures appear via continuous or very weakly first-order transitions. Outside these parameter intervals, icosahedral symmetry is broken along a three-fold axis or a five-fold axis. The predictions of the theory are compared with recent numerical simulations.

  13. Wave propagation in a chiral fluid an undergraduate study

    CERN Document Server

    Garel, T

    2003-01-01

    We study the propagation of electromagnetic waves in a chiral fluid, where the molecules are described by a simplified version of the Kuhn coupled oscillator model. The eigenmodes of Maxwell's equations are circularly polarized waves. The application of a static magnetic field further leads to a magnetochiral term in the index of refraction of the fluid, which is independent of the wave polarization. A similar result holds when absorption is taken into account. Interference experiments and photochemical reactions have recently demonstrated the existence of the magnetochiral term. The comparison with Faraday rotation in an achiral fluid emphasizes the different symmetry properties of the two effects.

  14. Cyclodextrin-clicked silica/CdTe fluorescent nanoparticles for enantioselective recognition of amino acids

    Science.gov (United States)

    Zhou, Jie; Liu, Yun; Zhang, Zhixing; Yang, Sha; Tang, Jian; Liu, Wei; Tang, Weihua

    2016-03-01

    Fluorescent sensors based on semiconductor quantum dots (QDs) have been immensely investigated for achiral molecular recognition. For chiral discrimination of amino acids (AAs), we herein report a versatile fluorescent sensor, i.e., CdTe QDs encapsulated with cyclodextrin (CD) clicked silica via layer-by-layer modification. The as-obtained hybrid molecular recognition platform exhibited excellent chirality sensing of AAs at micromolar concentrations in water. By taking advantage of the inclusion complexation of CD and the optical properties of the QD core, chiral discrimination was realized on the basis of the different binding energies of the CD-AA enantiomer complexes, as revealed using density-functional theory calculation. The fluorescent probe exhibited linearly enhanced photoluminescence with increased concentration of d-histidine at 0-60 μM and l-histidine at 0-20 μM. These water-soluble fluorescent sensors using a chiral host with a covalently linked chromophore may find applications in the robust sensing of a wide range of achiral and chiral molecules in water.Fluorescent sensors based on semiconductor quantum dots (QDs) have been immensely investigated for achiral molecular recognition. For chiral discrimination of amino acids (AAs), we herein report a versatile fluorescent sensor, i.e., CdTe QDs encapsulated with cyclodextrin (CD) clicked silica via layer-by-layer modification. The as-obtained hybrid molecular recognition platform exhibited excellent chirality sensing of AAs at micromolar concentrations in water. By taking advantage of the inclusion complexation of CD and the optical properties of the QD core, chiral discrimination was realized on the basis of the different binding energies of the CD-AA enantiomer complexes, as revealed using density-functional theory calculation. The fluorescent probe exhibited linearly enhanced photoluminescence with increased concentration of d-histidine at 0-60 μM and l-histidine at 0-20 μM. These water

  15. Glutamate receptor agonists

    DEFF Research Database (Denmark)

    Vogensen, Stine Byskov; Greenwood, Jeremy R; Bunch, Lennart;

    2011-01-01

    The neurotransmitter (S)-glutamate [(S)-Glu] is responsible for most of the excitatory neurotransmission in the central nervous system. The effect of (S)-Glu is mediated by both ionotropic and metabotropic receptors. Glutamate receptor agonists are generally a-amino acids with one or more...... stereogenic centers due to strict requirements in the agonist binding pocket of the activated state of the receptor. By contrast, there are many examples of achiral competitive antagonists. The present review addresses how stereochemistry affects the activity of glutamate receptor ligands. The review focuses...

  16. A Dual Modulated Homochiral Helical Nanofilament Phase with Local Columnar Ordering Formed by Bent Core Liquid Crystals: Effects of Molecular Chirality.

    Science.gov (United States)

    Li, Lin; Salamonczyk, Miroslaw; Jákli, Antal; Hegmann, Torsten

    2016-08-01

    Helical nanofilament (HNF) phases form as a result of an intralayer mismatch between top and bottom molecular halves in bent-core liquid crystals (BC-LCs) that is relieved by local saddle-splay geometry. HNFs are immensely attractive for photovoltaic and chiral separation applications and as templates for the chiral spatial assembly of guest molecules. Here, the synthesis and characterization of two unichiral BC-LCs and one racemic mixture with tris-biphenyl-diester cores featuring chiral (R,R) and (S,S) or racemic 2-octyloxy aliphatic side chains are presented. In comparison to the achiral compound with linear side chains forming an intralayer modulated HNF phase (HNFmod ), synchrotron small angle X-ray diffraction indicates that the unichiral derivatives form a dual modulated HNF phase with intra- as well as interlayer modulations (HNFmod2 ) suggesting a columnar local structure of the nanofilaments. Transmission electron microscopy and circular dichroism spectropolarimetry confirm that the unichiral materials exclusively form homochiral HNFs with a twist sense-matching secondary twist. A contact preparation provides the first example of two identical chiral liquid crystal phases only differing in their handedness that do not mix and form an achiral liquid crystal phase with an entirely different structure in the contact zone. PMID:27334846

  17. Synthesis of novel room temperature chiral ionic liquids: application as reaction media for the heck arylation of aza-endocyclic acrylates

    International Nuclear Information System (INIS)

    New achiral and chiral RTILs were prepared using novel and/or optimized synthetic routes. These new series of imidazolinium, imidazolium, pyridinium and nicotine-derived ionic liquids were fully characterized including differential scanning calorimetry (DSC) analysis. The performance of these achiral and chiral room temperature ionic liquids (RTILs) was demonstrated by means of the Heck arylation of endocyclic acrylates employing arenediazonium salts and aryl iodides. The Heck arylations performed in the presence of these ionic entities, either as a solvent or as an additive, were effective leading to complete conversion of the substrate and good to excellent yield of the Heck adduct. In spite of the good performances, no asymmetric induction was observed in any of the cases studied. Two new diastereoisomeric NHC-palladium complexes were prepared in good yields from a chiral imidazolium salt and their structure characterized by X-ray diffraction. Overall, the Heck arylations employing arenediazonium tetrafluoroborates in RTILs were more effective than the traditional protocols employing aryl iodides in terms of reactivity and yields. (author)

  18. Switching of chiral magnetic skyrmions by picosecond magnetic field pulses via transient topological states

    Science.gov (United States)

    Heo, Changhoon; Kiselev, Nikolai S.; Nandy, Ashis Kumar; Blügel, Stefan; Rasing, Theo

    2016-06-01

    Magnetic chiral skyrmions are vortex like spin structures that appear as stable or meta-stable states in magnetic materials due to the interplay between the symmetric and antisymmetric exchange interactions, applied magnetic field and/or uniaxial anisotropy. Their small size and internal stability make them prospective objects for data storage but for this, the controlled switching between skyrmion states of opposite polarity and topological charge is essential. Here we present a study of magnetic skyrmion switching by an applied magnetic field pulse based on a discrete model of classical spins and atomistic spin dynamics. We found a finite range of coupling parameters corresponding to the coexistence of two degenerate isolated skyrmions characterized by mutually inverted spin structures with opposite polarity and topological charge. We demonstrate how for a wide range of material parameters a short inclined magnetic field pulse can initiate the reliable switching between these states at GHz rates. Detailed analysis of the switching mechanism revealed the complex path of the system accompanied with the excitation of a chiral-achiral meron pair and the formation of an achiral skyrmion.

  19. Comparison of reversed-phase enantioselective HPLC methods for determining the enantiomeric purity of (S)-omeprazole in the presence of its related substances$

    Institute of Scientific and Technical Information of China (English)

    Bruno Gallinella; Rosella Ferretti; Leo Zanitti; Isabella Sestili; Antonina Mosca; Roberto Cirilli n

    2016-01-01

    A simple analytical high-performance liquid chromatography (HPLC) method was applied for the en-antiomeric excess determination of esomeprazole ((S)-OME), the enantiopure active ingredient con-tained in drug products, in the presence of its potential organic impurities A-E. The enantioselective separation was accomplished on the immobilized-type Chiralpak ID-3 chiral stationary phase (CSP) under reversed-phase conditions. The results were evaluated and compared with those obtained by the official enantioselective method of European Pharmacopoeia used as the reference for checking the enantiomeric excess of (S)-OME. It has been established that the use of the Chiralpak ID-3 CSP allows the determination of the enantiomeric purity of (S)-OME without any interference coming from its chiral and achiral related substances. The analytical procedure of the drug regulatory agencies based on the AGP CSP suffered instead from poor specificity due to overlap of the peaks pertinent to the achiral impurity A and the chiral impurity (R)-OME (impurity F).

  20. Comparison of reversed-phase enantioselective HPLC methods for determining the enantiomeric purity of (S-omeprazole in the presence of its related substances

    Directory of Open Access Journals (Sweden)

    Bruno Gallinella

    2016-04-01

    Full Text Available A simple analytical high-performance liquid chromatography (HPLC method was applied for the enantiomeric excess determination of esomeprazole ((S-OME, the enantiopure active ingredient contained in drug products, in the presence of its potential organic impurities A-E. The enantioselective separation was accomplished on the immobilized-type Chiralpak ID-3 chiral stationary phase (CSP under reversed-phase conditions. The results were evaluated and compared with those obtained by the official enantioselective method of European Pharmacopoeia used as the reference for checking the enantiomeric excess of (S-OME. It has been established that the use of the Chiralpak ID-3 CSP allows the determination of the enantiomeric purity of (S-OME without any interference coming from its chiral and achiral related substances. The analytical procedure of the drug regulatory agencies based on the AGP CSP suffered instead from poor specificity due to overlap of the peaks pertinent to the achiral impurity A and the chiral impurity (R-OME (impurity F.

  1. Chiral selection of single helix formed by diblock copolymers confined in nanopores.

    Science.gov (United States)

    Deng, Hanlin; Qiang, Yicheng; Zhang, Tingting; Li, Weihua; Yang, Tao

    2016-09-21

    Chiral selection has attracted tremendous attention from the scientific communities, especially from biologists, due to the mysterious origin of homochirality in life. The self-assembly of achiral block copolymers confined in nanopores offers a simple but useful model of forming helical structures, where the helical structures possess random chirality selection, i.e. equal probability of left-handedness and right-handedness. Based on this model, we study the stimulus-response of chiral selection to external conditions by introducing a designed chiral pattern onto the inner surface of a nanopore, aiming to obtain a defect-free helix with controllable homochirality. A cell dynamics simulation based on the time-dependent Ginzburg-Landau theory is carried out to demonstrate the tuning effect of the patterned surface on the chiral selection. Our results illustrate that the chirality of the helix can be successfully controlled to be consistent with that of the tailored surface patterns. This work provides a successful example for the stimulus response of the chiral selection of self-assembled morphologies from achiral macromolecules to external conditions, and hence sheds light on the understanding of the mechanism of the stimulus response. PMID:27536966

  2. Stereogenicity revisited. Proposal of holantimers for comprehending the relationship between stereogenicity and chirality.

    Science.gov (United States)

    Fujita, Shinsaku

    2004-04-30

    The close relationship between stereogenicity and chirality has frequently caused serious confusion in the stereochemistry of organic molecules and inorganic complexes. To clarify the entangled relationship between them, we have proposed the concept of "holantimer". In addition, we have newly defined the concept of "stereoisogram" in order to correlate a set of stereoiomers based on holantimeric and enantiomeric relationships. These concepts have been applied to tetrahedral organic molecules as well as to square-planar inorganic complexes. The stereogenicity characterized by a stereoisogram has been called "RS-stereogenicity", which has been clarified to be a property that should be correlated to chirality. The stereoisograms of tetrahedral molecules have been examined and classified into five types, i.e., type I (chiral/RS-stereogenic), type II (chiral/RS-astereogenic), type III (chiral/RS-stereogenic), type IV (achiral/RS-astereogenic), and type V (achiral/RS-stereogenic), where RS descriptors are concluded to be specified in cases of types I, III, and V. On the other hand, the stereoisograms of square-planar complexes have been classified to two types, i.e., type II and type IV. As a result, the confusion on the RS-nomenclature has been concluded to appear within the RS-stereogenic relationships. Such a new viewpoint of stereogenicity and chirality as described in the present paper provides us with a methodology for restructuring stereochemistry. PMID:15104457

  3. Ligand induced circular dichroism and circularly polarized luminescence in CdSe quantum dots.

    Science.gov (United States)

    Tohgha, Urice; Deol, Kirandeep K; Porter, Ashlin G; Bartko, Samuel G; Choi, Jung Kyu; Leonard, Brian M; Varga, Krisztina; Kubelka, Jan; Muller, Gilles; Balaz, Milan

    2013-12-23

    Chiral thiol capping ligands L- and D-cysteines induced modular chiroptical properties in achiral cadmium selenide quantum dots (CdSe QDs). Cys-CdSe prepared from achiral oleic acid capped CdSe by postsynthetic ligand exchange displayed size-dependent electronic circular dichroism (CD) and circularly polarized luminescence (CPL). Opposite CPL signals were measured for the CdSe QDs capped with D- and L-cysteine. The CD profile and CD anisotropy varied with size of CdSe nanocrystals with largest anisotropy observed for CdSe nanoparticles of 4.4 nm. Magic angle spinning solid state NMR (MAS ssNMR) experiments suggested bidentate interaction between cysteine and the surface of CdSe. Time Dependent Density Functional Theory (TDDFT) calculations verified that attachment of L- and D-cysteine to the surface of model (CdSe)13 nanoclusters induces measurable opposite CD signals for the exitonic band of the nanocluster. The origin of the induced chirality is consistent with the hybridization of highest occupied CdSe molecular orbitals with those of the chiral ligand.

  4. Long Range Chiral Imprinting of Cu(110) by Tartaric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Lawton, T J; Pushkarev, V; Wei, D; Lucci, F R; Sholl, D S; Gellman, A J; Sykes, E C. H.

    2013-10-31

    Restructuring of metals by chiral molecules represents an important route to inducing and controlling enantioselective surface chemistry. Tartaric acid adsorption on Cu(110) has served as a useful system for understanding many aspects of chiral molecule adsorption and ordering on a metal surface, and a number of chiral and achiral unit cells have been reported. Herein, we show that given the appropriate annealing treatment, singly deprotonated tartaric acid monolayers can restructure the Cu metal itself, and that the resulting structure is both highly ordered and chiral. Molecular resolution scanning tunneling microscopy reveals that singly deprotonated tartaric acid extracts Cu atoms from the Cu(110) surface layer and incorporates them into highly ordered, chiral adatom arrays capped by a continuous molecular layer. Further evidence for surface restructuring comes from images of atom-deep trenches formed in the Cu(110) surface during the process. These trenches also run in low symmetry directions and are themselves chiral. Simulated scanning tunneling microscopy images are consistent with the appearance of the added atom rows and etched trenches. The chiral imprinting results in a long-range, highly ordered unit cell covering the whole surface as confirmed by low energy electron diffraction. Details of the restructuring mechanism were further investigated via time-lapse imaging at elevated temperature. This work reveals the stages of nanoscale surface restructuring and offers an interesting method for chiral modification of an achiral metal surface.

  5. Cyclodextrin-clicked silica/CdTe fluorescent nanoparticles for enantioselective recognition of amino acids.

    Science.gov (United States)

    Zhou, Jie; Liu, Yun; Zhang, Zhixing; Yang, Sha; Tang, Jian; Liu, Wei; Tang, Weihua

    2016-03-14

    Fluorescent sensors based on semiconductor quantum dots (QDs) have been immensely investigated for achiral molecular recognition. For chiral discrimination of amino acids (AAs), we herein report a versatile fluorescent sensor, i.e., CdTe QDs encapsulated with cyclodextrin (CD) clicked silica via layer-by-layer modification. The as-obtained hybrid molecular recognition platform exhibited excellent chirality sensing of AAs at micromolar concentrations in water. By taking advantage of the inclusion complexation of CD and the optical properties of the QD core, chiral discrimination was realized on the basis of the different binding energies of the CD-AA enantiomer complexes, as revealed using density-functional theory calculation. The fluorescent probe exhibited linearly enhanced photoluminescence with increased concentration of d-histidine at 0-60 μM and L-histidine at 0-20 μM. These water-soluble fluorescent sensors using a chiral host with a covalently linked chromophore may find applications in the robust sensing of a wide range of achiral and chiral molecules in water. PMID:26893164

  6. Universal spin-momentum locked optical forces

    Energy Technology Data Exchange (ETDEWEB)

    Kalhor, Farid [Department of Electrical and Computer Engineering, University of Alberta, Edmonton, Alberta T6G 1H9 (Canada); Thundat, Thomas [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9 (Canada); Jacob, Zubin, E-mail: zjacob@purdue.edu [Department of Electrical and Computer Engineering, University of Alberta, Edmonton, Alberta T6G 1H9 (Canada); Birck Nanotechnology Center, Department of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana 47906 (United States)

    2016-02-08

    Evanescent electromagnetic waves possess spin-momentum locking, where the direction of propagation (momentum) is locked to the inherent polarization of the wave (transverse spin). We study the optical forces arising from this universal phenomenon and show that the fundamental origin of recently reported non-trivial optical chiral forces is spin-momentum locking. For evanescent waves, we show that the direction of energy flow, the direction of decay, and the direction of spin follow a right hand rule for three different cases of total internal reflection, surface plasmon polaritons, and HE{sub 11} mode of an optical fiber. Furthermore, we explain how the recently reported phenomena of lateral optical force on chiral and achiral particles are caused by the transverse spin of the evanescent field and the spin-momentum locking phenomenon. Finally, we propose an experiment to identify the unique lateral forces arising from the transverse spin in the optical fiber and point to fundamental differences of the spin density from the well-known orbital angular momentum of light. Our work presents a unified view on spin-momentum locking and how it affects optical forces on chiral and achiral particles.

  7. The meso Helix: Symmetry and Symmetry-Breaking in Dynamic Oligourea Foldamers with Reversible Hydrogen-Bond Polarity.

    Science.gov (United States)

    Wechsel, Romina; Raftery, James; Cavagnat, Dominique; Guichard, Gilles; Clayden, Jonathan

    2016-08-01

    Oligoureas (up to n=6) of meso cyclohexane-1,2-diamine were synthesized by chain extension with an enzymatically desymmetrized monomer 2. Despite being achiral, the meso oligomers adopt chiral canonical 2.5-helical conformations, the equally populated enantiomeric screw-sense conformers of which are in slow exchange on the NMR timescale, with a barrier to screw-sense inversion of about 70 kJ mol(-1) . Screw-sense inversion in these helical foldamers is coupled with cyclohexane ring-flipping, and results in a reversal of the directionality of the hydrogen bonding in the helix. The termini of the meso oligomers are enantiotopic, and desymmetrized analogues of the oligoureas with differentially and enantioselectively protected termini display moderate screw-sense preferences. A screw-sense preference may furthermore be induced in the achiral, meso oligoureas by formation of a 1:1 hydrogen-bonded complex with the carboxylate anion of Boc-d-proline. The meso oligoureas are the first examples of hydrogen-bonded foldamers with reversible hydrogen-bond directionality. PMID:27298097

  8. Universal spin-momentum locked optical forces

    Science.gov (United States)

    Kalhor, Farid; Thundat, Thomas; Jacob, Zubin

    2016-02-01

    Evanescent electromagnetic waves possess spin-momentum locking, where the direction of propagation (momentum) is locked to the inherent polarization of the wave (transverse spin). We study the optical forces arising from this universal phenomenon and show that the fundamental origin of recently reported non-trivial optical chiral forces is spin-momentum locking. For evanescent waves, we show that the direction of energy flow, the direction of decay, and the direction of spin follow a right hand rule for three different cases of total internal reflection, surface plasmon polaritons, and HE11 mode of an optical fiber. Furthermore, we explain how the recently reported phenomena of lateral optical force on chiral and achiral particles are caused by the transverse spin of the evanescent field and the spin-momentum locking phenomenon. Finally, we propose an experiment to identify the unique lateral forces arising from the transverse spin in the optical fiber and point to fundamental differences of the spin density from the well-known orbital angular momentum of light. Our work presents a unified view on spin-momentum locking and how it affects optical forces on chiral and achiral particles.

  9. Liquid Crystal Phases of Molecular Bananas: Polarity and Chirality as Broken Symmetries

    Science.gov (United States)

    Clark, Noel

    2006-03-01

    The study of the interplay of chirality and polarity has been a particularly rich theme of soft matter science since Meyer's seminal discovery that tilted smectics of chiral molecules are macroscopically polar. This event, and the subsequent realization of polar domains and high-speed electro-optic switching in chiral smectics, engaged the liquid crystal community in a worldwide pursuit of novel smectics for applications, featured by the synthesis of more than 50,000 new liquid crystal compounds, and by a consequent broad diversification of the palette of liquid crystal phases and possibilities for supermolecular ordering. A current important activity in this scenario is the study of polar order in synthetically achiral molecules, for example, in molecular bananas, which, as their shape suggests, might be expected to organize in a polar way. Indeed they do, but beyond this, almost everything learned about them has been surprising, including their persistent tendency to exhibit chirality as a spontaneously broken symmetry. I will discuss some of these new phases and phenomena, including the discovery of fluid conglomerates (Pasteur's experiment in a fluid), triclinic fluid order, chiral twist grain boundary phases of achiral molecules, chirality flipping and field-induced deracemization, ferroelectric and antiferroelectric phases with supermolecular- scale polarization modulation, and chiral thermotropic sponge phases.

  10. Universal spin-momentum locked optical forces

    International Nuclear Information System (INIS)

    Evanescent electromagnetic waves possess spin-momentum locking, where the direction of propagation (momentum) is locked to the inherent polarization of the wave (transverse spin). We study the optical forces arising from this universal phenomenon and show that the fundamental origin of recently reported non-trivial optical chiral forces is spin-momentum locking. For evanescent waves, we show that the direction of energy flow, the direction of decay, and the direction of spin follow a right hand rule for three different cases of total internal reflection, surface plasmon polaritons, and HE11 mode of an optical fiber. Furthermore, we explain how the recently reported phenomena of lateral optical force on chiral and achiral particles are caused by the transverse spin of the evanescent field and the spin-momentum locking phenomenon. Finally, we propose an experiment to identify the unique lateral forces arising from the transverse spin in the optical fiber and point to fundamental differences of the spin density from the well-known orbital angular momentum of light. Our work presents a unified view on spin-momentum locking and how it affects optical forces on chiral and achiral particles

  11. Evidence for small-molecule-mediated loop stabilization in the structure of the isolated Pin1 WW domain

    Energy Technology Data Exchange (ETDEWEB)

    Mortenson, David E.; Kreitler, Dale F.; Yun, Hyun Gi; Gellman, Samuel H., E-mail: gellman@chem.wisc.edu; Forest, Katrina T., E-mail: gellman@chem.wisc.edu [University of Wisconsin-Madison, Madison, WI 53706 (United States)

    2013-12-01

    Two structures of a small protein with a defined tertiary fold, the isolated Pin1 WW domain, have been determined via racemic crystallization with small-molecule additives. These additives, which are either racemic or achiral, appear to stabilize a dynamic loop region of the structure. The human Pin1 WW domain is a small autonomously folding protein that has been useful as a model system for biophysical studies of β-sheet folding. This domain has resisted previous attempts at crystallization for X-ray diffraction studies, perhaps because of intrinsic conformational flexibility that interferes with the formation of a crystal lattice. Here, the crystal structure of the human Pin1 WW domain has been obtained via racemic crystallization in the presence of small-molecule additives. Both enantiomers of a 36-residue variant of the Pin1 WW domain were synthesized chemically, and the l- and d-polypeptides were combined to afford diffracting crystals. The structural data revealed packing interactions of small carboxylic acids, either achiral citrate or a d,l mixture of malic acid, with a mobile loop region of the WW-domain fold. These interactions with solution additives may explain our success in crystallization of this protein racemate. Molecular-dynamics simulations starting from the structure of the Pin1 WW domain suggest that the crystal structure closely resembles the conformation of this domain in solution. The structural data presented here should provide a basis for further studies of this important model system.

  12. Precursors for sergeant-and-soldiers experiments: dimethyl succinic acid on Cu(110)

    Energy Technology Data Exchange (ETDEWEB)

    Karageorgaki, Chrysanthi; Roth, Christian; Parschau, Manfred; Ernst, Karl-Heinz [EMPA, Swiss Federal Laboratories for Materials Science and Technology, Duebendorf (Switzerland)

    2011-07-01

    In order to better understand chiral recognition at the molecular level, we are currently studying interactions between different chiral butanedioc acids, like tartaric acid (TA), malic acid (MA) and 2,3-dimethyl succinic acid (DMSU) as well as achiral analogues like succinic acid (SU), meso-TA and meso-DMSU on metal surfaces. This led to first a observation of chiral amplification 2D crystals via the so-called ''sergeant-and soldiers effect''. In order to discriminate if through-substrate or lateral hydrogen bonding dominates the chiral recognition at surfaces, we currently synthesize chiral DMSU, i.e., replacing the hydroxyl groups of TA by methyl. Here we present LEED, XPS, TPD and RAIRS results of achiral meso-DMSU (HOOC-CH(CH{sub 3})-CH(CH{sub 3})-COOH) on Cu(110). Besides coverage-dependent ''surface-explosion'' decomposition chemistry and ordered C{sub 2}-symmetric structures, DMSU spontaneously undergoes symmetry breaking, observed as superposition of mirror domains in LEED, which makes this system indeed interesting for doping experiments with chiral DMSU.

  13. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations.

    Science.gov (United States)

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim A

    2013-10-01

    Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

  14. Liquid crystal display modes in a nontilted bent-core biaxial smectic liquid crystal

    Science.gov (United States)

    Nagaraj, Mamatha; Panarin, Y. P.; Vij, J. K.; Keith, C.; Tschierske, C.

    2010-11-01

    Liquid crystal display (LCD) modes associated with the rotation of the secondary director in nontilted, biaxial smectic phase of an achiral bent-core compound are demonstrated. For LCDs, we find that at least four display modes are possible using SmAPA phase of the studied material, in which the minor directors in adjacent layers are aligned antiferroelectrically. The advantages of these modes include low driving field (1-2 V/μm), high contrast ratio 1000:1, relatively fast switching time of 0.5 ms and continuous gray scale. The molecular short axis or the polar axis in a negative dielectric, biaxial material is oriented by the in-plane electric field by a combination dielectric biaxiality and polarity at low electric fields and polarity at higher fields.

  15. Enantioselective Synthesis of (+)-Peganumine A.

    Science.gov (United States)

    Piemontesi, Cyril; Wang, Qian; Zhu, Jieping

    2016-09-01

    A gram-scale enantioselective total synthesis of (+)-peganumine A was accomplished in 7 steps from commercially available 6-methoxytryptamine. Key steps included (a) a Liebeskind-Srogl cross-coupling; (b) a one-pot construction of the tetracyclic skeleton from an ω-isocyano-γ-oxo-aldehyde via a sequence of an unprecedented C-C bond forming lactamization and a transannular condensation; (c) a one-pot organocatalytic process merging two achiral building blocks into an octacyclic structure via a sequence of enantioselective Pictet-Spengler reaction followed by a transannular cyclization. This last reaction created two spirocycles and a 2,7-diazabicyclo[2.2.1]heptan-3-one unit with excellent control of both the absolute and relative stereochemistry of the two newly created quaternary stereocenters. PMID:27558528

  16. Thin film phase and local chirality of surface-bound MOP4 nanofibers

    DEFF Research Database (Denmark)

    Balzer, Frank; Röthel, Christian; Rubahn, Horst-Günter;

    2016-01-01

    epitaxially (point-on-line coincidence) along two directions on a single muscovite domain. The crystal structure of the fibers was induced by the substrate. Molecular packing was calculated by molecular dynamics simulations. A wetting layer from the lying molecules was observed using low-energy electron...... diffraction (LEED) that had a crystal structure different from that of the fibers. Transfer of the sample from a vacuum to ambient conditions led to dewetting and the formation of clusters from the lying molecules. The samples aged via Ostwald ripening due to the presence of water vapor, which was monitored...... by atomic force microscopy (AFM). The fibers represent chiral organization into single-handed aggregates of both handednesses, which is not affected by aging. On a global level, the sample remained achiral....

  17. Equilibrium of nematic vesicles

    Energy Technology Data Exchange (ETDEWEB)

    Napoli, Gaetano [Dipartimento di Ingegneria dell' Innovazione, Universita del Salento, via per Monteroni, Edificio ' Corpo O' , 73100 Lecce (Italy); Vergori, Luigi, E-mail: gaetano.napoli@unisalento.i, E-mail: luigi.vergori@unisalento.i [Dipartimento di Matematica, Universita del Salento, Strada Prov. Lecce-Arnesano, 73100 Lecce (Italy)

    2010-11-05

    A variational scheme is proposed which allows the derivation of a concise and elegant formulation of the equilibrium equations for closed fluid membranes, endowed with a nematic microstructure. The nematic order is described by an in-plane nematic director and a degree of orientation, as customary in the theory of uniaxial nematics. The only constitutive ingredient in this scheme is a free-energy density which depends on the vesicle geometry and order parameters. The stress and the couple stress tensors related to this free-energy density are provided. As an application of the proposed scheme, a certain number of special theories are deduced: soap bubbles, lipid vesicles, chiral and achiral nematic membranes, and nematics on curved substrates.

  18. Preparation of optical active polydiacetylene through gelating and the control of supramolecular chirality

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Achiral diacetylene 10,12-pentacosadinoic acid (PCDA) and a chiral low-molecular-weight organogelator could form co-gel in organic solvent and it could be polymerized in the presence of Zn(II) ion or in the corresponding xerogel under UV-irradiation. Optically active polydiacetylene (PDA) were subsequently obtained. Supramolecular chirality of PDA could be controlled by the chirality of gelators. Left-handed and right-handed helical fibers were obtained by using Land D-gelators in xerogels respectively, and CD spectra exhibited mirror-image circular dichroism. The PDA in xerogel exhibited typical blue-to-red transition responsive to the temperature and pH, while the supramolecular chirality of PDA showed a corresponding change.

  19. Mirror image proteins.

    Science.gov (United States)

    Zhao, Le; Lu, Wuyuan

    2014-10-01

    Proteins composed entirely of unnatural d-amino acids and the achiral amino acid glycine are mirror image forms of their native l-protein counterparts. Recent advances in chemical protein synthesis afford unique and facile synthetic access to domain-sized mirror image d-proteins, enabling protein research to be conducted through 'the looking glass' and in a way previously unattainable. d-Proteins can facilitate structure determination of their native l-forms that are difficult to crystallize (racemic X-ray crystallography); d-proteins can serve as the bait for library screening to ultimately yield pharmacologically superior d-peptide/d-protein therapeutics (mirror-image phage display); d-proteins can also be used as a powerful mechanistic tool for probing molecular events in biology. This review examines recent progress in the application of mirror image proteins to structural biology, drug discovery, and immunology.

  20. Derivatization in Capillary Electrophoresis.

    Science.gov (United States)

    Marina, M Luisa; Castro-Puyana, María

    2016-01-01

    Capillary electrophoresis is a well-established separation technique in analytical research laboratories worldwide. Its interesting advantages make CE an efficient and potent alternative to other chromatographic techniques. However, it is also recognized that its main drawback is the relatively poor sensitivity when using optical detection. One way to overcome this limitation is to perform a derivatization reaction which is intended to provide the analyte more suitable analytical characteristics enabling a high sensitive detection. Based on the analytical step where the CE derivatization takes place, it can be classified as precapillary (before separation), in-capillary (during separation), or postcapillary (after separation). This chapter describes the application of four different derivatization protocols (in-capillary and precapillary modes) to carry out the achiral and chiral analysis of different compounds in food and biological samples with three different detection modes (UV, LIF, and MS). PMID:27645730

  1. The elusive thermotropic biaxial nematic phase in rigid bent-core molecules

    Indian Academy of Sciences (India)

    Bharat R Acharya; Andrew Primak; Theo J Dingemans; Edward T Samulski; Satyendra Kumar

    2003-08-01

    The biaxial nematic liquid crystalline phase was predicted several decades ago. Several vigorous attempts to find it in various systems resulted in mis-identifications. The results of X-ray diffraction and optical texture studies of the phases exhibited by rigid bent-core molecules derived from 2,5-bis-(-hydroxyphenyl)-1,3,4-oxadiazole reveal that the biaxial nematic phase is formed by three compounds of this type. X-ray diffraction studies reveal that the nematic phase of these compounds has the achiral symmetry D2h, in which the overall long axes of the molecules are oriented parallel to each other to define the major axis of the biaxial phase. The apex of the bent-cores defines the minor axis of this phase along which the planes containing the bent-cores of neighboring molecules are oriented parallel to each other.

  2. Punctuated Chirality

    Science.gov (United States)

    Gleiser, Marcelo; Thorarinson, Joel; Walker, Sara Imari

    2008-12-01

    Most biomolecules occur in mirror, or chiral, images of each other. However, life is homochiral: proteins contain almost exclusively L-amino acids, while only D-sugars appear in RNA and DNA. The mechanism behind this fundamental asymmetry of life remains an open problem. Coupling the spatiotemporal evolution of a general autocatalytic polymerization reaction network to external environmental effects, we show through a detailed statistical analysis that high intensity and long duration events may drive achiral initial conditions towards chirality. We argue that life’s homochirality resulted from sequential chiral symmetry breaking triggered by environmental events, thus extending the theory of punctuated equilibrium to the prebiotic realm. Applying our arguments to other potentially life-bearing planetary platforms, we predict that a statistically representative sampling will be racemic on average.

  3. Spontaneous helix formation in non-chiral bent-core liquid crystals with fast linear electro-optic effect

    Science.gov (United States)

    Sreenilayam, Sithara P.; Panarin, Yuri P.; Vij, Jagdish K.; Panov, Vitaly P.; Lehmann, Anne; Poppe, Marco; Prehm, Marko; Tschierske, Carsten

    2016-05-01

    Liquid crystals (LCs) represent one of the foundations of modern communication and photonic technologies. Present display technologies are based mainly on nematic LCs, which suffer from limited response time for use in active colour sequential displays and limited image grey scale. Herein we report the first observation of a spontaneously formed helix in a polar tilted smectic LC phase (SmC phase) of achiral bent-core (BC) molecules with the axis of helix lying parallel to the layer normal and a pitch much shorter than the optical wavelength. This new phase shows fast (~30 μs) grey-scale switching due to the deformation of the helix by the electric field. Even more importantly, defect-free alignment is easily achieved for the first time for a BC mesogen, thus providing potential use in large-scale devices with fast linear and thresholdless electro-optical response.

  4. Cyclodextrins in capillary electrophoresis: recent developments and new trends.

    Science.gov (United States)

    Escuder-Gilabert, L; Martín-Biosca, Y; Medina-Hernández, M J; Sagrado, S

    2014-08-29

    Despite the fact that extensive research in the field of separations by capillary electrophoresis (CE) has been carried out and many reviews have been published in the last years, a specific review on the use and future potential of cyclodextrins (CDs) in CE is not available. This review focuses the attention in the CD-CE topic over the January 2013-February 2014 period (not covered by previous more general CE-reviews). Recent contributions (reviews and research articles) including practical uses (e.g. solute-CD binding constant estimation and further potentials; 19% of publications), developments and applications (mainly chiral and achiral analysis; 38 and 24% of publications, respectively) are summarized in nine comprehensive tables and are commented. Statistics and predictions related to the CD-CE publications are highlighted in order to infer the current and expected research interests. Finally, trends and initiatives on CD-CE attending to real needs or practical criteria are outlined.

  5. Supramolecular chirality in self-assembled peptide amphiphile nanostructures.

    Science.gov (United States)

    Garifullin, Ruslan; Guler, Mustafa O

    2015-08-11

    Induced supramolecular chirality was investigated in the self-assembled peptide amphiphile (PA) nanosystems. Having shown that peptide chirality can be transferred to the covalently-attached achiral pyrene moiety upon PA self-assembly, the chiral information is transferred to molecular pyrene via weak noncovalent interactions. In the first design of a supramolecular chiral system, the chromophore was covalently attached to a peptide sequence (VVAGH) via an ε-aminohexanoic acid spacer. Covalent attachment yielded a PA molecule self-assembling into nanofibers. In the second design, the chromophore was encapsulated within the hydrophobic core of self-assembled nanofibers of another PA consisting of the same peptide sequence attached to lauric acid. We observed that supramolecular chirality was induced in the chromophore by PA assembly into chiral nanostructures, whether it was covalently attached, or noncovalently bound. PMID:26146021

  6. Spin-polarized Voltages on a 2D Self-assembled Plasmonic Crystal

    CERN Document Server

    Proscia, Nicholas V; Chang, Roger; Kretzschmar, Ilona; Menon, Vinod M; Vuong, Luat T

    2015-01-01

    The Photon Drag Effect (PDE) is a nonlinear process akin to optical rectification in which the momentum of light is transferred to charged carriers and converted to a DC voltage. Here, we experimentally demonstrate the spin-polarized voltage, associated with the transference of light's spin angular momenta to the linear momenta of charges, with visible-light illumination on a nanovoid self-assembled plasmonic crystal surface. Numerical calculations show that the gradient force, generally considered independent of polarization, is responsible for the majority of the momentum transfer. The PDE in this achiral system represents a distinct spin-orbit interaction that produces asymmetric hotspots whose locations change with circular polarization handedness. Our results significantly advance our understanding of the PDE and demonstrate realistic potential for scalable plasmonic materials that utilize PDE.

  7. Brilliant Sm, Eu, Tb and Dy chiral lanthanide complexes withstrong circularly polarized luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Petoud, Stephane; Muller, Gilles; Moore, Evan G.; Xu, Jide; Sokolnicki, Jurek; Riehl, James P.; Le, Uyen; Cohen, Seth M.; Raymond,Kenneth N.

    2006-07-10

    The synthesis, characterization and luminescent behavior of trivalent Sm, Eu, Dy and Tb complexes of two enantiomeric, octadentate, chiral, 2-hydroxyisophthalamide ligands are reported. These complexes are highly luminescent in solution. Functionalization of the achiral parent ligand with a chiral 1-phenylethylamine substituent on the open face of the complex in close proximity to the metal center yields complexes with strong circularly polarized luminescence (CPL) activity. This appears to be the first example of a system utilizing the same ligand architecture to sensitize four different lanthanide cations and display CPL activity. The luminescence dissymmetry factor, g{sub lum}, recorded for the Eu(III) complex is one of the highest values reported, and this is the first time the CPL effect has been demonstrated for a Sm(III) complex with a chiral ligand. The combination of high luminescence intensity with CPL activity should enable new bioanalytical applications of macromolecules in chiral environments.

  8. Synthesizing Skyrmion Molecules in Fe-Gd Thin Films

    Science.gov (United States)

    Lee, J. C. T.; Chess, J.; Montoya, S. A.; Shi, X. W.; Tamura, Nobumichi; Mishra, S. K.; Parks, D. H.; Fischer, P.; McMorran, B.; Sinha, S. K.; Fullerton, E.; Kevan, S. D.; Roy, S.

    Controlled creation of tunable skyrmion phases at room temperature holds the promise of advanced spintronics applications using these topological entities. By varying the composition and thickness of an amorphous Fe-Gd thin film and optimizing the applied field protocol, we produced at room temperature an ordered, achiral phase of skyrmion molecules, that is, bound pairs of magnetic skyrmions having the same polarity but opposite helicity. This phase appears between stripe and uniform magnetization phase and its origin lies in the existence of mirror planes in the stripe domain structure. Dipolar, exchange, and anisotropy forces are the dominant interactions in these materials, while the role of bulk and surface chiral exchange interactions is small. Supported by the Basic Energy Sciences, US DOE: DE-AC02-05CH11231; DE- FG02-11ER46831; and DE-SC0003678.

  9. Laser R2PI spectroscopic and mass spectrometric studies of chiral neurotransmitters

    Science.gov (United States)

    Giardini, A.; Marotta, V.; Paladini, A.; Piccirillo, S.; Rondino, F.; Satta, M.; Speranza, M.

    2007-07-01

    One color, mass selected resonant two-photon ionization (1cR2PI) spectra of supersonically expanded bare neurotransmitter, (1 S,2 S)-(+)- N-methyl pseudoephedrine (MPE), and its complexes with chiral and achiral molecules have been investigated. The excitation spectrum of bare MPE has been analyzed and discussed on the basis of theoretical predictions at the B3LYP/6-31G** level of theory. The results allowed to get information on the possible conformers of MPE molecule and on the intermolecular forces on its cluster formed with a variety of solvent molecules, including chiral alcohols, lactates and water. Further information on intermolecular interactions have been obtained with ESI-CID-MS 2 technique, applied to chiral biomolecules linked through a metal ion to the neurotransmitter. The experimental results are compared with theoretical predictions.

  10. Review on the symmetry-related properties of carbon nanotubes

    International Nuclear Information System (INIS)

    In this work we review the basic properties of carbon nanotubes from the standpoint of group theory. The zone folding scheme is reviewed in the light of the helical symmetry of the nanotube. The group theory for chiral and achiral nanotubes is reviewed, and the representations of the factor group of the wavevector k are obtained. The similarities and differences between the formalism of the group of the wavevector and that of line groups are addressed with respect to the irreducible representations and quantum numbers associated with linear and angular momenta. Finally, we extend the results of group theory to illuminate the electronic and vibrational properties of carbon nanotubes. Selection rules for the optical absorption and double resonance Raman scattering are discussed for the case where the electron-electron interaction is negligible (metallic nanotubes) and for the case where exciton binding energies are strong and cannot be neglected

  11. Mass transfer mechanism in chiral reversed phase liquid chromatography.

    Science.gov (United States)

    Gritti, Fabrice; Guiochon, Georges

    2014-03-01

    The mechanism of mass transfer in chiral chromatography was investigated using an experimental protocol already applied in RPLC and HILIC chromatography. The different contributions to the reduced height equivalent to a theoretical plate (HETP) include the longitudinal diffusion HETP term, the solid-liquid mass transfer resistance HETP term, the short-range eddy dispersion HETP term, and the long-range eddy dispersion HETP term. Their accurate measurement permits the determination of the adsorption rate constant kads of trans-stilbene enantiomers on a column packed with Lux 5 μm Cellulose-1 particles. The experimental results demonstrate that the number of adsorption-desorption steps per unit time of chiral compounds on polysaccharide-based chiral stationary phases is four orders of magnitude smaller than that of achiral compounds.

  12. Carbon Nanomaterials: Applications in Physico-chemical Systemsand Biosystems

    Directory of Open Access Journals (Sweden)

    Maheshwar Sharon

    2008-07-01

    Full Text Available In the present article, various forms of carbon and carbon nanomaterials (CNMs and a new approach to classify them on the basis of sp2-sp3 configuration are presented. Utilising the concept of junction formation (like p:n junction a concept is developed to explain the special reactivity of nanosized carbon materials. Geometric consideration of chiral and achiral symmetry of single-walled carbon nanotubes is presented which is also responsible for manifesting special propertiesof carbon nanotubes. A brief introduction to various common synthesis techniques of CNMs is given. These is increased chemical and biological activities have resulted in many engineer ednanoparticles, which are being designed for specific purposes, including diagnostic or the rapeuticmedical uses and environmental remediation.Defence Science Journal, 2008, 58(4, pp.460-485, DOI:http://dx.doi.org/10.14429/dsj.58.1668

  13. Chiral light by symmetric optical antennas

    CERN Document Server

    Mekonnen, Addis; Zubritskaya, Irina; Jönsson, Gustav Edman; Dmitriev, Alexandre

    2014-01-01

    Chirality is at the origin of life and is ubiquitous in nature. An object is deemed chiral if it is non-superimposable with its own mirror image. This relates to how circularly polarized light interacts with such object, a circular dichroism, the differential absorption of right and left circularly polarized light. According to the common understanding in biology, chemistry and physics, the circular dichroism results from an internal chiral structure or external symmetry breaking by illumination. We show that circular dichroism is possible with simple symmetric optical nanoantennas at symmetric illumination. We experimentally and theoretically demonstrate that two electromagnetic dipole-like modes with a phase lag, in principle, suffice to produce circular dichroism in achiral structure. Examples of the latter are all visible spectrum optical nanoantennas, symmetric nanoellipses and nanodimers. The simplicity and generality of this finding reveal a whole new significance of the electromagnetic design at a nan...

  14. Sensing and tuning microfiber chirality with nematic chirogyral effect

    Science.gov (United States)

    Čopar, Simon; Seč, David; Aguirre, Luis E.; Almeida, Pedro L.; Dazza, Mallory; Ravnik, Miha; Godinho, Maria H.; Pieranski, Pawel; Žumer, Slobodan

    2016-03-01

    Microfibers with their elongated shape and translation symmetry can act as important components in various soft materials, notably for their mechanics on the microscopic level. Here we demonstrate the mechanical response of a micro-object to imposed chirality, in this case, the tilt of disclination rings in an achiral nematic medium caused by the chiral surface anchoring on an immersed microfiber. This coupling between chirality and mechanical response, used to demonstrate sensing of chirality of electrospun cellulose microfibers, is revealed in the optical micrographs due to anisotropy in the elastic response of the host medium. We provide an analytical explanation of the chirogyral effect supported with numerical simulations and perform an experiment to test the effect of the cell confinement and fiber size. We controllably twist the microfibers and demonstrate the response of the nematic medium. More generally the demonstrated study provides means for experimental discrimination of surface properties and allows mechanical control over the shape of disclination rings.

  15. Three-dimensional hybrid networks based on aspartic acid

    Indian Academy of Sciences (India)

    Anupama Ghosh; R A Sanguramath

    2008-01-01

    Three-dimensional achiral coordination polymers of the general formula M2(D, L-NHCH (COO)CH2COO)2.C4H4N2 where M = Ni and Co and pyrazine acts as the linker molecule have been prepared under hydrothermal conditions starting with [M(L-NHCH(COO)CH2COO).3H2O] possessing a helical chain structure. A three-dimensional hybrid compound of the formula Pb2.5[N{CH(COO)CH2COO}22H2O] has also been prepared hydrothermally starting with aspartic acid and Pb(NO3)2. In this lead compound, where a secondary amine formed by the dimerisation of aspartic acid acts as the ligand, there is two-dimensional inorganic connectivity and one-dimensional organic connectivity.

  16. Novel routes to either racemic or enantiopure α-amino-(4-hydroxy-pyrrolidin-3-yl)acetic acid derivatives and biological evaluation of a new promising pharmacological scaffold.

    Science.gov (United States)

    Cecioni, Samy; Aouadi, Kaïss; Guiard, Julie; Parrot, Sandrine; Strazielle, Nathalie; Blondel, Sandrine; Ghersi-Egea, Jean-François; Chapelle, Christian; Denoroy, Luc; Praly, Jean-Pierre

    2015-06-15

    Cycloaddition between (+) or (-)-menthone-derived nitrones and N-benzyl-3-pyrroline afforded enantiopure spiro-fused heterocycles. The reaction occurred enantio- and diastereo-selectively on the less hindered side of the nitrone, the 3-pyrroline N-benzyl group being oriented outwards, thus controlling the configurations of three simultaneously created chiral centers. From either (+) or (-)-menthone, both enantiomeric cycloadducts were synthesized in excellent yield. Removing the chiral auxiliary and the N-benzyl group delivered a series of enantiopure 4-hydroxy-3-glycinyl-pyrrolidine derivatives in 3-5 steps and 36 to 81 overall yields. Using two other achiral nitrones, shorter routes to racemic analogues were developed. Two of the synthesized compounds markedly lowered extracellular glutamate level and modestly interacted with cannabinoid type-1 receptors. As these two neuroactive compounds were devoid of in vitro toxicity and did not cross the blood brain interface, they might represent potential pharmacological agents to target peripheral organs.

  17. A Submarine Journey: The Pyrrole-Imidazole Alkaloids

    Directory of Open Access Journals (Sweden)

    Alessandra Scolaro

    2009-11-01

    Full Text Available In his most celebrated tale “The Picture of Dorian Gray”, Oscar Wilde stated that “those who go beneath the surface do so at their peril”. This sentence could be a prophetical warning for the practitioner who voluntarily challenges himself with trying to synthesize marine sponge-deriving pyrrole-imidazole alkaloids. This now nearly triple-digit membered community has been growing exponentially in the last 20 years, both in terms of new representatives and topological complexity − from simple, achiral oroidin to the breathtaking 12-ring stylissadines A and B, each possessing 16 stereocenters. While the biosynthesis and the role in the sponge economy of most of these alkaloids still lies in the realm of speculations, significant biological activities for some of them have clearly emerged. This review will account for the progress in achieving the total synthesis of the more biologically enticing members of this class of natural products.

  18. A submarine journey: the pyrrole-imidazole alkaloids.

    Science.gov (United States)

    Forte, Barbara; Malgesini, Beatrice; Piutti, Claudia; Quartieri, Francesca; Scolaro, Alessandra; Papeo, Gianluca

    2009-11-27

    In his most celebrated tale "The Picture of Dorian Gray", Oscar Wilde stated that "those who go beneath the surface do so at their peril". This sentence could be a prophetical warning for the practitioner who voluntarily challenges himself with trying to synthesize marine sponge-deriving pyrrole-imidazole alkaloids. This now nearly triple-digit membered community has been growing exponentially in the last 20 years, both in terms of new representatives and topological complexity--from simple, achiral oroidin to the breathtaking 12-ring stylissadines A and B, each possessing 16 stereocenters. While the biosynthesis and the role in the sponge economy of most of these alkaloids still lies in the realm of speculations, significant biological activities for some of them have clearly emerged. This review will account for the progress in achieving the total synthesis of the more biologically enticing members of this class of natural products.

  19. A Submarine Journey: The Pyrrole-Imidazole Alkaloids †

    Science.gov (United States)

    Forte, Barbara; Malgesini, Beatrice; Piutti, Claudia; Quartieri, Francesca; Scolaro, Alessandra; Papeo, Gianluca

    2009-01-01

    In his most celebrated tale “The Picture of Dorian Gray”, Oscar Wilde stated that “those who go beneath the surface do so at their peril”. This sentence could be a prophetical warning for the practitioner who voluntarily challenges himself with trying to synthesize marine sponge-deriving pyrrole-imidazole alkaloids. This now nearly triple-digit membered community has been growing exponentially in the last 20 years, both in terms of new representatives and topological complexity – from simple, achiral oroidin to the breathtaking 12-ring stylissadines A and B, each possessing 16 stereocenters. While the biosynthesis and the role in the sponge economy of most of these alkaloids still lies in the realm of speculations, significant biological activities for some of them have clearly emerged. This review will account for the progress in achieving the total synthesis of the more biologically enticing members of this class of natural products. PMID:20098608

  20. Polarimetric scattering and transmitting of the Stokes vector from a layer of chiral small spheroids

    Institute of Scientific and Technical Information of China (English)

    常梅; 金亚秋

    2002-01-01

    To measure fully polarimetric scattering from random chiral small spheroids,the 2 × 2 dimensional (2 × 2-D) complex scattering amplitude matrix of randomly oriented,chiral small spheroid is derived.Polarimetric scattering from a bounded layer of non-uniformly oriented,chirally-active small spheroids in the Mueller matrix solution is obtained.Co-polarized and cross-polarized backscattering and polarization degree for any polarized incidence (X,ψ) are numerically calculated.Transmitting of coherent Stokes parameters through the layer are also discussed.Either non-uniform orientation or chirality can yield non-diagonal extinction matrix κe and full eigenmatrix E due to the fact of forward depolarized-scattering functions , ≠ 0.Comparisons of fully polarimetric scattering from the chiral and achiral particulate media demonstrate the chirality effect on wave scattering and transmitting.``

  1. Postmortem Femoral Blood Concentrations of Risperidone

    DEFF Research Database (Denmark)

    Linnet, Kristian; Johansen, Sys Stybe

    2014-01-01

    Postmortem femoral blood concentrations of the antipsychotic drug risperidone and the active metabolite 9-hydroxyrisperidone were determined by an achiral LC-MS/MS method in 38 cases. The cause of death was classified as unrelated to risperidone in 30 cases, in which the sum of the concentration of...... the drug and metabolite ranged from below the limit of quantification to 0.058 mg/kg (median 0.0098 mg/kg). This concentration range, which largely corresponds to published in vivo plasmalevels under therapy, may serve as a reference for judgment of postmortem cases involving risperidone. In one case......, risperidone was judged to be a contributing factor to death, and the sum of concentrations was 0.29 mg/kg. This concentration is of the same order of magnitude as observed for plasma levels in clinical intoxication cases. For the remaining seven cases, the cause of death was unclear. The measurements observed...

  2. Enantioselective Degradation of Rac-Metolachlor and S-Metolachlor in Soil

    Institute of Scientific and Technical Information of China (English)

    MA Yun; LIU Wei-Ping; WEN Yue-Zhong

    2006-01-01

    Separation of chiral enantiomers and the dissipation of rac-metolachlor and S-metolachlor in soil were evaluated using achiral high-performance liquid chromatography (HPLC) and chiral gas chromatography (GC) methods. Under the experimental conditions the possible metabolite was considered to be N-(2-ethyl-6-methyl-phenyl)-2-hydroxy-acetamide.Because of the presence of two chiral elements (asymmetrically substituted carbon and chiral axis), the baseline separation of metolachlor enantiomers was not achieved. S-metolachlor degraded faster in soil than rac-metolachlor. After a 42-day incubation, 73.4% of rac-metolachlor and 90.0% of S-metolachlor were degraded. However, due to the absence of biological processes the degradation process in sterilized soil showed no enantioselectivity. The results indicated that enantioselective degradations could greatly affect the environmental fate of metolachlor and should be considered when the environmental behavior of these compounds was assessed.

  3. Large Enhancement of Circular Dichroism Using an Embossed Chiral Metamaterial

    CERN Document Server

    Mousavi, S Hamed Shams; El-Sayed, Mostafa A; Eftekhar, Ali A; Adibi, Ali

    2016-01-01

    In the close vicinity of a chiral nanostructure, the circular dichroism of a biomolecule could be greatly enhanced, due to the interaction with the local superchiral fields. Modest enhancement of optical activity using a planar metamaterial, with some chiral properties, and achiral nanoparticles has been previously reported. A more substantial chirality enhancement can be achieved in the local filed of a chiral nanostructure with a three-dimensional arrangement. Using an embossed chiral nanostructure designed for chiroptical sensing, we measure the circular dichroism spectra of two biomolecules, Chlorophylls A and B, at the molecular level, using a simple polarization resolved reflection measurement. This experiment is the first realization of the on-resonance surface-enhanced circular dichroism, achieved by matching the chiral resonances of a strongly chiral metamaterial with that of a chiral molecule, resulting in an unprecedentedly large differential CD spectrum from a monolayer of a chiral material.

  4. Punctuated Chirality

    CERN Document Server

    Gleiser, Marcelo; Walker, Sara Imari

    2008-01-01

    Most biomolecules occur in mirror, or chiral, images of each other. However, life is homochiral: proteins contain almost exclusively levorotatory (L) amino acids, while only dextrorotatory (R) sugars appear in RNA and DNA. The mechanism behind this fundamental asymmetry of life remains an open problem. Coupling the spatiotemporal evolution of a general autocatalytic polymerization reaction network to external environmental effects, we show through a detailed statistical analysis that high intensity and long duration events may drive achiral initial conditions towards chirality. We argue that life's homochirality resulted from sequential chiral symmetry breaking triggered by environmental events, thus extending the theory of punctuated equilibrium to the prebiotic realm. Applying our arguments to other potentially life-bearing planetary platforms, we predict that a statistically representative sampling will be racemic on average.

  5. Stirring competes with chemical induction in chiral selection of Langmuir monolayer domains

    Directory of Open Access Journals (Sweden)

    Petit-Garrido Nuria

    2013-08-01

    Full Text Available Chirality, the absence of mirror symmetry, can be equally invoked in relation to physical forces and chemical induction processes, yet a competition between these two types of influences is rarely reported. Here, we employ Langmuir monolayers of azobenzene surfactants as a prototypical self-assembled two-dimensional system in which chiral selection is controlled by the combined independent action of a chiral dopant and vortical stirring. The two effects can be arbitrarily coupled, either constructively or destructively, leading to a situation of perfect compensation. The induced enantiomorphic excess is measured in terms of the statistical imbalance of an ensemble of sub-millimeter monolayer domains, where achiral molecules self-assemble with a well-defined orientational chirality, which is unambiguously resolved using Brewster angle microscopy.

  6. Universal Spin-Momentum Locked Optical Forces

    CERN Document Server

    Kalhor, Farid; Jacob, Zubin

    2015-01-01

    Evanescent electromagnetic waves possess spin-momentum locking, where the direction of propagation (momentum) is locked to the inherent polarization of the wave (transverse spin). We study the optical forces arising from this universal phenomenon and show that the fundamental origin of recently reported non-trivial optical chiral forces is spin-momentum locking. For evanescent waves, we show that the direction of energy flow, direction of decay, and direction of spin follow a right hand rule for three different cases of total internal reflection, surface plasmon polaritons, and $HE_{11}$ mode of an optical fiber. Furthermore, we explain how the recently reported phenomena of lateral optical force on chiral and achiral particles is caused by the transverse spin of the evanescent field and the spin-momentum locking phenomenon. Finally, we propose an experiment to identify the unique lateral forces arising from the transverse spin in the optical fiber and point to fundamental differences of the spin density from...

  7. Diastereomeric liquid crystal domains at the mesoscale

    Science.gov (United States)

    Chen, Dong; Tuchband, Michael R.; Horanyi, Balazs; Korblova, Eva; Walba, David M.; Glaser, Matthew A.; Maclennan, Joseph E.; Clark, Noel A.

    2015-08-01

    In many technologies used to achieve separation of enantiomers, chiral selectors are designed to display differential affinity for the two enantiomers of a chiral compound. Such complexes are diastereomeric, differing in structure and free energy for the two enantiomers and enabling chiral discrimination. Here we present evidence for strong diastereomeric interaction effects at the mesoscale, manifested in chiral liquid crystal guest materials confined in a chiral, nanoporous network of semi-crystalline helical nanofilaments. The nanoporous host is itself an assembly of achiral, bent-core liquid crystal molecules that phase-separate into a conglomerate of 100 micron-scale, helical nanofilament domains that differ in structure only in the handedness of their homogeneous chirality. With the inclusion of a homochiral guest liquid crystal, these enantiomeric domains become diastereomeric, exhibiting unexpected and markedly different mesoscale structures and orientation transitions producing optical effects in which chirality has a dominant role.

  8. Stereoselective Metabolism of the Sterol Biosynthesis Inhibitor Fungicides Fenpropidin, Fenpropimorph, and Spiroxamine in Grapes, Sugar Beets, and Wheat.

    Science.gov (United States)

    Buerge, Ignaz J; Krauss, Jürgen; López-Cabeza, Rocío; Siegfried, Werner; Stüssi, Michael; Wettstein, Felix E; Poiger, Thomas

    2016-07-01

    Metabolism of chiral pesticides in crops is typically studied using achiral analytical methods and, consequently, the stereoisomer composition of residues is unknown. In this study, we developed an enantioselective GC-MS/MS method to quantify residues of the fungicides fenpropidin, fenpropimorph, and spiroxamine in plant matrices. In field trials, the fungicides were applied to grapevines, sugar beets, or wheat. Fenpropidin was metabolized with no or only weak enantioselectivity. For fenpropimorph, slightly enantioselective metabolism was observed in wheat but more pronounced in sugar beets. This enantioselectivity was due to different rates of metabolism and not due to interconversion of enantiomers. The four stereoisomers of spiroxamine were also metabolized at different rates, but selectivity was only found between diastereomers and not between enantiomers. trans-Spiroxamine was preferentially degraded in grapes and cis-spiroxamine in wheat. These findings may affect the consumer dietary risk assessment because toxicological end points were determined using racemic test substances. PMID:27248479

  9. Optical detection of PNA/DNA hybridization in resonant porous silicon-based devices

    Science.gov (United States)

    Rotiroti, Lucia; Arcari, Paolo; Lamberti, Annalisa; Sanges, Carmen; De Tommasi, Edoardo; Rea, Ilaria; Rendina, Ivo; De Stefano, Luca

    2008-04-01

    The development of label-free optical biosensors could have a great impact on life sciences as well as on screening techniques for medical and environmental applications. Peptide nucleic acid (PNA) is a nucleic acid analog in which the sugar phosphate backbone of natural nucleic acid has been replaced by a synthetic peptide backbone, resulting in an achiral and uncharged mimic. Due to the uncharged nature of PNA, PNA-DNA duplexes show a better thermal stability respect the DNA-DNA equivalents. In this work, we used an optical biosensor, based on the porous silicon (PSi) nanotechnology, to detect PNA-DNA interactions. PSi optical sensors are based on changes of reflectivity spectrum when they are exposed to the target analytes. The porous silicon surface was chemically modified to covalently link the PNA which acts as a very specific probe for its ligand (cDNA).

  10. PNA(T).DNA(AT) triplexes with Hoogsteen base pairing are more favorable

    Institute of Scientific and Technical Information of China (English)

    XIE Jun; LIU Ciquan; QU Lianghu

    2003-01-01

    Peptide nucleic acids (PNAs) are nucleic acid analogs with the deoxyribose phosphate backbone replaced by pseudo-peptide polymers to which the nucleobases are linked. The achiral, uncharged and rather flexible properties of the peptide backbone permit peptide nucleic acids more potential than oligonucleotides in application to antisence and antigenic reagents. The process of PNA binding to DNA duplex and forming triplex is the first step of PNA interacting with PNA. But there are no PNA.2DNA triplex crystal data up to date and little has been reported on the structure features and the force of the PNA.2DNA triplex. In this work,PNA(T).DNA(AT) triplexes are successfully built and the structures and forces to stabilize the triplex after optimizations and molecule dynamics are systematically examined,which are expected to aid in the application of PNAs as anticense and antigene agents.

  11. Synthesis of Cis,syndiotactic A-alt-B Copolymers from Two Enantiomerically Pure Trans-2,3-Disubstituted-5,6-Norbornenes

    Science.gov (United States)

    2016-01-01

    Cis,syndiotacticA-alt-B copolymers, where A and B are two enantiomerically pure trans-2,3-disubstituted-5,6-norbornenes with “opposite” chiralities, can be prepared with stereogenic-at-metal initiators of the type M(NR)(CHR′)(OR”)(pyrrolide). Formation of a high percentage of alternating AB copolymer linkages relies on an inversion of chirality at the metal with each propagating step and a relatively fast formation of an AB sequence as a consequence of a preferred diastereomeric relationship between the chirality at the metal and the chirality of the monomer. This approach to formation of an alternating AB copolymer contrasts dramatically with the principle of forming AB copolymers from achiral monomers and catalysts.

  12. Engineering Cyclodextrin Clicked Chiral Stationary Phase for High-Efficiency Enantiomer Separation

    Science.gov (United States)

    Tang, Jian; Zhang, Shapopeng; Lin, Yuzhou; Zhou, Jie; Pang, Limin; Nie, Xuemei; Zhou, Baojing; Tang, Weihua

    2015-08-01

    The separation of racemic molecules is of crucial significance not only for fundamental research but also for technical application. Enantiomers remain challenging to be separated owing to their identical physical and chemical properties in achiral environments. Chromatographic techniques employing chiral stationary phases (CSPs) have been developed as powerful tools for the chiral analysis and preparation of pure enantiomers, most of which are of biological and pharmaceutical interests. Here we report our efforts in developing high-performance phenylcarbamated cyclodextrin (CD) clicked CSPs. Insights on the impact of CD functionalities in structure design are provided. High-efficiency enantioseparation of a range of aryl alcohols and flavanoids with resolution values (Rs) over 10 were demonstrated by per(3-chloro-4-methyl)phenylcarbamated CD clicked CSP. Comparison study and molecular simulations suggest the improved enantioselectivity was attributed to higher interactions energy difference between the complexes of enantiomers and CSPs with phenylcarbamated CD bearing 3-chloro and 4-methyl functionalities.

  13. Transfer of chirality from adsorbed chiral molecules to the substrates highlighted by circular dichroism in angle-resolved valence photoelectron spectroscopy

    DEFF Research Database (Denmark)

    Contini, G.; Turchini, S.; Sanna, Simone;

    2012-01-01

    state, that the presence of molecular chiral domains induces asymmetry in the interaction with the substrate and locally transfers the chiral character to the underlying metal atoms participating in the adsorption process; combined information related to the asymmetry of the initial electronic state......Studies of self-assembled chiral molecules on achiral metallic surfaces have mostly focused on the determination of the geometry of adsorbates and their electronic structure. The aim of this paper is to provide direct information on the chirality character of the system and on the chirality......, which is expected to be chiral, and the final electronic state, which locally probes the asymmetry of the potential, has been obtained. Identification of chirality in the adsorption footprint sheds new light on the transfer of chirality from a chiral modifier to a symmetric metal surface and represents...

  14. Chiral optical fields: A unified formulation of helicity scattered from particles and dichroism enhancement

    CERN Document Server

    Nieto-Vesperinas, Manuel

    2016-01-01

    We establish a general unified formulation which, using the optical theorem of electromagnetic helicity, shows that dichorism is a phenomenon arising in any scattering -or diffraction- process, elastic or not, of chiral electromagnetic fields by objects either chiral or achiral. It is shown how this approach paves the way to overcoming well-known limitations of standard circular dichroism, like its weak signal or the difficulties of using it with magnetodielectric particles. Based on the angular spectrum representation of optical fields with only right circular or left circular plane waves, we introduce beams with transverse elliptic polarization and posessing a longitudinal component. Then our formulation for general optical fields shows how to enhance the helicity, (and therefore the dichroism signal), versus the energy of the light scattered or emitted by a particle, or viceversa.

  15. Synthesis of Stable and Soluble One-Handed Helical Homopoly(substituted acetylenes without the Coexistence of Any Other Chiral Moieties via Two-Step Polymer Reactions in Membrane State: Molecular Design of the Starting Monomer

    Directory of Open Access Journals (Sweden)

    Takashi Kaneko

    2012-01-01

    Full Text Available A soluble and stable one-handed helical poly(substituted phenylacetylene without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer followed by two-step polymer reactions in membrane state: (1 removing the chiral groups (desubstitution; and (2 introduction of achiral long alkyl groups at the same position as the desubstitution to enhance the solubility of the resulting one-handed helical polymer (resubstitution. The starting chiral monomer should have four characteristic substituents: (i a chiral group bonded to an easily hydrolyzed spacer group; (ii two hydroxyl groups; (iii a long rigid hydrophobic spacer between the chiral group and the polymerizing group; (iv a long achiral group near the chiral group. As spacer group a carbonate ester was selected. The two hydroxyl groups formed intramolecular hydrogen bonds stabilizing a one-handed helical structure in solution before and after the two-step polymer reactions in membrane state. The rigid long hydrophobic spacer, a phenylethynylphenyl group, enhanced the solubility of the starting polymer, and realized effective chiral induction from the chiral side groups to the main chain in the asymmetric-induced polymerization. The long alkyl group near the chiral group avoided shrinkage of the membrane and kept the reactivity of resubstitution in membrane state after removing the chiral groups. The g value (g = ([θ]/3,300/ε for the CD signal assigned to the main chain in the obtained final polymer was almost the same as that of the starting polymer in spite of the absence of any other chiral moieties. Moreover, since the one-handed helical structure was maintained by the intramolecular hydrogen bonds in a solution, direct observation of the one-handed helicity of the final homopolymer has been realized in CD for the solution for the first time.

  16. Diastereo- and enantioseparation of a Nα-Boc amino acid with a zwitterionic quinine-based stationary phase: Focus on the stereorecognition mechanism

    International Nuclear Information System (INIS)

    Highlights: • The ZWIX(+) column allowed getting the Boc-Aph(Hor)-OH (1) isomeric peaks resolved. • ECD studies and molecular dynamic simulations allowed to assign the elution order. • Molecular descriptors revealed the active role of achiral elements of the CSP. - Abstract: A chiral chromatography method enabling the simultaneous diastereo- and enantioseparation of Nα-Boc-N4-(hydroorotyl)-4-aminophenylalanine [Boc-Aph(Hor)-OH, 1] was optimized with a quinine-based zwitterionic stationary phase. The polar-ionic eluent system consisting of ACN:MeOH:water—49.7:49.7:0.6 (v/v/v) with formic acid (4.0 mM) and diethylamine (2.5 mM), allowed the successful separation of the four acid stereoisomers: αD,D-/D,L-1 = 1.08; αD,L-/L,D-1 = 1.08; αL,D-/L,L-1 = 1.40. According to the in-house developed synthetic procedure and the recorded electronic circular dichroism spectra, the following stereoisomeric elution order was readily established in the optimal chromatographic conditions: D,D-1 < D,L-1 < L,D-1 < L,L-1. With the aim of better understanding the molecular basis of the retention behaviour of the four stereoisomers in the employed chromatographic system and conditions, a computational protocol consisting in molecular dynamics simulations was applied. The use of the three descriptors INTER (in kcal mol−1, encoding for the interaction energy between the selector SO unit and the whole system), INTER-SA (in kcal mol−1, encoding for the interaction energy between SO and the sole selectand SA), and SELF (in kcal mol−1, encoding for the conformational energy of SA relative to its minimum energy registered by the collected snapshots) revealed the active role of achiral sub-structural elements of the chiral stationary phase and eluent components in the overall stereorecognition mechanism

  17. Ultra-fast high-efficiency enantioseparations by means of a teicoplanin-based chiral stationary phase made on sub-2 μm totally porous silica particles of narrow size distribution.

    Science.gov (United States)

    Ismail, Omar H; Ciogli, Alessia; Villani, Claudio; De Martino, Michela; Pierini, Marco; Cavazzini, Alberto; Bell, David S; Gasparrini, Francesco

    2016-01-01

    A new ultra-high performance teicoplanin-based stationary phase was prepared starting from sub-2 μm totally porous silica particles of narrow size distribution. Columns of different lengths were packed at high pressure and a deep and systematic evaluation of kinetic performance, in terms of van Deemter analysis, was performed under different elution conditions (HILIC, POM, RP and NP) by using both achiral and chiral probes. For the achiral probes, the efficiency of the columns at the minimum of the van Deemter curves were very high leading to some 278,000, 270,000, 262,000 and 232,000 plates/m in hydrophilic interaction liquid chromatography (HILIC), polar organic mode (POM), normal phase (NP) and reversed phase (RP) respectively. The lowest plate height, Hmin=3.59 μm (h(/)=1.89), was obtained under HILIC conditions at a flow rate of 1.4 mL/min. Efficiency as high as 200,000-250,000 plates/m (at the optimum flow rate) was obtained in the separation of the enantiomers of chiral probes under HILIC/POM conditions. N-protected amino acids, α-aryloxy acids, herbicides, anti-inflammatory agents were baseline separated on short (2-cm) and ultra-short (1-cm) columns, with analysis time in the order of 1 min. The enantiomers of N-BOC-d,l-methionine were successfully baseline separated in only 11s in HILIC mode. Several examples of fast and efficient resolutions in sub/supercritical fluid chromatography were also obtained for a range of chiral carboxylic acids. PMID:26687167

  18. Hydrodynamic-induced enantiomeric enrichment of self-assemblies: Role of the solid-liquid interface in chiral nucleation and seeding

    Science.gov (United States)

    Raudino, Antonio; Pannuzzo, Martina

    2012-10-01

    A simple hydrodynamic model has been developed to explain the experimentally observed chirality selection in stirred solutions of self-assembling achiral dyes. Selection depends on the stirring direction: the dichroic signal reverses its shape in clockwise or anti-clockwise rotations. Our model investigates the possible role of the liquid-solid interface in nucleating, growing, and transferring to the bulk of chiral seeds. The nucleation step requires a double modulation of the hydrodynamic field exhibiting different velocity along two orthogonal axes. Under a series of restrictions, such a condition is easily met at the solid-liquid interface and it is dictated by the boundary conditions and geometry of stirring. In stagnant conditions, growing helices made-up of self-assembled achiral dyes have no chiral preference forming a racemic mixture that contains identical amount of right-handed (R) and left-handed (L) configurations. The application of a hydrodynamic torque (related to the velocity gradient and width of the helix) breaks down the original symmetry, a further velocity gradient perpendicular to the first one ensures, after averaging, a slightly different population of R and L conformations. The yields of the hydrodynamic-induced chirality excess are extremely tiny, hence the suggested mechanism is significant only if next chirality amplification processes are efficient. Again, hydrodynamics provides a tool for the detachment of weakly bound aggregates once they have reached a critical length. Aggregates are transported in the bulk where the ripening process goes to completion. The efficiency of the surface catalytic effect strongly depends on the aggregate-surface sticking energy, reaching a maximum at intermediate sticking energies (of order of 10 kT). Numerical estimates show that the proposed mechanism is rather efficient, giving rise to entatiomeric excesses near (but smaller than) those experimentally found.

  19. Principles of self-assembly of helical pores from dendritic dipeptides

    Science.gov (United States)

    Percec, Virgil; Dulcey, Andrés E.; Peterca, Mihai; Ilies, Monica; Nummelin, Sami; Sienkowska, Monika J.; Heiney, Paul A.

    2006-01-01

    The self-assembly of the dendritic dipeptides (4-3,4-3,5)nG2-CH2-Boc-l-Tyr-l-Ala-OMe and their achiral dendritic alcohol (4-3,4-3,5)nG2-CH2OH precursors, both with n = 1–16, where n represents the number of methylenic units in the alkyl groups of the dendron, are reported. All chiral dendritic dipeptides and achiral dendritic alcohols self-assemble into helical porous columns that are stable in both solution and solid state. The pore diameter (Dpore) of the columns self-assembled from dendritic dipeptides is ≈10 Å larger than that of structures assembled from dendritic alcohols. The increase of the Dpore at the transition from dendritic alcohol to dendritic dipeptide is accompanied by a decreased solid angle of the building block. This trend is in agreement with previous pore size-solid angle dependences observed with different protective groups of the dipeptide and primary structures of the dendron. However, within the series of dendritic alcohols and dendritic dipeptides with various n, the Dpore increases when the solid angle increases. The results of these investigations together with those of previous studies on the role of dipeptide stereochemistry and protective groups on this self-assembly process provide the molecular principles required to program the construction of supramolecular helical pores with diameter controlled at the Å level from a single dendritic dipeptide architecture. These principles are expected to be valid for libraries of dendritic dipeptides based on dendrons and dipeptides with various primary structures. PMID:16469843

  20. How to control optical activity in organic-silver hybrid nanoparticles

    Science.gov (United States)

    Hidalgo, Francisco; Noguez, Cecilia

    2016-07-01

    The mechanisms that originate and control optical activity in organic-metal hybrid nanoparticles (NPs) are identified using a time-perturbed density functional theory. Electronic circular dichroism (CD) is studied in terms of the intrinsic chirality of the ligands, the number of ligands and the induced chirality by the arrangement of the ligands on the NP. Left-handed cysteine and achiral methylthio ligands adsorbed on an icosahedral silver NP are investigated. The analysis of CD allows the identification of the spectral regions when the induced chirality by the ligand array dominates over the intrinsic chirality of the ligands, determining conditions for CD control and enlargement. These results would be significant in the discussion of experimental CD spectra of organic-metal hybrid NPs, which might allow the development of new strategies to improve the sensitivity of chiroptical spectroscopies for the identification of bio and organic molecules.The mechanisms that originate and control optical activity in organic-metal hybrid nanoparticles (NPs) are identified using a time-perturbed density functional theory. Electronic circular dichroism (CD) is studied in terms of the intrinsic chirality of the ligands, the number of ligands and the induced chirality by the arrangement of the ligands on the NP. Left-handed cysteine and achiral methylthio ligands adsorbed on an icosahedral silver NP are investigated. The analysis of CD allows the identification of the spectral regions when the induced chirality by the ligand array dominates over the intrinsic chirality of the ligands, determining conditions for CD control and enlargement. These results would be significant in the discussion of experimental CD spectra of organic-metal hybrid NPs, which might allow the development of new strategies to improve the sensitivity of chiroptical spectroscopies for the identification of bio and organic molecules. Electronic supplementary information (ESI) available. See DOI: 10.1039/C6

  1. Ultra-fast high-efficiency enantioseparations by means of a teicoplanin-based chiral stationary phase made on sub-2 μm totally porous silica particles of narrow size distribution.

    Science.gov (United States)

    Ismail, Omar H; Ciogli, Alessia; Villani, Claudio; De Martino, Michela; Pierini, Marco; Cavazzini, Alberto; Bell, David S; Gasparrini, Francesco

    2016-01-01

    A new ultra-high performance teicoplanin-based stationary phase was prepared starting from sub-2 μm totally porous silica particles of narrow size distribution. Columns of different lengths were packed at high pressure and a deep and systematic evaluation of kinetic performance, in terms of van Deemter analysis, was performed under different elution conditions (HILIC, POM, RP and NP) by using both achiral and chiral probes. For the achiral probes, the efficiency of the columns at the minimum of the van Deemter curves were very high leading to some 278,000, 270,000, 262,000 and 232,000 plates/m in hydrophilic interaction liquid chromatography (HILIC), polar organic mode (POM), normal phase (NP) and reversed phase (RP) respectively. The lowest plate height, Hmin=3.59 μm (h(/)=1.89), was obtained under HILIC conditions at a flow rate of 1.4 mL/min. Efficiency as high as 200,000-250,000 plates/m (at the optimum flow rate) was obtained in the separation of the enantiomers of chiral probes under HILIC/POM conditions. N-protected amino acids, α-aryloxy acids, herbicides, anti-inflammatory agents were baseline separated on short (2-cm) and ultra-short (1-cm) columns, with analysis time in the order of 1 min. The enantiomers of N-BOC-d,l-methionine were successfully baseline separated in only 11s in HILIC mode. Several examples of fast and efficient resolutions in sub/supercritical fluid chromatography were also obtained for a range of chiral carboxylic acids.

  2. A 3D chiral metal-organic framework based on left-handed helices containing 3-amino-1 H-1,2,4-triazole ligand

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Bing, E-mail: bliu_1203@163.com [College of Chemistry and Chemical Engineering, Shaanxi University of Sciences and Technology, Xi’an, 710021 Shaanxi (China); Yang, Tian-Yi [The High School Affricated to Shaanxi Normal University, Xi’an, 710061 Shaanxi (China); Feng, Hui-Jun; Zhang, Zong-Hui [Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an, 710062 Shaanxi (China); Xu, Ling, E-mail: xuling@snnu.edu.cn [Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an, 710062 Shaanxi (China)

    2015-10-15

    A chiral metal-organic framework, [Cu(atr)(OH)]·0.5H{sub 2}O·0.5en (1) (Hatr=3-amino-1 H-1,2,4-triazole, en=ethylenediamine), was constructed via diffusion reaction of the achiral Hatr ligand and CuSO{sub 4} as starting materials. Compound 1 crystallizes in the chiral space group P3{sub 2}21 and features a porous metal-organic framework with 44.1% solvent-accessible volume fabricated by left-handed helices with a pitch height of l{sub p}=10.442 Å. Six helices gather around in a cycle forming a large honeycomb channel with a 6.58 Å inner diameter. Cu(II) center and atr{sup ‒} ligand regarded as 3-connected nodes, compound 1 can be simplified to a 3-c uninodal (4.12{sup 2}) (qtz-h) topological network. A gradual decreasing in the magnetic moment depending on temperature decreasing indicates an antiferromagnetic interaction in 1. The powder XRD confirms the bulk sample is a single crystal pure phase, and the thermogravimetric analysis shows the thermal stability of 1 is up to ca. 240 °C. - Highlights: • The present 3D chiral MOF is built from achiral Hatr ligand. • Six left-handed helices gather into a honeycomb channel in chiral sp P3{sub 2}21. • Compound 1 shows a 3-c uninodal (4.12{sup 2}) or qtz-h topological network. • Compound 1 indicates an antiferromagnetic interaction.

  3. Chirality and its spontaneous symmetry breaking in two liquid crystal systems

    Science.gov (United States)

    Kang, Louis

    Chirality, or handedness, is a key concept spanning all fields of natural science, from biology to mathematics. Chiral structures can arise from achiral building blocks that lack a handedness if their assembly is unstable to chiral deformations, a phenomenon called spontaneous symmetry breaking. We theoretically study the role of chirality in two systems composed of liquid crystals dissolved or suspended in water, and our results match those obtained experimentally by our collaborators. In the first system, we study achiral liquid crystals whose Frank twist modulus is much lower than their splay and bend Frank moduli and which are confined in capillaries. Under homeotropic anchoring, their ground state configuration undergoes spontaneous chiral symmetry breaking when the twist modulus decreases enough relative to the splay and bend moduli. Under degenerate planar anchoring, a small twist-to-saddle-splay ratio of elastic moduli leads to degenerate twisted configurations even though an undeformed configuration is possible. Measuring the twist profile of an experimental system produces a value for the saddle-splay constant, which has been difficult to achieve previously. Under either boundary condition, domain walls and point defects, whose topological charges depend on chirality, separate domains with different degenerate configurations, and certain ones are energetically preferred over others. In the second system, we study filamentous viruses acting as colloidal liquid crystals under the influence of depletion, which promotes condensation of the viruses into 2D colloidal monolayers. These membranes have tunable chirality and show a rich array of emergent behaviors, including a transition from a circular shape to a striking starfish shape upon changing the chirality of constituent viruses, partial coalescence via domain walls through which the viruses twist by 180 degrees, and phase-separated rafts of a particular size when two virus species with different lengths

  4. Diastereo- and enantioseparation of a N{sup α}-Boc amino acid with a zwitterionic quinine-based stationary phase: Focus on the stereorecognition mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Ianni, Federica; Carotti, Andrea; Marinozzi, Maura; Marcelli, Gloria [Department of Pharmaceutical Sciences, University of Perugia, Via Fabretti 48, 06123 Perugia (Italy); Di Michele, Alessandro [Department of Physics and Geology, University of Perugia, Via Pascoli 1, 06123 Perugia (Italy); Sardella, Roccaldo, E-mail: roccaldo.sardella@unipg.it [Department of Pharmaceutical Sciences, University of Perugia, Via Fabretti 48, 06123 Perugia (Italy); Lindner, Wolfgang [Department of Analytical Chemistry, University of Vienna, Währinger Strasse 38, 1090 Vienna (Austria); Natalini, Benedetto [Department of Pharmaceutical Sciences, University of Perugia, Via Fabretti 48, 06123 Perugia (Italy)

    2015-07-23

    Highlights: • The ZWIX(+) column allowed getting the Boc-Aph(Hor)-OH (1) isomeric peaks resolved. • ECD studies and molecular dynamic simulations allowed to assign the elution order. • Molecular descriptors revealed the active role of achiral elements of the CSP. - Abstract: A chiral chromatography method enabling the simultaneous diastereo- and enantioseparation of N{sup α}-Boc-N{sup 4}-(hydroorotyl)-4-aminophenylalanine [Boc-Aph(Hor)-OH, 1] was optimized with a quinine-based zwitterionic stationary phase. The polar-ionic eluent system consisting of ACN:MeOH:water—49.7:49.7:0.6 (v/v/v) with formic acid (4.0 mM) and diethylamine (2.5 mM), allowed the successful separation of the four acid stereoisomers: α{sub D,D-/D,L-1} = 1.08; α{sub D,L-/L,D-1} = 1.08; α{sub L,D-/L,L-1} = 1.40. According to the in-house developed synthetic procedure and the recorded electronic circular dichroism spectra, the following stereoisomeric elution order was readily established in the optimal chromatographic conditions: D,D-1 < D,L-1 < L,D-1 < L,L-1. With the aim of better understanding the molecular basis of the retention behaviour of the four stereoisomers in the employed chromatographic system and conditions, a computational protocol consisting in molecular dynamics simulations was applied. The use of the three descriptors INTER (in kcal mol{sup −1}, encoding for the interaction energy between the selector SO unit and the whole system), INTER-SA (in kcal mol{sup −1}, encoding for the interaction energy between SO and the sole selectand SA), and SELF (in kcal mol{sup −1}, encoding for the conformational energy of SA relative to its minimum energy registered by the collected snapshots) revealed the active role of achiral sub-structural elements of the chiral stationary phase and eluent components in the overall stereorecognition mechanism.

  5. The real gordian knot: racemic mixtures versus pure enantiomers.

    Science.gov (United States)

    Szelenyi, I; Geisslinger, G; Polymeropoulos, E; Paul, W; Herbst, M; Brune, K

    1998-04-01

    Many drugs exist as asymmetric three-dimensional (chiral) molecules and will therefore have several stereoisomers. There are often pharmacodynamic, pharmacokinetic and/or toxicological differences between enantiomers. The choice between developing a racemate or single enantiomers depends on therapeutic advances and developmental costs involved. Regarding the target environment for drug intervention, even if natural physiological mediators are achiral, their receptors may demonstrate a preference for the (-)- or (+)-enantiomer of agonists or antagonists. It is also obvious that the majority of enzymes and channels are stereospecific, at least to a variable extent. From a pharmacokinetics point of view, chirality can have an influence on drug absorption, distribution, metabolism and elimination. With a few exceptions, toxicological differences between isomers of known drugs are less dramatic than thought to be and only seldom substantiate the necessity of a racemic switch. The pharmaceutical industry is currently very interested in the so-called "racemic switch." Before proceeding to a racemic switch it is necessary to determine if 1) it is chemically feasible to produce a single enantiomer; 2) a clinical advantage is obtainable through a racemic switch; and 3) a marketing advantage is obtainable. The real goal of a racemic switch should be the rational development of compounds that are profitable for the company and--first of all--beneficial for the patient. PMID:15616615

  6. Facts and fictions about polymorphism.

    Science.gov (United States)

    Cruz-Cabeza, Aurora J; Reutzel-Edens, Susan M; Bernstein, Joel

    2015-12-01

    We present new facts about polymorphism based on (i) crystallographic data from the Cambridge Structural Database (CSD, a database built over 50 years of community effort), (ii) 229 solid form screens conducted at Hoffmann-La Roche and Eli Lilly and Company over the course of 8+ and 15+ years respectively and (iii) a dataset of 446 polymorphic crystals with energies and properties computed with modern DFT-d methods. We found that molecular flexibility or size has no correlation with the ability of a compound to be polymorphic. Chiral molecules, however, were found to be less prone to polymorphism than their achiral counterparts and compounds able to hydrogen bond exhibit only a slightly higher propensity to polymorphism than those which do not. Whilst the energy difference between polymorphs is usually less than 1 kcal mol(-1), conformational polymorphs are capable of differing by larger values (up to 2.5 kcal mol(-1) in our dataset). As overall statistics, we found that one in three compounds in the CSD are polymorphic whilst at least one in two compounds from the Roche and Lilly set display polymorphism with a higher estimate of up to three in four when compounds are screened intensively. Whilst the statistics provide some guidance of expectations, each compound constitutes a new challenge and prediction and realization of targeted polymorphism still remains a holy grail of materials sciences.

  7. High-resolution polypeptide structure and dynamics in anisotropic environments: The gramicidin channel

    Energy Technology Data Exchange (ETDEWEB)

    Cross, T.A.; Lee, K.C.; Ketchem, R.R.; Hu, W.; Lazo, N.D.; Huo, S. [Florida State Univ., Tallahassee, FL (United States)

    1994-12-01

    To understand the details of macromolecular function, high-resolution structural and dynamic detail is essential. The polypeptide fold of the gramicidin channel has been effectively modeled for the past 20 years, yet the functional changes in conductance and channel lifetime associated with amino acid substitutions cannot be predicted. To accomplish this goal, high-resolution electrostatic modeling and the precise orientation of all dipoles are required. Furthermore, an enhanced knowledge of the complex molecular environment of this membrane-bound peptide is needed. An aqueous environment is relatively uniform and achiral. The membrane environment is very heterogenous and chiral. A knowledge of the interactions, specific and nonspecific, between peptide and lipid will aid in developing a better understanding of this environment. To accomplish this goal, it is necessary to study the peptide in an extended lipid bilayer, rather than in a vesicular or micellar form. These latter environments are likely to possess increased dynamics, increased water penetration, and distorted interactions between the polypeptide and membrane surface. To perform NMR studies on bilayer bound peptides, solid state NMR methods are required, and for specific site information, isotopic labels are incorporated using solid phase peptide synthesis.

  8. Benefit of liquid crystal moieties in the MIP technique.

    Science.gov (United States)

    Binet, Corinne; Ferrère, Sandrine; Lattes, Armand; Laurent, Elisabeth; Marty, Jean-Daniel; Mauzac, Monique; Mingotaud, Anne-Françoise; Palaprat, Guillaume; Weyland, Marie

    2007-05-15

    Several liquid crystalline imprinted materials have been synthesized from polysiloxanes or polyacrylates bearing mesogenic side-chains and low contents of cross-linkers. They were imprinted by various achiral or chiral templates, then tested for molecular recognition or assessed as specific catalysts. All mesogenic imprinted networks exhibit a much higher affinity towards the template than non-imprinted networks. On the other hand, the molecular trapping capacity was shown to be much greater than that of most of the previously studied non-mesomorphous systems. Moreover, it was shown that mesomorphic order provides significant enhancement to the bonding between the template and the liquid crystalline network and reinforces the shape memory of the imprinted cavities. Some of these materials were used to catalyze the isomerization of benzisoxazole. They exhibited an acceleration effect close to 100 between imprinted sites and non-imprinted ones. Lastly, cholesteric networks, that were imprinted by a chiral template, showed good properties for the enantiomer separation leading to an enantiomeric excess of 35% and a capacity of around 1 mmol g(-1). PMID:17456417

  9. Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

    Directory of Open Access Journals (Sweden)

    Hironori Izawa

    2010-07-01

    Full Text Available Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized.

  10. Characterization of pharmaceutically active compounds in Dongting Lake, China: Occurrence, chiral profiling and environmental risk.

    Science.gov (United States)

    Ma, Ruixue; Wang, Bin; Lu, Shaoyong; Zhang, Yizhe; Yin, Lina; Huang, Jun; Deng, Shubo; Wang, Yujue; Yu, Gang

    2016-07-01

    Twenty commonly used pharmaceuticals including eight chiral drugs were investigated in Dongting Lake, China. The contamination level was relatively low on a global scale. Twelve pharmaceuticals were identified. The most abundant compound was caffeine followed by diclofenac, DEET, mefenamic acid, fluoxetine, ibuprofen and carbamazepine with mean concentrations from 2.0 to 80.8ngL(-1). Concentrations between East and West Dongting Lake showed spatial difference, with the West Dongting Lake less polluted. The relatively high ratio of caffeine versus carbamazepine (over 50) may indicate there was possible direct discharge of domestic wastewater into the lake. This is the first study presenting a survey allowing for comprehensive analysis of multiclass achiral and chiral pharmaceuticals including beta-blockers, antidepressants and anti-inflammatory drugs in freshwater lake. The enantiomeric compositions presented racemic to weakly enantioselective, with the highest enantiomeric fraction (EF) of 0.63 for fluoxetine. Meanwhile, venlafaxine was identified and evaluated the environment risk in surface water in China for the first time. The results of risk assessment suggested that fluoxetine, venlafaxine and diclofenac acid might pose a significant risk to aquatic organisms in Dongting Lake. The resulting data will be useful to enrich the research of emerging pollutants in freshwater lake and stereochemistry for environment investigations. PMID:27016674

  11. Coherence specific signal detection via chiral pump-probe spectroscopy.

    Science.gov (United States)

    Holdaway, David I H; Collini, Elisabetta; Olaya-Castro, Alexandra

    2016-05-21

    We examine transient circular dichroism (TRCD) spectroscopy as a technique to investigate signatures of exciton coherence dynamics under the influence of structured vibrational environments. We consider a pump-probe configuration with a linearly polarized pump and a circularly polarized probe, with a variable angle θ between the two directions of propagation. In our theoretical formalism the signal is decomposed in chiral and achiral doorway and window functions. Using this formalism, we show that the chiral doorway component, which beats during the population time, can be isolated by comparing signals with different values of θ. As in the majority of time-resolved pump-probe spectroscopy, the overall TRCD response shows signatures of both excited and ground state dynamics. However, we demonstrate that the chiral doorway function has only a weak ground state contribution, which can generally be neglected if an impulsive pump pulse is used. These findings suggest that the pump-probe configuration of optical TRCD in the impulsive limit has the potential to unambiguously probe quantum coherence beating in the excited state. We present numerical results for theoretical signals in an example dimer system. PMID:27208941

  12. Controlling the stereochemistry and regularity of butanethiol self-assembled monolayers on au(111).

    Science.gov (United States)

    Yan, Jiawei; Ouyang, Runhai; Jensen, Palle S; Ascic, Erhad; Tanner, David; Mao, Bingwei; Zhang, Jingdong; Tang, Chunguang; Hush, Noel S; Ulstrup, Jens; Reimers, Jeffrey R

    2014-12-10

    The rich stereochemistry of the self-assembled monolayers (SAMs) of four butanethiols on Au(111) is described, the SAMs containing up to 12 individual C, S, or Au chiral centers per surface unit cell. This is facilitated by synthesis of enantiomerically pure 2-butanethiol (the smallest unsubstituted chiral alkanethiol), followed by in situ scanning tunneling microscopy (STM) imaging combined with density functional theory molecular dynamics STM image simulations. Even though butanethiol SAMs manifest strong headgroup interactions, steric interactions are shown to dominate SAM structure and chirality. Indeed, steric interactions are shown to dictate the nature of the headgroup itself, whether it takes on the adatom-bound motif RS(•)Au(0)S(•)R or involves direct binding of RS(•) to face-centered-cubic or hexagonal-close-packed sites. Binding as RS(•) produces large, organizationally chiral domains even when R is achiral, while adatom binding leads to rectangular plane groups that suppress long-range expression of chirality. Binding as RS(•) also inhibits the pitting intrinsically associated with adatom binding, desirably producing more regularly structured SAMs.

  13. Tailoring the chirality of light emission with spherical Si-based antennas.

    Science.gov (United States)

    Zambrana-Puyalto, Xavier; Bonod, Nicolas

    2016-05-21

    Chirality of light is of fundamental importance in several enabling technologies with growing applications in life sciences, chemistry and photodetection. Recently, some attention has been focused on chiral quantum emitters. Consequently, optical antennas which are able to tailor the chirality of light emission are needed. Spherical nanoresonators such as colloids are of particular interest to design optical antennas since they can be synthesized at a large scale and they exhibit good optical properties. Here, we show that these colloids can be used to tailor the chirality of a chiral emitter. To this purpose, we derive an analytic formalism to model the interaction between a chiral emitter and a spherical resonator. We then compare the performances of metallic and dielectric spherical antennas to tailor the chirality of light emission. It is seen that, due to their strong electric dipolar response, metallic spherical nanoparticles spoil the chirality of light emission by yielding achiral fields. In contrast, thanks to the combined excitation of electric and magnetic modes, dielectric Si-based particles feature the ability to inhibit or to boost the chirality of light emission. Finally, it is shown that dual modes in dielectric antennas preserve the chirality of light emission.

  14. Thermal conductivity of freestanding single wall carbon nanotube sheet by Raman spectroscopy.

    Science.gov (United States)

    Sahoo, Satyaprakash; Chitturi, Venkateswara Rao; Agarwal, Radhe; Jiang, Jin-Wu; Katiyar, Ram S

    2014-11-26

    Thermal properties of single wall carbon nanotube sheets (SWCNT-sheets) are of significant importance in the area of thermal management, as an isolated SWCNT possesses high thermal conductivity of the value about 3000 W m(-1) K(-1). Here we report an indirect method of estimating the thermal conductivity of a nanometer thick suspended SWCNT-sheet by employing the Raman scattering technique. Tube diameter size is examined by the transmissions electron microscopy study. The Raman analysis of the radial breathing modes predicts narrow diameter size distribution with achiral (armchair) symmetry of the constituent SWCNTs. From the first order temperature coefficient of the A1g mode of the G band along with the laser power dependent frequency shifting of this mode, the thermal conductivity of the suspended SWCNT-sheet is estimated to be about ∼18.3 W m(-1) K(-1). Our theoretical study shows that the thermal conductivity of the SWCNT-sheet has contributions simultaneously from the intratube and intertube thermal transport. The intertube thermal conductivity (with contributions from the van der Waals interaction) is merely around 0.7 W m(-1) K(-1), which is three orders smaller than the intratube thermal conductivity, leading to an abrupt decrease in the thermal conductivity of the SWCNT-sheet as compared to the reported value for isolated SWCNT.

  15. Chiral benzamidinate ligands in rare-earth-metal coordination chemistry.

    Science.gov (United States)

    Benndorf, Paul; Kratsch, Jochen; Hartenstein, Larissa; Preuss, Corinna M; Roesky, Peter W

    2012-11-01

    The treatment of the recently reported potassium salt (S)-N,N'-bis-(1-phenylethyl)benzamidinate ((S)-KPEBA) and its racemic isomer (rac-KPEBA) with anhydrous lanthanide trichlorides (Ln = Sm, Er, Yb, Lu) afforded mostly chiral complexes. The tris(amidinate) complex [{(S)-PEBA}(3)Sm], bis(amidinate) complexes [{Ln(PEBA)(2)(μ-Cl)}(2)] (Ln = Sm, Er, Yb, Lu), and mono(amidinate) compounds [Ln(PEBA)(Cl)(2)(thf)(n)] (Ln = Sm, Yb, Lu) were isolated and structurally characterized. As a result of steric effects, the homoleptic 3:1 complexes of the smaller lanthanide atoms Yb and Lu were not accessible. Furthermore, chiral bis(amidinate)-amido complexes [{(S)-PEBA}(2)Ln{N(SiMe(3))(2)}] (Ln = Y, Lu) were synthesized by an amine-elimination reaction and salt metathesis. All of these chiral bis- and tris(amidinate) complexes had additional axial chirality and they all crystallized as diastereomerically pure compounds. By using rac-PEBA as a ligand, an achiral meso arrangement of the ligands was observed. The catalytic activities and enantioselectivities of [{(S)-PEBA}(2)Ln{N(SiMe(3))(2)}] (Ln = Y, Lu) were investigated in hydroamination/cyclization reactions. A clear dependence of the rate of reaction and enantioselectivity on the ionic radius was observed, which showed higher reaction rates but poorer enantioselectivities for the yttrium compound. PMID:23015310

  16. Stereochemical diversity in lignan biosynthesis of Arctium lappa L.

    Science.gov (United States)

    Suzuki, Shiro; Umezawa, Toshiaki; Shimada, Mikio

    2002-06-01

    The stereochemistry of lignan biosynthesis in Arctium lappa L. is regulated organ-specifically. (+)-Secoisolariciresinol [81% enantiomeric excess (e.e.)] was isolated from A. lappa petioles. In sharp contrast, lignans whose predominant enantiomers have the opposite absolute configuration to that of (+)-secoisolariciresinol [i.e., (-)-matairesinol (>99% e.e.), (-)-arctigenin (>99% e.e.), and (-)-secoisolariciresinol (65% e.e.)] were isolated from seeds of the species. The stereochemical diversity of secoisolariciresinol was demonstrated with enzyme preparations from A. lappa petioles and seeds. Thus, a petiole enzyme preparation catalyzed the formation of (+)-pinoresinol (33% e.e.), (+)-lariciresinol (30% e.e.), and (+)-secoisolariciresinol (20% e.e.) from achiral coniferyl alcohol in the presence of NADPH and H202, whereas that from ripening seeds catalyzed the formation of (-)-pinoresinol (22% e.e.), (-)-lariciresinol (>99% e.e.), and (-)-secoisolariciresinol (38% e.e.) under the same conditions. In addition, the ripening seed enzyme preparation mediated the selective formation of the optically pure (>99% e.e.) (-)-enantiomer of matairesinol from racemic (+/-)-secoisolariciresinols in the presence of NADP. These results indicate that the stereochemical mechanism for lignan biosynthesis in A. lappa varies with organs, suggesting that multiple lignan-synthesizing isozymes are involved in the stereochemical control of lignan formation in A. lappa.

  17. Homochiral and meso figure eight knots and a Solomon link.

    Science.gov (United States)

    Ponnuswamy, Nandhini; Cougnon, Fabien B L; Pantoş, G Dan; Sanders, Jeremy K M

    2014-06-11

    A homochiral naphthalenediimide-based building block forms in water a disulfide library of macrocycles containing topological isomers. We attempted to identify each of these isomers, and explored the mechanisms leading to their formation. The two most abundant species of the library were assigned as a topologically chiral Solomon link (60% of the library, as measured by high-performance liquid chromatography (HPLC)) and a topologically achiral figure eight knot (18% by HPLC), competing products with formally different geometries but remarkably similar 4-fold symmetries. In contrast, a racemic mixture of building blocks gives the near-quantitative formation of another new and more stable structure, assigned as a meso figure eight knot. Taken together, these results seem to uncover a correlation between the point chirality of the building block used and the topological chirality of the major structure formed. These and the earlier discovery of a trefoil knot also suggest that the number of rigid components in the building block may translate into corresponding knot symmetry and could set the basis of a new strategy for constructing complex topologies. PMID:24831779

  18. Laser spectroscopy and mass spectrometry of biologically relevant systems: chiral discrimination

    Science.gov (United States)

    Piccirillo, Susanna; Satta, Mauro; Coreno, Marcello; Catone, Daniele; Rondino, Flaminia; Scuderi, Debora; Paladini, Alessandra; Speranza, Maurizio; Giardini, Anna

    2005-06-01

    Radical ions are open-shell elusive species of paramount importance in many organic reactions and in biological processes. Oxidative bond breaking and forming involving radical ions are common process taking place in asymmetric enzyme cavities. Side-chain Cα-CΒ bond fragmentation in the radical cations of aromatic alcohols is a common process in solution [1-3], whose efficiency is enhanced in polar solvents such as water. Hydrogen-bonding between the ion and the solvent in the relevant transition structure is thought as responsible of the rate acceleration [4]. Effects of achiral and chiral microsolvation on the radical cation of R-(+)-l-phenyl-l-propanol, have been investigated. The energy thresholds of the homolytic Cα-Cβ bond breaking of R-(+)-1-phenyl-1-propanol radical cation, its mono-hydrated cluster, and its clusters with (2R,3R)-(-)-2,3-butanediol and (2S,3S)-(+)-2,3-butanediol have been studied through two color Resonant Two Photon Ionization, Photodissociation and Mass Spectrometry. The barrier of the Cα-Cβ fragmentation is appreciably higher for the unsolvated molecular ion than for its adducts with solvent molecules. Moreover, marked differences in the ethyl loss fragmentation energy are observed for the clusters with water and with the two diols. In particular the homochiral cluster with (2R, 3R)-(-)-2,3-butanediol exhibits a fragmentation barrier higher than that of the corresponding heterochiral adduct with (25, 35)-(+)-2,3-butanediol.

  19. Dynamic localization of electronic excitation in photosynthetic complexes revealed with chiral two-dimensional spectroscopy

    Science.gov (United States)

    Fidler, Andrew F.; Singh, Ved P.; Long, Phillip D.; Dahlberg, Peter D.; Engel, Gregory S.

    2014-02-01

    Time-resolved ultrafast optical probes of chiral dynamics provide a new window allowing us to explore how interactions with such structured environments drive electronic dynamics. Incorporating optical activity into time-resolved spectroscopies has proven challenging because of the small signal and large achiral background. Here we demonstrate that two-dimensional electronic spectroscopy can be adapted to detect chiral signals and that these signals reveal how excitations delocalize and contract following excitation. We dynamically probe the evolution of chiral electronic structure in the light-harvesting complex 2 of purple bacteria following photoexcitation by creating a chiral two-dimensional mapping. The dynamics of the chiral two-dimensional signal directly reports on changes in the degree of delocalization of the excitonic states following photoexcitation. The mechanism of energy transfer in this system may enhance transfer probability because of the coherent coupling among chromophores while suppressing fluorescence that arises from populating delocalized states. This generally applicable spectroscopy will provide an incisive tool to probe ultrafast transient molecular fluctuations that are obscured in non-chiral experiments.

  20. An NMR study of the solution conformations of some metal complexes

    CERN Document Server

    Rhodes, L A

    2001-01-01

    is attributed to steric interactions involving a naphthyl proton and the methyl group and the proton attached to the chiral carbon. When the chelating di(tertiaryphosphine) is chiral then marked conformational preferences are found for both the chiral orthopalladated Me sub 2 NCMeHPh and Me sub 2 NCMeHNap rings. It is concluded that this behaviour stems from steric interactions between the orhtopalladated rings and the chelating di(tertiaryphosphine rings) via the intermediacy of the other (usually phenyl) substituents of phosphorus and the N-methyl groups. In general the available conformations of the achiral di(tertiaryphosphine) chelate ring are of similar stability, but in with the chiral di(tertiaryphosphines) one conformation is considerably more stable than the other. This dominance of one conformation in the second case leads to preferred orientations of the substituents on the phosphorus and hence (via their steric interactions with the N-Me groups) to effects upon stability and consequently the conf...

  1. The first N-terminal unprotected (Gly-Aib)n peptide: H-Gly-Aib-Gly-Aib-OtBu.

    Science.gov (United States)

    Gessmann, Renate; Brückner, Hans; Petratos, Kyriacos

    2015-12-01

    Glycine (Gly) is incorporated in roughly half of all known peptaibiotic (nonribosomally biosynthesized antibiotic peptides of fungal origin) sequences and is the residue with the greatest conformational flexibility. The conformational space of Aib (α-aminoisobutyric acid) is severely restricted by the second methyl group attached to the Cα atom. Most of the crystal structures containing Aib are N-terminal protected. Deprotection of the N- or C-terminus of peptides may alter the hydrogen-bonding scheme and/or the structure and may facilitate crystallization. The structure reported here for glycyl-α-aminoisobutyrylglycyl-α-aminoisobutyric acid tert-butyl ester, C16H30N4O5, describes the first N-terminal-unprotected (Gly-Aib)n peptide. The achiral peptide could form an intramolecular hydrogen bond between the C=O group of Gly1 and the N-H group of Aib4. This hydrogen bond is found in all tetrapeptides and N-terminal-protected tripeptides containing Aib, apart from one exception. In the present work, this hydrogen bond is not observed (N...O = 5.88 Å). Instead, every molecule is hydrogen bonded to six other symmetry-related molecules with a total of eight hydrogen bonds per molecule. The backbone conformation starts in the right-handed helical region (and the left-handed helical region for the inverted molecule) and reverses the screw sense in the last two residues. PMID:26632841

  2. Chirality Inversion of CdSe and CdS Quantum Dots without Changing the Stereochemistry of the Capping Ligand.

    Science.gov (United States)

    Choi, Jung Kyu; Haynie, Benjamin E; Tohgha, Urice; Pap, Levente; Elliott, K Wade; Leonard, Brian M; Dzyuba, Sergei V; Varga, Krisztina; Kubelka, Jan; Balaz, Milan

    2016-03-22

    L-cysteine derivatives induce and modulate the optical activity of achiral cadmium selenide (CdSe) and cadmium sulfide (CdS) quantum dots (QDs). Remarkably, N-acetyl-L-cysteine-CdSe and L-homocysteine-CdSe as well as N-acetyl-L-cysteine-CdS and L-cysteine-CdS showed "mirror-image" circular dichroism (CD) spectra regardless of the diameter of the QDs. This is an example of the inversion of the CD signal of QDs by alteration of the ligand's structure, rather than inversion of the ligand's absolute configuration. Non-empirical quantum chemical simulations of the CD spectra were able to reproduce the experimentally observed sign patterns and demonstrate that the inversion of chirality originated from different binding arrangements of N-acetyl-L-cysteine and L-homocysteine-CdSe to the QD surface. These efforts may allow the prediction of the ligand-induced chiroptical activity of QDs by calculating the specific binding modes of the chiral capping ligands. Combined with the large pool of available chiral ligands, our work opens a robust approach to the rational design of chiral semiconducting nanomaterials.

  3. Phenomenological modeling of geometric metasurfaces.

    Science.gov (United States)

    Ye, Weimin; Guo, Qinghua; Xiang, Yuanjiang; Fan, Dianyuan; Zhang, Shuang

    2016-04-01

    Metasurfaces, with their superior capability in manipulating the optical wavefront at the subwavelength scale and low manufacturing complexity, have shown great potential for planar photonics and novel optical devices. However, vector field simulation of metasurfaces is so far limited to periodic-structured metasurfaces containing a small number of meta-atoms in the unit cell by using full-wave numerical methods. Here, focusing on achiral meta-atoms only with electric polarizability and thickness far less than the wavelength of light, and ignoring the coupling between meta-atoms, we propose a general phenomenological method to analytically model the metasurfaces based on the assumption that the meta-atoms possess localized resonances with Lorentz-Drude forms, whose exact form can be retrieved from the full wave simulation of a single element. Applied to phase modulated geometric metasurfaces constituted by identical meta-atoms with different orientations, our analytical results show good agreement with full-wave numerical simulations. The proposed theory provides an efficient method to model and design optical devices based on metasurfaces. PMID:27137005

  4. Highly Active Chiral Ruthenium Catalysts for Asymmetric Ring-Closing Olefin Metathesis

    Science.gov (United States)

    Funk, Timothy W.; Berlin, Jacob M.

    2008-01-01

    The synthesis of olefin metathesis catalysts containing chiral, monodentate N-heterocyclic carbenes and their application to asymmetric ring-closing metathesis (ARCM) is reported. These catalysts retain the high levels of reactivity found in the related achiral variants (1a and 1b). Using the parent chiral catalysts 2a and 2b and derivatives that contain steric bulk in the meta positions of the N-bound aryl rings (catalysts 3-5), five- through seven-membered rings were formed in up to 92% ee. The addition of sodium iodide to catalysts 2a-4a (to form 2b-4bin situ) caused a dramatic increase in enantioselectivity for many substrates. Catalyst 5a, which gave high enantiomeric excesses for certain substrates without the addition of NaI, could be used in loadings of ≤1 mol %. Mechanistic explanations for the large sodium iodide effect as well as possible mechanistic pathways leading to the observed products are discussed. PMID:16464082

  5. catena-Poly[zinc-tris(μ-dimethylcarbamato-κ2O:O′-zinc-μ-(2-phenylbenzimidazolido-κ2N:N′

    Directory of Open Access Journals (Sweden)

    Mark A. Rodriguez

    2012-01-01

    Full Text Available The crystal structure of the title compound, [Zn2(C13H9N2(C3H6NO23]n, displays a long chiral chain. This is composed of zinc-dimer clusters capped by dimethylcarbamate ligands, which lie on crystallographic twofold rotation axes and are polymerically linked in one dimension by 2-phenylbenzimidadole (2–PBImi organic ligands. The two Zn2+ ions defining the dimetal cluster are crystallographically independent, but display very similar coordination modes and tetrahedral geometry. As such, each Zn2+ ion is coordinated on one side by the N-donor imidazole linker, while the other three available coordination sites are fully occupied by the O atoms from the capping dimethylcarbamates. The chirality of the chain extends along the c axis, generating a rather long 52.470 (11 Å cell axis. Interestingly, the chiral material crystallizes from completely achiral precursors. A twofold axis and 31 screw axis serve to generate the long asymmetric unit.

  6. Multistep continuous-flow synthesis of (R)- and (S)-rolipram using heterogeneous catalysts

    Science.gov (United States)

    Tsubogo, Tetsu; Oyamada, Hidekazu; Kobayashi, Shū

    2015-04-01

    Chemical manufacturing is conducted using either batch systems or continuous-flow systems. Flow systems have several advantages over batch systems, particularly in terms of productivity, heat and mixing efficiency, safety, and reproducibility. However, for over half a century, pharmaceutical manufacturing has used batch systems because the synthesis of complex molecules such as drugs has been difficult to achieve with continuous-flow systems. Here we describe the continuous-flow synthesis of drugs using only columns packed with heterogeneous catalysts. Commercially available starting materials were successively passed through four columns containing achiral and chiral heterogeneous catalysts to produce (R)-rolipram, an anti-inflammatory drug and one of the family of γ-aminobutyric acid (GABA) derivatives. In addition, simply by replacing a column packed with a chiral heterogeneous catalyst with another column packed with the opposing enantiomer, we obtained antipole (S)-rolipram. Similarly, we also synthesized (R)-phenibut, another drug belonging to the GABA family. These flow systems are simple and stable with no leaching of metal catalysts. Our results demonstrate that multistep (eight steps in this case) chemical transformations for drug synthesis can proceed smoothly under flow conditions using only heterogeneous catalysts, without the isolation of any intermediates and without the separation of any catalysts, co-products, by-products, and excess reagents. We anticipate that such syntheses will be useful in pharmaceutical manufacturing.

  7. Three luminescent d10 metal coordination polymers assembled from a semirigid V-shaped ligand with high selective detecting of Cu2+ ion and nitrobenzene

    Science.gov (United States)

    Wu, Wei-Ping; Liu, Ping; Liang, Yu-Tong; Cui, Lin; Xi, Zheng-Ping; Wang, Yao-Yu

    2015-08-01

    Three 2D luminescent coordination polymers with helical frameworks, [ZnL2]n (1) and {[ML2]·(H2O)}n (M=Zn (2), Cd (3)) (HL=4-((2-methyl-1 H-imidazol-1-yl)methyl)benzoic acid), have been assembled under hydro(solvo)thermal conditions. Complex 1 is in chiral space group and displays a rare 2D→2D 2-fold parallel interpenetrated layer network with two types of chiral double helixes. Interestingly, the single crystal structure analyses indicate the coexistence of enantiomers la and 1b in one pot, while the bulk crystallization of 1 are racemic mixtures based on the CD measurement. 2 and 3 are isostructural, in the structure, there are two kinds of 2D chiral helical-layers which stack in an -ABAB- sequence leading to the overall structure are mesomer and achiral. All compounds display intense luminescence in solid state at room temperature with high chemical and thermal stability. More importantly, 1 has been successfully applied in the detection of Cu2+ ions in aqueous media and nitrobenzene and the probable detecting mechanism was also discussed.

  8. Validation of an enantioselective analysis for (l)-pidolic acid by chiral gas chromatography with derivatization.

    Science.gov (United States)

    Salisbury, John J; Li, Mingshu; Boyd, Aisha

    2016-02-20

    A sensitive and rapid analytical method has been validated for the enantiomeric purity determination of l-pidolic acid, a biological lactam and metabolite of glutamic acid commonly found in urine, skin, bones, brain and is available commercially as a food supplement. An efficient, two-step achiral derivatization was implemented which consisted of an alkylation step (using HCl-IPA) followed by an acylation step (using TFAA) of the carboxy and amide functional groups. This allowed detection with high sensitivity using gas chromatography with flame ionization detection. The described procedure employs a CP-Chiralsil-L Val column (25m×0.25mm) at a constant flow rate of 1.5mLmin(-1), a gradient temperature program from 80°C to 160°C and an injector and detector temperature of 250°C. The proposed method was validated according to ICH Q2 standards and included such parameters as specificity, system precision, analyst repeatability, intermediate precision, accuracy, linearity, LOD/LOQ and solution stability. PMID:26710173

  9. Spectroscopic Detection of Chiral Aggregation at Liquid-Liquid Interfaces

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Two new spectroscopic methods to detect the optical activity of liquid-liquid interfaces have been developed. The first one is the centrifugal liquid membrane (CLM) method combined with a conventional circular dichroism (CD) spectropolarimetry and the second one is a more interfacial specific second harmonic generation CD (SHG-CD) spectrometry. In the CLM-CD method, a cylindrical glass cell containing small amounts of organic and aqueous phases was rotated at about 7000 r/min in a sample chamber of a CD spectropolarimeter to generate an interface with a high specific interfacial area between the two-phase liquid membranes. The CD spectra of the J-aggregate of protonated 5,10,15, 20-tetraphenylporphyrin formed at the toluene-sulfuric acid interface have been measured. As for the SHG-CD, a circularly polarized wavelength-variable fs-laser system was constructed to measure the interfacial SHG spectra of a flat liquid-liquid interface. The ion-associated aggregation of a water-soluble anionic porphyrin promoted with a cationic amphiphile at the heptane-water interface was observed by this technique and the observed SHG-CD spectra proved the generation of a characteristic optical activity accompanied by the formation of the interfacial aggregate of inherently achiral porphyrin molecules. These methods will pioneer a new field of interfacial chiral chemistry in the studies of solvent extraction mechanisms.

  10. Enantiomeric excesses of chiral amines in ammonia-rich carbonaceous meteorites

    Science.gov (United States)

    Pizzarello, Sandra; Yarnes, Christopher T.

    2016-06-01

    Chiral homogeneity is essential to the structure and function of terrestrial biopolymers but the origin of this "homochirality" is poorly understood and remains one of the many unknowns surrounding the origins of life. Several amino acids extracted from Carbonaceous Chondrite meteorites display L-enantiomeric excesses (ee) and their findings have encouraged suggestions that an input of non-racemic meteoritic compounds to early Earth might have led to terrestrial homochirality. Motivated by occasional indications of possible ee in other classes of soluble meteoritic compounds, we have undertaken a systematic study of the chiral distribution of amines in Renazzo-type (CR) meteorites, where they are the second most abundant organic molecular species and ammonia is by far the most abundant single molecule. We report here the first time finding of L-ee for two chiral amines in several pristine CR meteorites from Antarctica and outline a proposal by which the compounds possibly formed from the same ketone precursors as some of the chiral amino acids. This would occur during a warm hydrous stage of the asteroidal parent body, via a reductive amination process in the presence of a large abundance of ammonia, where the precursors' adsorption upon mineral phases possessing asymmetry offered the opportunity for chiral induction. Because the precursor ketones are achiral, the proposal underscores the likelihood of diverse asymmetric influences and processes in cosmochemistry.

  11. The first N-terminal unprotected (Gly-Aib)n peptide: H-Gly-Aib-Gly-Aib-OtBu.

    Science.gov (United States)

    Gessmann, Renate; Brückner, Hans; Petratos, Kyriacos

    2015-12-01

    Glycine (Gly) is incorporated in roughly half of all known peptaibiotic (nonribosomally biosynthesized antibiotic peptides of fungal origin) sequences and is the residue with the greatest conformational flexibility. The conformational space of Aib (α-aminoisobutyric acid) is severely restricted by the second methyl group attached to the Cα atom. Most of the crystal structures containing Aib are N-terminal protected. Deprotection of the N- or C-terminus of peptides may alter the hydrogen-bonding scheme and/or the structure and may facilitate crystallization. The structure reported here for glycyl-α-aminoisobutyrylglycyl-α-aminoisobutyric acid tert-butyl ester, C16H30N4O5, describes the first N-terminal-unprotected (Gly-Aib)n peptide. The achiral peptide could form an intramolecular hydrogen bond between the C=O group of Gly1 and the N-H group of Aib4. This hydrogen bond is found in all tetrapeptides and N-terminal-protected tripeptides containing Aib, apart from one exception. In the present work, this hydrogen bond is not observed (N...O = 5.88 Å). Instead, every molecule is hydrogen bonded to six other symmetry-related molecules with a total of eight hydrogen bonds per molecule. The backbone conformation starts in the right-handed helical region (and the left-handed helical region for the inverted molecule) and reverses the screw sense in the last two residues.

  12. Photoinduced electro-optics measurements of biosilica transformation to cristobalite

    Energy Technology Data Exchange (ETDEWEB)

    Fuchs, Ido [Department of Chemistry and the Institute of Nanotechnology, Bar-Ilan University, Ramat-Gan 52900 (Israel); Aluma, Yaniv; Ilan, Micha [Department of Zoology, George S. Wise Faculty of Life Sciences, Tel Aviv University, Tel Aviv 6997801 (Israel); Kityk, Iwan [Institute of Electronic Systems, Faculty of Electrical Engineering, Czestochowa University, Czestochowa 42-201 (Poland); Mastai, Yitzhak, E-mail: Yitzhak.Mastai@biu.ac.il [Department of Chemistry and the Institute of Nanotechnology, Bar-Ilan University, Ramat-Gan 52900 (Israel)

    2015-03-15

    In this paper we studied the photoinduced electro optics effects in the thermal transformation process of biosilica to cristobalite, at a relatively low temperature and ambient pressure. This process was characterized by a variety of standards techniques with emphasis on linear electro optic effect measurements. Overall we demonstrated that photoinduced electro optics measurements are very sensitive to the transformation from amorphous structure of silica in the natural sponge samples to laminar string morphology of cristobalite. With this technique we could probe the change in the samples chirality from achiral bio silica to chiral cristobalite structure. Furthermore it is shown that natural biosilica have photoinduced linear electro optics respond indicating the chiral natural of biosilica. - Graphical abstract: The phase transformation of biosilica from marine sponges to Cristobalite under thermal treatment was investigated using photoinduced electro optics measurements. The figure shows the changes of the electro-optic coefficient of cristobalite and biosilica. - Highlights: • We examine phase transformation of biosilica. • We report transition from amorphous biosilica to crystalline Cristobalite. • Biosilica transformation to Cristobalite at temperature of 850 °C. • Biosilica transformation is studied with photoinduced measurements. • We examine changes in the photoinduced linear electro optics properties.

  13. Molecular cloning of isoflavone reductase from pea (Pisum sativum L.): evidence for a 3R-isoflavanone intermediate in (+)-pisatin biosynthesis.

    Science.gov (United States)

    Paiva, N L; Sun, Y; Dixon, R A; VanEtten, H D; Hrazdina, G

    1994-08-01

    Isoflavone reductase (IFR) reduces achiral isoflavones to chiral isoflavanones during the biosynthesis of chiral pterocarpan phytoalexins. A cDNA clone for IFR from pea (Pisum sativum) was isolated using the polymerase chain reaction and expressed in Escherichia coli. Analysis of circular dichroism (CD) spectra of the reduction product sophorol obtained using the recombinant enzyme indicated that the isoflavanone possessed the 3R stereochemistry, in contrast to previous reports indicating a 3S-isoflavanone as the product of the pea IFR. Analysis of CD spectra of sophorol produced using enzyme extracts of CuCl2-treated pea seedlings confirmed the 3R stereochemistry. Thus, the stereochemistry of the isoflavanone intermediate in (+)-pisatin biosynthesis in pea is the same as that in (-)-medicarpin biosynthesis in alfalfa, although the final pterocarpans have the opposite stereochemistry. At the amino acid level the pea IFR cDNA was 91.8 and 85.2% identical to the IFRs from alfalfa and chickpea, respectively. IFR appears to be encoded by a single gene in pea. Its transcripts are highly induced in CuCl2-treated seedlings, consistent with the appearance of IFR enzyme activity and pisatin accumulation.

  14. In-depth characterization of six cellulose tris-(3,5-dimethylphenylcarbamate) chiral stationary phases in supercritical fluid chromatography.

    Science.gov (United States)

    Khater, Syame; Zhang, Yingru; West, Caroline

    2013-08-16

    Since the expiration of the patent protection of Chiralcel OD, similar chiral stationary phases (CSPs), all based on the same chiral selector, have been introduced on the market with the promise to reproduce or improve the performance of the original cellulose tris-(3,5-dimethylphenylcarbamate) CSP. We report here-in an in-depth evaluation of four generic versions of Chiralcel OD (CelluCoat, RegisCell, Lux Cellulose-1, Reprosil-OM) and the immobilized version (Chiralpak IB) in comparison to the original Chiralcel OD in terms of retention and enantioselectivity, with the help of chemometrics. First of all, the CSPs are compared based on the retentions of 230 achiral compounds. Agglomerative hierarchical clustering and quantitative structure-retention relationships based on a modified version of the solvation parameter model are used to assess the differences in non-enantioselective interactions contributing to retention. Secondly, the CSPs are compared based on the separation factors measured for 130 racemates. Discriminant analysis is then used to unravel the structural features contributing to the successful enantioselective separations. Chiralcel OD is shown to be the most versatile of the six tested CSPs, and involves a unique and unequalled mechanism to achieve enantioseparation. PMID:23838300

  15. Highly selective single nucleotide polymorphism recognition by a chiral (5S) PNA beacon.

    Science.gov (United States)

    Totsingan, Filbert; Tedeschi, Tullia; Sforza, Stefano; Corradini, Roberto; Marchelli, Rosangela

    2009-01-01

    A chiral peptide nucleic acid (PNA) beacon containing a C-5 modified monomer based on L-lysine was synthesized. The terminal amino group of the lysine side chain was linked to a spacer for future applications on surfaces. The PNA beacon bears a carboxyfluorescein fluorophore and a dabcyl quencher at opposite ends. The DNA binding properties were compared with those of a homologous PNA beacon containing only achiral monomers. Both beacons underwent a fluorescence increase in the presence of complementary DNA, with higher efficiency and higher selectivity (evaluated using single mismatched DNA sequences) observed for the chiral monomer containing PNA. Ion exchange (IE) HPLC with fluorimetric detection was used in combination with the beacon for the selective detection of complementary DNA. A fluorescent peak corresponding to the PNA beacon:DNA duplex was observed at a very low detection limit (1 nM). The discriminating capacity of the chiral PNA beacon for a single mismatch was found to be superior to those observed with the unmodified one, thus confirming the potency of chirality for increasing the affinity and specificity of DNA recognition.

  16. Three chiral ionic liquids as additives for enantioseparation in capillary electrophoresis and their comparison with conventional modifiers.

    Science.gov (United States)

    Zhang, Qi; Qi, Xueyong; Feng, Chunlai; Tong, Shanshan; Rui, Mengjie

    2016-09-01

    The combined use of chiral ionic liquids (ILs) and conventional chiral selectors in CE to establish synergistic system has proven to be a convenient and effective approach for enantioseparation. In this work, three amino acid chiral ILs, tetramethylammonium-l-arginine (TMA-l-Arg), tetramethylammonium-l-hydroxyproline (TMA-l-Hyp) and tetramethylammonium-l-isoleucine (TMA-l-Ile), were first applied in CE enantioseparation to investigate their potential synergistic effect with hydroxypropyl-β-cyclodextrin (HP-β-CD). Markedly improved separations were obtained in the chiral ILs/HP-β-CD synergistic systems compared with single HP-β-CD system. Parameters, such as the chiral ILs concentration, HP-β-CD concentration, buffer pH, applied voltage and capillary temperature, were optimized. A systematic comparison of chiral ILs with conventional (commonly used) modifiers was also performed, including the use of achiral ILs, conventional salts and molecular organic solvents. In addition, the chiral configuration of ILs was investigated to demonstrate the existence of synergistic effect between chiral ILs and HP-β-CD. All these results indicate that chiral ILs, as additives for CE chiral separation, has significant superiority over conventional modifiers in certain cases. PMID:27515552

  17. Sign inversion of the spontaneous polarization in a "de Vries"-type ferroelectric liquid crystal.

    Science.gov (United States)

    Nonnenmacher, Dorothee; Lemieux, Robert P; Osipov, Mikhail A; Giesselmann, Frank

    2014-05-19

    In contrast to common ferroelectric smectic C* liquid crystals, the siloxane-terminated smectic mesogen E6 is characterized by an unusual temperature variation of the spontaneous polarization. The polarization starts to grow from nearly zero despite the first-order SmA*-SmC* transition, and increases faster than linearly over a large temperature interval while the tilt angle rapidly saturates. To study this behavior in more detail, binary mixtures of different concentrations of E6 in the achiral SmC material C8Cl, which has a similar chemical structure, were investigated. Surprisingly, all mixtures show a temperature dependent polarization sign inversion, which shifts towards the SmC*-SmA* transition with increasing E6 concentration. For the pure E6 the inversion temperature meets the SmA*-SmC* phase transition temperature. In a second binary mixture with E6 and a conventional material C9-2PhP we found out, that the dependence of the inversion temperature on the concentration of E6 changes qualitatively when the nanosegregation is partially destroyed. A molecular theory of the polarization sign inversion in smectics C* with strong polar intermolecular interactions is developed which enables one to explain the concentration dependence of the inversion temperature in both mixtures.

  18. Slow magnetic relaxation in four square-based pyramidal dysprosium hydroxo clusters ligated by chiral amino acid anions - a comparative study.

    Science.gov (United States)

    Thielemann, Dominique T; Wagner, Anna T; Lan, Yanhua; Anson, Christopher E; Gamer, Michael T; Powell, Annie K; Roesky, Peter W

    2013-10-01

    The synthesis and characterization of three chiral and one achiral amino acid anion ligated dysprosium hydroxo clusters [Dy5(OH)5(α-AA)4(Ph2acac)6] (α-AA = d-PhGly, l-Pro, l-Trp, Ph2Gly; Ph2acac = dibenzoylmethanide) are reported. The solid state structures were determined using single crystal X-ray diffraction and show that five Dy(iii) ions are arranged in a square-based pyramidal geometry with NO7-donor-sets for the basal and O8-donor-sets for the apical Dy atom. Both static (dc) and dynamic (ac) magnetic properties were investigated for all four compounds and show a slow relaxation of magnetization, indicative of single molecule magnet (SMM) behaviour below 10 K in all cases. The similar SMM behaviour observed for all four compounds suggests that the very similar coordination geometries seen for the dysprosium atoms in all members of this family, which are independent of the amino acid ligand used, play a decisive role in steering the contribution of the single ion anisotropies to the observed magnetic relaxation. PMID:23986134

  19. Total Syntheses of (-)-Mersicarpine, (-)-Scholarisine G, (+)-Melodinine E, (-)-Leuconoxine, (-)-Leuconolam, (-)-Leuconodine A, (+)-Leuconodine F, and (-)-Leuconodine C: Self-Induced Diastereomeric Anisochronism (SIDA) Phenomenon for Scholarisine G and Leuconodines A and C.

    Science.gov (United States)

    Xu, Zhengren; Wang, Qian; Zhu, Jieping

    2015-05-27

    Enantioselective total syntheses of title natural products from a common cyclohexenone derivative (S)-18 were reported. Ozonolysis of (S)-18 afforded a stable diketo ester (R)-17 that was subsequently converted to two skeletally different natural products, i.e., (-)-mersicarpine (8) with a [6.5.6.7] fused tetracyclic ring system and (-)-scholarisine G (9) with a [6.5.6.6.5] fused pentacyclic skeleton, respectively. The postcyclization diversification was realized by taking advantage of the facile conversion of (+)-melodinine E (6) to N-acyliminium ion 7, from which a hydroxy group was selectively introduced to the C6, C7, C10 and the central C21 position of diazafenestrane system, leading to (-)-leuconodine A (11), (+)-leuconodine F (12), (-)-scholarisine G (9), (-)-leuconodine C (13), and skeletally different (-)-leuconolam (5). Furthermore, an unprecedented non-natural oxabridged oxadiazafenestrane 68 was formed by oxidation of (+)-melodinine E (6). During the course of this study, a strong self-induced diastereomeric anisochronism (SIDA) phenomenon was observed for scholarisine G (9), leuconodines A (11) and C (13). X-ray structures of both the racemic and the enantiopure natural products 9, 11, and 13 were obtained. The different crystal packing of these two forms nicely explained the chemical shift differences observed in the (1)H NMR spectra of the racemic and the enantio-enriched compounds in an achiral environment.

  20. Total synthesis and in vitro bioevaluation of clavaminols A, C, H & deacetyl clavaminol H as potential chemotherapeutic and antibiofilm agents.

    Science.gov (United States)

    Vijai Kumar Reddy, T; Jyotsna, A; Prabhavathi Devi, B L A; Prasad, R B N; Poornachandra, Y; Ganesh Kumar, C

    2016-09-14

    A highly concise and expedient total synthesis of bioactive clavaminols (1-4) has been executed using commercially available achiral compound decanol. The synthetic strategy relied on trans-Wittig olefination, Sharpless asymmetric epoxidation, regioselective azidolysis and in situ detosylation followed by reduction as key reactions with good overall yield. Based on biological evaluation studies of all the synthesized compounds, it was observed that the clavaminol A (1) exhibited good cytotoxicity against DU145 and SKOV3 cell lines with IC50 value of 10.8 and 12.5 μM, respectively. Clavaminol A (1) and deacetyl clavaminol H (3) displayed selective promising inhibition towards Gram-positive pathogenic bacterial strains and showed good antifungal activity against the tested Candida strains. In addition, compounds 1 and 3 have demonstrated significant bactericidal activity. Compound 3 was found to be equipotent to the standard drug Miconazole displaying MFC value of 15.6 μg/mL against Candida albicans MTCC 854, C. albicans MTCC 1637, C. albicans MTCC 3958 and Candida glabrata MTCC 3019. Compounds 1 and 3 were also able to inhibit the biofilm formation of Micrococcus luteus MTCC 2470 and Staphylococcus aureus MLS16 MTCC 2940. Clavaminol A (1) increased the levels of reactive oxygen species (ROS) accumulation in M. luteus MTCC 2470. PMID:27187861

  1. 7-Chloro-5-(furan-3-yl)-3-methyl-4H-benzo[e][1,2,4]thiadiazine 1,1-Dioxide as Positive Allosteric Modulator of α-Amino-3-hydroxy-5-methyl-4-isoxazolepropionic Acid (AMPA) Receptor. The End of the Unsaturated-Inactive Paradigm?

    Science.gov (United States)

    Citti, Cinzia; Battisti, Umberto M; Cannazza, Giuseppe; Jozwiak, Krzysztof; Stasiak, Natalia; Puja, Giulia; Ravazzini, Federica; Ciccarella, Giuseppe; Braghiroli, Daniela; Parenti, Carlo; Troisi, Luigino; Zoli, Michele

    2016-02-17

    5-Arylbenzothiadiazine type compounds acting as positive allosteric modulators of α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptor (AMPA-PAMs) have received particular attention in the past decade for their nootropic activity and lack of the excitotoxic side effects of direct agonists. Recently, our research group has published the synthesis and biological activity of 7-chloro-5-(3-furanyl)-3-methyl-3,4-dihydro-2H-1,2,4-benzothiadiazine 1,1-dioxide (1), one of the most active benzothiadiazine-derived AMPA-PAMs in vitro to date. However, 1 exists as two stereolabile enantiomers, which rapidly racemize in physiological conditions, and only one isomer is responsible for the pharmacological activity. In the present work, experiments carried out with rat liver microsomes show that 1 is converted by hepatic cytochrome P450 to the corresponding unsaturated derivative 2 and to the corresponding pharmacologically inactive benzenesulfonamide 3. Surprisingly, patch-clamp experiments reveal that 2 displays an activity comparable to that of the parent compound. Molecular modeling studies were performed to rationalize these results. Furthermore, mice cerebral microdialysis studies suggest that 2 is able to cross the blood-brain barrier and increases acetylcholine and serotonin levels in the hippocampus. The experimental data disclose that the achiral hepatic metabolite 2 possesses the same pharmacological activity of its parent compound 1 but with an enhanced chemical and stereochemical stability, as well as an improved pharmacokinetic profile compared with 1. PMID:26580317

  2. Supramolecular Chirality: Solvent Chirality Transfer in Molecular Chemistry and Polymer Chemistry

    Directory of Open Access Journals (Sweden)

    Michiya Fujiki

    2014-08-01

    Full Text Available Controlled mirror symmetry breaking arising from chemical and physical origin is currently one of the hottest issues in the field of supramolecular chirality. The dynamic twisting abilities of solvent molecules are often ignored and unknown, although the targeted molecules and polymers in a fluid solution are surrounded by solvent molecules. We should pay more attention to the facts that mostly all of the chemical and physical properties of these molecules and polymers in the ground and photoexcited states are significantly influenced by the surrounding solvent molecules with much conformational freedom through non-covalent supramolecular interactions between these substances and solvent molecules. This review highlights a series of studies that include: (i historical background, covering chiral NaClO3 crystallization in the presence of d-sugars in the late 19th century; (ii early solvent chirality effects for optically inactive chromophores/fluorophores in the 1960s–1980s; and (iii the recent development of mirror symmetry breaking from the corresponding achiral or optically inactive molecules and polymers with the help of molecular chirality as the solvent use quantity.

  3. Chiral discrimination in optical trapping and manipulation

    Science.gov (United States)

    Bradshaw, David S.; Andrews, David L.

    2014-10-01

    When circularly polarized light interacts with chiral molecules or nanoscale particles powerful symmetry principles determine the possibility of achieving chiral discrimination, and the detailed form of electrodynamic mechanisms dictate the types of interaction that can be involved. The optical trapping of molecules and nanoscale particles can be described in terms of a forward-Rayleigh scattering mechanism, with trapping forces being dependent on the positioning within the commonly non-uniform intensity beam profile. In such a scheme, nanoparticles are commonly attracted to local potential energy minima, ordinarily towards the centre of the beam. For achiral particles the pertinent material response property usually entails an electronic polarizability involving transition electric dipole moments. However, in the case of chiral molecules, additional effects arise through the engagement of magnetic counterpart transition dipoles. It emerges that, when circularly polarized light is used for the trapping, a discriminatory response can be identified between left- and right-handed polarizations. Developing a quantum framework to accurately describe this phenomenon, with a tensor formulation to correctly represent the relevant molecular properties, the theory leads to exact analytical expressions for the associated energy landscape contributions. Specific results are identified for liquids and solutions, both for isotropic media and also where partial alignment arises due to a static electric field. The paper concludes with a pragmatic analysis of the scope for achieving enantiomer separation by such methods.

  4. Crystallographic and Spectroscopic Studies of a Host-Guest Complex Consisting of a Novel Zinc Trisporphyrinate and a Chiral Monoamine.

    Science.gov (United States)

    Han, Zhen; Li, Li; Shi, Bo; Fang, Xianshi; Wang, Yong; Hu, Chuanjiang

    2016-04-18

    We have designed and synthesized a novel zinc trisporphyrinate with a benzene tricarboxamide as the linker. In the presence of a large excess of 1-phenylethylamine, single crystals of the corresponding 1:3 host-guest complex were obtained, which provide the crystallographic structure of a host-guest complex consisting of an achiral porphyrin and a chiral monoamine. The structure reveals the 1-phenylethylamines adopt the "inside" binding mode that is stabilized by intramolecular hydrogen bonds. The NH2 of the 1-phenylethylamine is involved in both coordination and hydrogen bonding interactions. Circular dichroism (CD) and ultraviolet-visible spectra revealed that the 1:3 host-guest complex is dominant in the presence of a large excess of 1-phenylethylamine. The crystal structure shows there are two diastereomers of the 1:3 host-guest complexes. Density functional theory and TDDFT calculations suggest that one of the diastereomers is more energetically favorable, which dominates the CD signals. PMID:27023769

  5. HPLC monitoring of spontaneous non-linear peptidization dynamics of selected amino acids in solution.

    Science.gov (United States)

    Godziek, Agnieszka; Maciejowska, Anna; Sajewicz, Mieczysław; Kowalska, Teresa

    2015-03-01

    This is our new study in a series of publications devoted to exploration of applicability of high-performance liquid chromatography (HPLC) to providing answers to difficult questions from the area of the reaction kinetics and mechanisms with non-linear reactions. Although an excellent analytical performance of HPLC is an indisputable fact, so far its performance as a tool in the kinetic and mechanistic studies has been tested to a lesser extent. In our earlier studies, spontaneous peptidization dynamics of amino acids in solution was demonstrated by means of HPLC upon a few amino acid examples, and on that basis a theoretical model has been developed, anticipating an interdependence of dynamics on chemical structures of amino acids involved. In order to expand the spectrum of experimentally investigated amino acid cases, in this study we present the results valid for three novel amino acids of significant life sciences importance, which differ in terms of peptidization dynamics. Experimental evidence originates from the achiral HPLC with the evaporative light scattering detection and MS detection. A conclusion is drawn that different spontaneous peptidization dynamics of amino acids may significantly influence chemical composition of proteins encountered in living organisms. Hence, a need emerges for systematic physicochemical studies on spontaneous non-linear peptidization dynamics of proteinogenic amino acids in liquid abiotic (but also in the biotic) systems.

  6. Experimental implementation of automatic 'cycle to cycle' control of a chiral simulated moving bed separation.

    Science.gov (United States)

    Amanullah, Mohammad; Grossmann, Cristian; Mazzotti, Marco; Morari, Manfred; Morbidelli, Massimo

    2007-09-21

    In the absence of a suitable controller, currently simulated moving beds (SMBs) are operated suboptimally to cope with system uncertainties and to guarantee robustness of operation. Recently, we have developed a 'cycle to cycle' optimizing controller that not only makes use of minimal system information, i.e. only the Henry constants and average bed voidage, but also optimizes the process performance and taps the full economic potential of the SMB technology. The experimental implementation of the 'cycle to cycle' optimizing controller had been carried out for achiral separation. For chiral separation however, application of any online controller has not been possible because an appropriate online monitoring system has not been available. This work reports and discusses the first experimental implementation of the 'cycle to cycle' optimizing control for chiral separations. A mixture of guaifenesin enantiomers is separated on Chiralcel OD columns with ethanol as mobile phase in a eight-column four sections laboratory SMB unit. The results show that the controller, although using minimal information about the retention of the two enantiomers, is able to meet product and process specifications, can optimize the process performance, and is capable of rejecting disturbances that may occur during the operation of the SMB plant. PMID:17707852

  7. Luminescent Gold Nanoparticles with Size-Independent Emission.

    Science.gov (United States)

    Liu, Jinbin; Duchesne, Paul N; Yu, Mengxiao; Jiang, Xingya; Ning, Xuhui; Vinluan, Rodrigo D; Zhang, Peng; Zheng, Jie

    2016-07-25

    Size-independent emission has been widely observed for ultrasmall thiolated gold nanoparticles (AuNPs) but our understanding of the photoluminescence mechanisms of noble metals on the nanoscale has remained limited. Herein, we report how the emission wavelength of a AuNP and the local binding geometry of a thiolate ligand (glutathione) on the AuNP are correlated, as these AuNPs emit at different wavelengths in spite of their identical size (ca. 2.5 nm). By using circular dichroism, X-ray absorption, and fluorescence spectroscopy, we found that a high Au-S coordination number (CN) and a high surface coverage resulted in strong Au(I) -ligand charge transfer, a chiral conformation, and 600 nm emission, whereas a low Au-S CN and a low surface coverage led to weak charge transfer, an achiral conformation, and 810 nm emission. These two size-independent emissions can be integrated into one single 2.5 nm AuNP by fine-tuning of the surface coverage; a ratiometric pH response was then observed owing to strong energy transfer between two emission centers, opening up new possibilities for the design of ultrasmall ratiometric pH nanoindicators. PMID:27348584

  8. Energetic selection of topology in ferredoxins.

    Directory of Open Access Journals (Sweden)

    J Dongun Kim

    Full Text Available Models of early protein evolution posit the existence of short peptides that bound metals and ions and served as transporters, membranes or catalysts. The Cys-X-X-Cys-X-X-Cys heptapeptide located within bacterial ferredoxins, enclosing an Fe₄S₄ metal center, is an attractive candidate for such an early peptide. Ferredoxins are ancient proteins and the simple α+β fold is found alone or as a domain in larger proteins throughout all three kingdoms of life. Previous analyses of the heptapeptide conformation in experimentally determined ferredoxin structures revealed a pervasive right-handed topology, despite the fact that the Fe₄S₄ cluster is achiral. Conformational enumeration of a model CGGCGGC heptapeptide bound to a cubane iron-sulfur cluster indicates both left-handed and right-handed folds could exist and have comparable stabilities. However, only the natural ferredoxin topology provides a significant network of backbone-to-cluster hydrogen bonds that would stabilize the metal-peptide complex. The optimal peptide configuration (alternating α(L,α(R is that of an α-sheet, providing an additional mechanism where oligomerization could stabilize the peptide and facilitate iron-sulfur cluster binding.

  9. Ligand dependent topology and spontaneous resolution in high-spin cyano-bridged Ni3W2 clusters.

    Science.gov (United States)

    Nowicka, Beata; Reczyński, Mateusz; Rams, Michał; Wasiutyński, Tadeusz; Nitek, Wojciech; Sieklucka, Barbara

    2016-08-01

    Two high-spin pentanuclear NiW clusters with diimine blocking ligands have been obtained: {[Ni(4,4'-MeObpy)2]3[W(CN)8]2}·12H2O (1) and {[Ni(phen)2(H2O)][Ni(phen)2]2[W(CN)8]2}·7H2O (2) (4,4'-MeObpy = 4,4'-dimethoxy-2,2'-bipyridine, phen = 1,10-phenanthroline). Despite the similarity of the building blocks and synthetic conditions the compounds show different topologies of the cluster core: 1 is a trigonal bipyramid while 2 is a decorated square. Both cluster structures are chiral with either ΔΔΔ or ΛΛΛ configuration around all three Ni centres. In 1 spontaneous resolution occurs and it crystallises in the P212121 space group forming a conglomerate containing both types of enantiomorphic crystals. 1Δ and 1Λ are the first pair of enantiomorphic structures of cyano-bridged clusters of trigonal bipyramidal topology obtained with achiral bidentate blocking ligands. 2 crystallises as a racemic compound in a centrosymmetric space group P1[combining macron] with both enantiomers present in the structure. 2 is an exceptional square-motif containing structure with an identical stereoconfiguration of all complex cations within one cluster. Ferromagnetic interactions are present in both clusters resulting in the ground spin state S = 4. PMID:27431481

  10. Mirror Symmetry Breaking in Helical Polysilanes: Preference between Left and Right of Chemical and Physical Origin

    Directory of Open Access Journals (Sweden)

    Michiya Fujiki

    2010-08-01

    Full Text Available From elemental particles to human beings, matter is dissymmetric with respect to mirror symmetry. In 1860, Pasteur conjectured that biomolecular handedness— homochirality—may originate from certain inherent dissymmetric forces existing in the universe. Kipping, a pioneer of organosilicon chemistry, was interested in the handedness of sodium chlorate during his early research life. Since Kipping first synthesized several Si-Si bonded oligomers bearing phenyl groups, Si-Si bonded high polymers carrying various organic groups—polysilanes—can be prepared by sodium-mediated condensation of the corresponding organodichlorosilanes. Among these polysilanes, optically active helical polysilanes with enantiomeric pairs of organic side groups may be used for testing the mirror symmetry-breaking hypothesis by weak neutral current (WNC origin in the realm of chemistry and material science. Several theoretical studies have predicted that WNC-existing chiral molecules with stereogenic centers and/or stereogenic bonds allow for distinguishing between image and mirror image molecules. Based on several amplification mechanisms, theorists claimed that minute differences, though still very subtle, may be detectable by precise spectroscopic and physicochemical measurements if proper chiral molecular pairs were employed. The present paper reports comprehensively an inequality between six pairs of helical polysilane high polymers, presumably, detectable by (chiroptical and achiral 29Si-/13C- NMR spectra, and viscometric measurements.

  11. Chirality in Nonlinear Optics

    Science.gov (United States)

    Haupert, Levi M.; Simpson, Garth J.

    2009-05-01

    The past decade has witnessed the emergence of new measurement approaches and applications for chiral thin films and materials enabled by the observations of the high sensitivity of second-order nonlinear optical measurements to chirality. In thin films, the chiral response to second harmonic generation and sum frequency generation (SFG) from a single molecular monolayer is often comparable with the achiral response. The chiral specificity also allows for symmetry-allowed SFG in isotropic chiral media, confirming predictions made ˜50 years ago. With these experimental demonstrations in hand, an important challenge is the construction of intuitive predictive models that allow the measured chiral response to be meaningfully related back to molecular and macromolecular structure. This review defines and considers three distinct mechanisms for chiral effects in uniaxially oriented assemblies: orientational chirality, intrinsic chirality, and isotropic chirality. The role of each is discussed in experimental and computational studies of bacteriorhodopsin films, binaphthol, and collagen. Collectively, these three model systems support a remarkably simple framework for quantitatively recovering the measured chiral-specific activity.

  12. Supercritical fluid chromatography-A Hybrid of GC and LC

    Directory of Open Access Journals (Sweden)

    Neha Sethi

    2010-01-01

    Full Text Available High performance specifications and unique functionality of chromatographic techniques is a demand of pharmaceutical industry and research. This leads to the origin of Supercritical Fluid Chromatography (SFC. It is a rapidly expanding analytical technique. The main feature that differentiates SFC from other chromatographic techniques is the replacement of either the liquid or gas mobile phase with a supercritical fluid mobile phase. It is considered a hybrid of GC and LC technique. High diffusion coefficient and low viscosity of supercritical fluids is responsible for high speed analysis, high efficiency and high sensitivity. Low mobile-phase flow rate, density programming and compatability with GC and LC detectors make SFC a versatile chromatographic technique in analytical re-search and development. It has a unique characteristic of analyzing thermo labile or non-volatile substances. This review highlights the role of supercritical fluid chromatography in the separation of polymers, thermally labile pesticides, fatty acids, metal chelates and organometallic compounds, chiral and achiral molecules, identification and analysis of polar samples, explosives, drugs of abuse and application of SFC in forensic science (fingerprint-ing.

  13. Supercritical Fluid Chromatography- A Hybrid of GC and LC

    Directory of Open Access Journals (Sweden)

    Kaushal K Chandrul

    2010-03-01

    Full Text Available

    High performance specifications and unique functionality of chromatographic techniques is a demand of pharmaceutical industry and research. This leads to the origin of Supercritical Fluid Chromatography (SFC. It is a rapidly expanding analytical technique. The main feature that differentiates SFC from other chromatographic techniques is the replacement of either the liquid or gas mobile phase with a supercritical fluid mobile phase. It is considered a hybrid of GC and LC technique. High diffusion coefficient and low viscosity of supercritical fluids is responsible for high speed analysis, high efficiency and high sensitivity. Low mobile-phase flow rate, density programming and compatability with GC and LC detectors make SFC a versatile chromatographic technique in analytical research and development. It has a unique characteristic of analyzing thermo labile or non-volatile substances. This review highlights the role of supercritical fluid chromatography in the separation of polymers, thermally labile pesticides, fatty acids, metal chelates and organometallic compounds, chiral and achiral molecules, identification and analysis of polar samples, explosives, drugs of abuse and application of SFC in forensic science (fingerprinting. 

  14. Mechanisms for the inversion of chirality: Global reaction route mapping of stereochemical pathways in a probable chiral extraterrestrial molecule, 2-aminopropionitrile

    Energy Technology Data Exchange (ETDEWEB)

    Kaur, Ramanpreet; Vikas, E-mail: qlabspu@pu.ac.in, E-mail: qlabspu@yahoo.com [Quantum Chemistry Group, Department of Chemistry and Centre of Advanced Studies in Chemistry, Panjab University, Chandigarh 160014 (India)

    2015-02-21

    2-Aminopropionitrile (APN), a probable candidate as a chiral astrophysical molecule, is a precursor to amino-acid alanine. Stereochemical pathways in 2-APN are explored using Global Reaction Route Mapping (GRRM) method employing high-level quantum-mechanical computations. Besides predicting the conventional mechanism for chiral inversion that proceeds through an achiral intermediate, a counterintuitive flipping mechanism is revealed for 2-APN through chiral intermediates explored using the GRRM. The feasibility of the proposed stereochemical pathways, in terms of the Gibbs free-energy change, is analyzed at the temperature conditions akin to the interstellar medium. Notably, the stereoinversion in 2-APN is observed to be more feasible than the dissociation of 2-APN and intermediates involved along the stereochemical pathways, and the flipping barrier is observed to be as low as 3.68 kJ/mol along one of the pathways. The pathways proposed for the inversion of chirality in 2-APN may provide significant insight into the extraterrestrial origin of life.

  15. Mechanisms for the inversion of chirality: global reaction route mapping of stereochemical pathways in a probable chiral extraterrestrial molecule, 2-aminopropionitrile.

    Science.gov (United States)

    Kaur, Ramanpreet; Vikas

    2015-02-21

    2-Aminopropionitrile (APN), a probable candidate as a chiral astrophysical molecule, is a precursor to amino-acid alanine. Stereochemical pathways in 2-APN are explored using Global Reaction Route Mapping (GRRM) method employing high-level quantum-mechanical computations. Besides predicting the conventional mechanism for chiral inversion that proceeds through an achiral intermediate, a counterintuitive flipping mechanism is revealed for 2-APN through chiral intermediates explored using the GRRM. The feasibility of the proposed stereochemical pathways, in terms of the Gibbs free-energy change, is analyzed at the temperature conditions akin to the interstellar medium. Notably, the stereoinversion in 2-APN is observed to be more feasible than the dissociation of 2-APN and intermediates involved along the stereochemical pathways, and the flipping barrier is observed to be as low as 3.68 kJ/mol along one of the pathways. The pathways proposed for the inversion of chirality in 2-APN may provide significant insight into the extraterrestrial origin of life. PMID:25702015

  16. Resolution of Enantiomers of (RS)-Baclofen by Ligand-Exchange Thin-Layer Chromatography.

    Science.gov (United States)

    Singh, Manisha; Malik, Poonam; Bhushan, Ravi

    2016-05-01

    A new chromatographic method has been developed for direct enantioresolution of (RS)-baclofen by ligand-exchange thin-layer chromatography (TLC) adopting two different approaches; (A) TLC plates were prepared by mixing the ligand exchange reagents (LER) with silica gel slurry and the chromatograms were developed with different achiral solvents or solvents having no chiral additive, and (B) the LER consisting of Cu(II)-l-amino acid complex was used as chiral mobile phase additive and the plain plates of silica gel having no chiral selector were used. Cu(II) acetate and fourl-amino acids (namely,l-tryptophan,l-histidine,l-proline andl-phenylalanine) were used for the preparation of LERs. Spots were located by the use of iodine vapor. Effect of temperature and the mole ratio of Cu(II)-to-amino acid on enantioresolution were also studied. The results for the two methods have been compared, and the issue of involvement of the Cu(II) cation for the best performance of the two methods has been discussed with respect to the same mobile phase.l-Trp proved to be a good ligand using a common mobile phase in each case. PMID:26896346

  17. Design, Fabrication and Characterization of Multilayered Chiral Metamaterials in Visible Frequency

    Science.gov (United States)

    Hung, Jenny

    In this thesis I report the design and fabrication of well aligned repeatable multilayered gold and silver chiral metamaterials of high uniformity in the 100nm scale which show significant circular dichroism in the visible range. Two layered Dolmen structure, two layered 3-4-5 right-angled-triangle structure and three layered 'V' structure are successfully fabricated, allowing possible applications in wave-plates and circular polarizers. These samples are produced by an e-beam direct write technique with a precise multi-layer alignment control and a lift-off process. The experimental results are well matched with simulations using a finite-integration technique from CST microwave studio. None of the structures show circular dichroism upon first layer fabrication due to the achiral property of single layer, except for the single layer 3-4-5 right-angled-triangle structure which processes 2-D chirality. All the multilayered structures exhibit circular dichroism showing qualitatively the same shape upon opposite incident direction because of the handedness of structures; and with deviations due to the presence of the substrate and buffer layers. For the 'V' structure within the first three layers the CD increases with number of layers, unveiling the importance between 3-D chirality and optical activity. The mastering of alignment technique is important for successful fabrication of multilayered optical metamaterials. This project achieves precise multi-layer alignment control which is difficult and challenging.

  18. Application of cyanuric chloride-based six new chiral derivatizing reagents having amino acids and amino acid amides as chiral auxiliaries for enantioresolution of proteinogenic amino acids by reversed-phase high-performance liquid chromatography.

    Science.gov (United States)

    Bhushan, Ravi; Dixit, Shuchi

    2012-04-01

    Six dichloro-s-triazine (DCT) reagents having L-Leu, D-Phg, L-Val, L-Met, L-Ala and L-Met-NH(2) as chiral auxiliaries in cyanuric chloride were introduced for enantioseparation of 13 proteinogenic amino acids. Four other DCTs and six monochloro-s-triazine (MCT) reagents having amino acid amides as chiral auxiliaries were also synthesized. These 16 chiral derivatizing reagents (CDRs) were used for synthesis of diastereomers of all the 13 analytes using microwave irradiation, which were resolved by reversed-phase high-performance liquid chromatography (RP-HPLC) using C18 column and gradient eluting mixture of aqueous TFA and acetonitrile with UV detection at 230 nm. It required only 60-90 s for derivatization using microwave irradiation. Better resolution and lower retention times were observed for the diastereomers prepared with CDRs having amino acids as chiral auxiliaries as compared to counterparts prepared with reagents having amino acid amides as chiral auxiliaries. As the best resolution of all the 13 analytes was observed for their diastereomers prepared using the DCT reagent having L-Leu as chiral auxiliary, this CDR was further employed for derivatization of Lys, Tyr, His and Arg followed by RP-HPLC analysis of resulting diastereomers. The results are discussed in light of acid and amide groups of chiral auxiliaries constituting CDRs, electronegativities of the atoms of achiral moieties constituting CDRs and hydrophobicities of side chains of amino acids constituting CDRs and analytes.

  19. Three 2D Ag(I)-framework isomers with helical structures controlled by the chirality of camphor-10-sulfonic acid.

    Science.gov (United States)

    Guo, Peng

    2011-02-28

    Three 2D Ag(I)-framework isomers were constructed from enantiopure camphor-10-sulfonic acids or racemic camphor-10-sulfonic acids, together with achiral 4-aminobenzoic acids. In complex 1, (+)-camphor-10-sulfonic acids bridge the single left-handed helices that are made up of Ag ions and 4-aminobenzoic acids, generating a homochiral 2D layer. In such a structure, the interweaving of triple left-handed homohelices was also found. It is worth noting that the helicity of complex 2 could be controlled by the handedness of the camphor-10-sulfonic acid. In complex 2, there are right-handed helical structures, including single right-handed and triple right-handed helical structures connected by (-)-camphor-10-sulfonic acids. For a comparative study, (±)-camphor-10-sulfonic acids were utilized to synthesize complex 3, in which equal numbers of right-handed or left-handed double-helical chains are created. All the complexes were characterized by single-crystal X-ray structure determination, powder X-ray diffraction, IR, TGA and element analysis. Circular dichroism spectra of complexes 1 and 2 were been studied to confirm the fact that enantiopure bridging ligands do not racemize. PMID:21264423

  20. Design, synthesis and biological evaluation of phosphorodiamidate prodrugs of antiviral and anticancer nucleosides

    Science.gov (United States)

    McGuigan, Christopher; Bourdin, Claire; Derudas, Marco; Hamon, Nadège; Hinsinger, Karen; Kandil, Sahar; Madela, Karolina; Meneghesso, Silvia; Pertusati, Fabrizio; Serpi, Michaela; Slusarczyk, Magdalena; Chamberlain, Stanley; Kolykhalov, Alexander; Vernachio, John; Vanpouille, Christophe; Introini, Andrea; Margolis, Leonid; Balzarini, Jan

    2014-01-01

    We herein report the application of the phosphorodiamidate phosphate prodrug approach to a series of thirteen nucleoside analogs with antiviral or anticancer activity. Twenty-five symmetrical phosphorodiamidates were synthesized, bearing esterified l-Alanine (and in one case d-alanine) in the prodrug moiety, each as single stereoisomer. The presence of an achiral phosphorus represents a potential advantage over the phosphoramidate ProTide approach, where diastereoisomeric mixtures are routinely obtained, and different biological profiles may be expected from the diastereoisomers. Optimization of the synthetic pathway allowed us to identify two general methods depending on the particular nucleoside analogs. All the compounds were biologically evaluated in antiviral and anticancer assays and several showed improvement of activity compared to their parent nucleosides, as in the case of ddA, d4T, abacavir and acyclovir against HIV-1 and/or HIV-2. The biological results were supported by metabolism studies with carboxypeptidase Y monitored by 31P NMR to investigate their bioactivation. This work further validates the phosphorodiamidate approach as a monophosphate prodrug motif with broad application in the antiviral and anticancer fields. PMID:24177359

  1. Simple chiral urea gelators, (R)- and (S)-2-heptylurea: their gelling ability enhanced by chirality.

    Science.gov (United States)

    Kim, Jong-Uk; Schollmeyer, Dieter; Brehmer, Martin; Zentel, Rudolf

    2011-05-15

    We present the first report on the synthesis of chiral ureas, (R)- and (S)-2-heptylurea, and their gelling behaviors. The ureas were prepared by the reactions of chiral amines and phenyl carbamate in the presence of triethylamine. On cooling from homogeneous solutions, the chiral ureas form gels in water and various nonpolar organic solvents, such as cyclohexane, toluene, and tetrachloromethane, while the racemate gelatinize only toluene and tetrachloromethane among the solvents we examined. The gelling ability of the enantiomeric urea is higher than the racemate, as the critical gelling concentrations in toluene, for example, were 0.2% and 0.7% (wt/wt), respectively. The enhanced gelling ability of the enantiomeric ureas is due to the 1D supramolecular structure formed during gelation. In contrast, the racemate crystallizes into two-dimensional lamellae, where the (R)- and (S)-2-heptylurea exist alternatingly in a plane (P2(1)/c space group). Powder X-ray diffraction pattern of the enantiomeric urea showed that it has a different crystal lattice from that of the racemate, implying that the steric effect by the methyl group at the chiral center prevents the pure enantiomers from having 2D hydrogen bonding networks, which lead to sheet-like structures for the racemate and the achiral analog. Thus the pure enantiomers self-organize into one-dimensional fibrous structures. The simplicity and the ambidextrous gelling behaviors of the chiral ureas in forming both hydrogels and organogels present numerous possibilities for future applications. PMID:21396655

  2. A loop-gap resonator for chirality-sensitive nuclear magneto-electric resonance (NMER)

    Science.gov (United States)

    Garbacz, Piotr; Fischer, Peer; Krämer, Steffen

    2016-09-01

    Direct detection of molecular chirality is practically impossible by methods of standard nuclear magnetic resonance (NMR) that is based on interactions involving magnetic-dipole and magnetic-field operators. However, theoretical studies provide a possible direct probe of chirality by exploiting an enantiomer selective additional coupling involving magnetic-dipole, magnetic-field, and electric field operators. This offers a way for direct experimental detection of chirality by nuclear magneto-electric resonance (NMER). This method uses both resonant magnetic and electric radiofrequency (RF) fields. The weakness of the chiral interaction though requires a large electric RF field and a small transverse RF magnetic field over the sample volume, which is a non-trivial constraint. In this study, we present a detailed study of the NMER concept and a possible experimental realization based on a loop-gap resonator. For this original device, the basic principle and numerical studies as well as fabrication and measurements of the frequency dependence of the scattering parameter are reported. By simulating the NMER spin dynamics for our device and taking the 19F NMER signal of enantiomer-pure 1,1,1-trifluoropropan-2-ol, we predict a chirality induced NMER signal that accounts for 1%-5% of the standard achiral NMR signal.

  3. Coherence specific signal detection via chiral pump-probe spectroscopy.

    Science.gov (United States)

    Holdaway, David I H; Collini, Elisabetta; Olaya-Castro, Alexandra

    2016-05-21

    We examine transient circular dichroism (TRCD) spectroscopy as a technique to investigate signatures of exciton coherence dynamics under the influence of structured vibrational environments. We consider a pump-probe configuration with a linearly polarized pump and a circularly polarized probe, with a variable angle θ between the two directions of propagation. In our theoretical formalism the signal is decomposed in chiral and achiral doorway and window functions. Using this formalism, we show that the chiral doorway component, which beats during the population time, can be isolated by comparing signals with different values of θ. As in the majority of time-resolved pump-probe spectroscopy, the overall TRCD response shows signatures of both excited and ground state dynamics. However, we demonstrate that the chiral doorway function has only a weak ground state contribution, which can generally be neglected if an impulsive pump pulse is used. These findings suggest that the pump-probe configuration of optical TRCD in the impulsive limit has the potential to unambiguously probe quantum coherence beating in the excited state. We present numerical results for theoretical signals in an example dimer system.

  4. Growth of single-walled gold nanotubes confined in carbon nanotubes, studied by molecular dynamics simulations

    Science.gov (United States)

    Han, Yang; Hu, Ting; Dong, Jinming

    2013-01-01

    Growth of the single-walled gold nanotube (SWGNT), confined in the single-walled carbon nanotube (SWCNT) has been studied by using the classical molecular dynamics (MD) simulations, in which two different empirical potentials (the glue and EAM potentials) are used for the interaction between gold atoms. It is found that under the glue potential, three new SWGNTs, (3, 2), (4, 2) and (6, 3) gold tubes can be formed, in addition to the previously found (3, 3), (4, 3) and (5, 3) ones, among which two achiral ones, (4, 2) and (6, 3) gold tubes are particularly interesting because they were thought to be not the tube-like structures, or to have large enough diameter, permitting an extra gold atom chain in it. However, when the EAM potential is used, only four SWGNTs, i.e., (3, 2), (4, 2), (4, 3) and (5, 3) gold tubes could be formed in our MD simulations. After comparing all the MD simulation results with those of the first principles calculations, it is found that the EAM potential is better to describe the interaction between gold atoms than the glue potential for the MD simulation on the growth of gold tubular structure in confined CNT.

  5. Chiral expression at the solid-liquid interface: a joint experimental and theoretical study of the self-assembly of chiral porphyrins on graphite.

    Science.gov (United States)

    Linares, Mathieu; Iavicoli, Patrizia; Psychogyiopoulou, Krystallia; Beljonne, David; De Feyter, Steven; Amabilino, David B; Lazzaroni, Roberto

    2008-09-01

    The chiral organization of an enantiopure functional molecule on an achiral surface has been studied with the aim of understanding the influence of stereogenic centers on the self-assembly in two dimensions. A chiral tetra meso-amidophenyl-substituted porphyrin containing long hydrophobic tails at the periphery of the conjugated pi-electron system was prepared for this purpose. Scanning tunneling microscopy (STM) images of the compound at the graphite-heptanol interface reveal a chiral arrangement of the molecules, with the porphyrin rows tilted by 13 degrees with respect to the normal to the graphite axes. In terms of molecular modeling, a combination of molecular dynamics simulations on systems constrained by periodic boundary conditions and on unconstrained large molecular aggregates has been applied to reach a quantitative interpretation on both the density of the layer and its orientation with respect to the graphite surface. The results show clearly that (i) the methyl groups of the stereogenic point toward the graphite surface and (ii) the porphyrin molecules self-assemble into an interdigitated structure where the alkyl chains align along one of the graphite axes and the porphyrin cores are slightly shifted with respect to one another. The direction of this shift, which defines the chirality of the monolayer, is set by the chirality of the stereogenic centers. Such an arrangement results in the formation of a dense chiral monolayer that is further stabilized by hydrogen bonding with protic solvents.

  6. Human antimicrobial peptide histatin 5 is a cell-penetrating peptide targeting mitochondrial ATP synthesis in Leishmania.

    Science.gov (United States)

    Luque-Ortega, Juan Román; van't Hof, Wim; Veerman, Enno C I; Saugar, José M; Rivas, Luis

    2008-06-01

    Histatin 5 (Hst5) is a human salivary antimicrobial peptide that targets fungal mitochondria. In the human parasitic protozoa Leishmania, the mitochondrial ATP production is essential, as it lacks the bioenergetic switch between glycolysis and oxidative phosphorylation described in some yeasts. On these premises, Hst5 activity was assayed on both stages of its life cycle, promastigotes and amastigotes (LC(50)=7.3 and 14.4 microM, respectively). In a further step, its lethal mechanism was studied. The main conclusions drawn were as follows: 1) Hst5 causes limited and temporary damage to the plasma membrane of the parasites, as assessed by electron microscopy, depolarization, and entrance of the vital dye SYTOX Green; 2) Hst5 translocates into the cytoplasm of Leishmania in an achiral receptor-independent manner with accumulation into the mitochondrion, as shown by confocal microscopy; and 3) Hst5 produces a bioenergetic collapse of the parasite, caused essentially by the decrease of mitochondrial ATP synthesis through inhibition of F(1)F(0)-ATPase, with subsequent fast ATP exhaustion. By using the Hst5 enantiomer, it was found that the key steps of its lethal mechanism involved no chiral recognition. Hst5 thus constitutes the first leishmanicidal peptide with a defined nonstereospecific intracellular target. The prospects of its development, by its own or as a carrier molecule for other leishmanicidal molecules, into a novel anti-Leishmania drug with a preferential subcellular accumulation are discussed. PMID:18230684

  7. Photochirogenesis: Photochemical models on the absolute asymmetric formation of amino acids in interstellar space

    Science.gov (United States)

    Meinert, Cornelia; de Marcellus, Pierre; Le Sergeant D'Hendecourt, Louis; Nahon, Laurent; Jones, Nykola C.; Hoffmann, Søren V.; Bredehöft, Jan Hendrik; Meierhenrich, Uwe J.

    2011-10-01

    Proteins of all living organisms including plants, animals, and humans are made up of amino acid monomers that show identical stereochemical L-configuration. Hypotheses for the origin of this symmetry breaking in biomolecules include the absolute asymmetric photochemistry model by which interstellar ultraviolet (UV) circularly polarized light (CPL) induces an enantiomeric excess in chiral organic molecules in the interstellar/circumstellar media. This scenario is supported by a) the detection of amino acids in the organic residues of UV-photo-processed interstellar ice analogues, b) the occurrence of L-enantiomer-enriched amino acids in carbonaceous meteorites, and c) the observation of CPL of the same helicity over large distance scales in the massive star-forming region of Orion. These topics are of high importance in topical biophysical research and will be discussed in this review. Further evidence that amino acids and other molecules of prebiotic interest are asymmetrically formed in space comes from studies on the enantioselective photolysis of amino acids by UV-CPL. Also, experiments have been performed on the absolute asymmetric photochemical synthesis of enantiomer-enriched amino acids from mixtures of astrophysically relevant achiral precursor molecules using UV-circularly polarized photons. Both approaches are based on circular dichroic transitions of amino acids that will be highlighted here as well. These results have strong implications on our current understanding of how life's precursor molecules were possibly built and how life selected the left-handed form of proteinogenic amino acids.

  8. Microwave-assisted stereospecific synthesis of novel tetrahydropyran adenine isonucleosides and crystal structures determination

    Science.gov (United States)

    Silva, Fábio P. L.; Cirqueira, Marilia L.; Martins, Felipe T.; Vasconcellos, Mário L. A. A.

    2013-11-01

    We describe in this article stereospecific syntheses for new isonucleosides analogs of adenine 5-7 from tosyl derivatives 2-4 accessing by microwave irradiations (50-80%). The adenine reacts entirely at the N(9) position. Compounds 2-4 were prepared in two steps from the corresponding alcohols 1, 8 and 9 (81-92%). These tetrahydropyrans alcohols 1, 8 and 9 are achiral (Meso compounds) and were prepared in two steps with complete control of 2,4,6-cis relative configuration by Prins cyclization reaction (60-63%) preceded by the Barbier reaction between allyl bromide with benzaldehyde, 4-fluorobenzaldehyde and 2-naphthaldehyde respectively under Lewis acid conditions (96-98%). The configurations and preferential conformations of 5-7 were determined by crystal structure of 6. These novel isonucleosides 5-7 present in silico potentiality to act as GPCR ligand, kinase inhibitor and enzyme inhibitor, evaluated by Molinspiration program, consistent with the expected antiviral and anticancer bioactivities.

  9. Light scattering study of the "pseudo-layer" compression elastic constant in a twist-bend nematic liquid crystal

    CERN Document Server

    Parsouzi, Z; Welch, C; Ahmed, Z; Mehl, G H; Baldwin, A R; Gleeson, J T; Lavrentovich, O D; Allender, D W; Selinger, J V; Jakli, A; Sprunt, S

    2016-01-01

    The nematic twist-bend (TB) phase, exhibited by certain achiral thermotropic liquid crystalline (LC) dimers, features a nanometer-scale, heliconical rotation of the average molecular long axis (director) with equally probable left- and right-handed domains. On meso to macroscopic scales, the TB phase may be considered as a stack of equivalent slabs or "pseudo-layers", each one helical pitch in thickness. The long wavelength fluctuation modes should then be analogous to those of a smectic-A phase, and in particular the hydrodynamic mode combining "layer" compression and bending ought to be characterized by an effective layer compression elastic constant $B_{eff}$ and average director splay constant $K_1^{eff}$. The magnitude of $K_1^{eff}$ is expected to be similar to the splay constant of an ordinary nematic LC, but due to the absence of a true mass density wave, $B_{eff}$ could differ substantially from the typical value of $\\sim 10^6$ Pa in a conventional smectic-A. Here we report the results of a dynamic l...

  10. Progress in Synthesis of Optically Active Polyamide%旋光性聚酰胺研究进展

    Institute of Scientific and Technical Information of China (English)

    张玲丽; 付鹏; 崔喆; 刘民英; 赵清香

    2015-01-01

    按化学结构对旋光性聚酰胺进行了分类,包括用非手性单体制备的旋光性酰胺、侧链含手性原子及主链含手性原子的旋光性聚酰胺。对旋光性聚酰胺的合成方法进行了总结,介绍了链增长缩聚法、溶液聚合法和界面缩聚法在合成旋光性聚酰胺方面的应用。%The category of optically active polyamide was introduced according to chemical structure,which was constructed by monomers bearing chiral side groups,monomers having chiral atoms in main chain and achiral monomers respectively. The synthesis methods of optically active polyamides were reviewed. Chain-grown condensation polymerization,solution polymerization and interfacial polymerization that were used to achieve optically active polyamides were introduced in detail.

  11. Enantioselective metabolism of the endocrine disruptor pesticide methoxychlor by human cytochromes P450 (P450s): major differences in selective enantiomer formation by various P450 isoforms.

    Science.gov (United States)

    Hu, Yiding; Kupfer, David

    2002-12-01

    Methoxychlor, a currently used pesticide that in mammals elicits proestrogenic/estrogenic activity and reproductive toxicity, has been classified as a prototype endocrine disruptor. Methoxychlor is prochiral, and its metabolites 1,1,1-trichloro-2-(4-hydroxyphenyl)-2-(4-methoxyphenyl)ethane (mono-OH-M); 1,1,1-trichloro- 2-(4-methoxyphenyl)-2-(3, 4-dihydroxyphenyl)ethane (catechol-M); and 1,1,1-trichloro-2-(4-hydroxyphenyl)-2-(3, 4-dihydroxyphenyl)ethane (tris-OH-M) are chiral; whereas 1,1,1-trichloro-2, 2-bis(4-hydroxyphenyl)ethane (bis-OH-M) is achiral. These metabolites are formed during methoxychlor incubation with liver microsomes or recombinant cytochrome p450s (rp450s). Since methoxychlor-metabolite enantiomers may have different estrogenic/antiestrogenic/antiandrogenic activities than corresponding racemates, the possibility that p450s preferentially generate or use R or S enantiomers, was examined. Indeed, rCYP1A2 and r2A6 mono-demethylated methoxychlor primarily into (R)-mono-OH-M at 91 and 75%, respectively, whereas rCYP1A1, 2B6, 2C8, 2C9, 2C19, and 2D6 formed the (S)-enantiomer at 69, 66, 75, 95, 96, and 80%, respectively. However, rCYP3A4, 3A5, and 2B1(rat) weakly demethylated methoxychlor without enantioselectivity. Human liver microsomes generated (S)-mono-OH-M (77-87%), suggesting that CYP1A2 and 2A6 display only minor catalytic contribution. P450 inhibitors demonstrated that CYP2C9 and possibly 2C19 are major hepatic catalysts forming (S)-mono-OH-M, and CYP1A2 is primarily involved in forming the (R)-mono-OH-M. Demethylation rate of (S)-mono-OH-M versus (R)-mono-OH-M forming achiral bis-OH-M by rCYP1A2 was 97/3, compared with 15/85 and 17/83 for rCYP2C9 and 2C19, respectively, indicating opposite substrate enantioselectivity of rCYP1A2 versus 2C9 and 2C19. Also, rCYP1A2 preferentially O-demethylated (R)-catechol-M into (R)-tris-OH-M (at 80%), contrasting r2C9 and r2C19 that yielded (S)-tris-OH-M at 80 and 77%, respectively. Ortho-hydroxylation of

  12. Transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates: Catalysts for asymmetric olefin hydroamination and acceptorless alcohol decarbonylation

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Kuntal [Ames Lab., Ames, IA (United States)

    2012-12-17

    The research presented and discussed in this dissertation involves the synthesis of transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates, and their application in catalytic enantioselective olefin hydroamination and acceptorless alcohol decarbonylation. Neutral oxazolinylboranes are excellent synthetic intermediates for preparing new borate ligands and also developing organometallic complexes. Achiral and optically active bis(oxazolinyl)phenylboranes are synthesized by reaction of 2-lithio-2-oxazolide and 0.50 equiv of dichlorophenylborane. These bis(oxazolinyl)phenylboranes are oligomeric species in solid state resulting from the coordination of an oxazoline to the boron center of another borane monomer. The treatment of chiral bis(oxazolinyl)phenylboranes with sodium cyclopentadienide provide optically active cyclopentadienyl-bis(oxazolinyl)borates H[PhB(C5H5)(OxR)2] [OxR = Ox4S-iPr,Me2, Ox4R-iPr,Me2, Ox4S-tBu]. These optically active proligands react with an equivalent of M(NMe2)4 (M = Ti, Zr, Hf) to afford corresponding cyclopentadienyl-bis(oxazolinyl)borato group 4 complexes {PhB(C5H4)(OxR)2}M(NMe2)2 in high yields. These group 4 compounds catalyze cyclization of aminoalkenes at room temperature or below, providing pyrrolidine, piperidine, and azepane with enantiomeric excesses up to 99%. Our mechanistic investigations suggest a non-insertive mechanism involving concerted C-N/C-H bond formation in the turnover limiting step of the catalytic cycle. Among cyclopentadienyl-bis(oxazolinyl)borato group 4 catalysts, the zirconium complex {PhB(C5H4)(Ox4S-iPr,Me2)2}Zr(NMe2)2 ({S-2}Zr(NMe2)2) displays highest activity and enantioselectivity. Interestingly, S-2

  13. Concentration-dependent structure and structural transition from chirality to nonchirality at the liquid-solid interface by coassembly

    Science.gov (United States)

    Xu, Li; Miao, Xinrui; Cui, Lihua; Liu, Pei; Chen, Xiaofeng; Deng, Wenli

    2015-07-01

    Understanding the formation and structural transition of the two-dimensional chirality of self-assembly is a subject which still gains significant interest in surface or interface chirality studies. Here, we present the solvent-induced chiral structural transition of a 2-hydroxy-7-pentadecyloxy-9-fluorenone (HPF) molecules' self-assembled adlayer through coassembly with achiral aliphatic solvents under different concentrations. Polymorphic chiral patterns are obtained at low concentrations of aliphatic solvents with different chain lengths. The HPF molecules form coassembled structures with these solvents through van der Waals interactions. At the same time, at high concentrations, HPF molecules uniformly form a nonchiral multimer structure without coadsorbed aliphatic solvent molecules. What is interesting is that these structures under different concentrations will finally change into a zigzag structure, which is the thermodynamically most stable configuration. Especially when using n-hexadecane as the solvent, the adlayer shows perfect steric matching due to the close chain length of HPF and n-hexadecane, which can maximize the molecule-solvent interactions. Thus, HPF molecules in n-hexadecane exhibit the most diversiform configuration. The distinct concentration-dependence has proven that the solvent molecules can act as a coadsorbed component through van der Waals interactions rather than simply a dispersant and further result in the probability and stability of chiral self-assembled monolayers by subtle tuning of the solvent-molecule and solvent-substrate interactions. This result provides a simple and alternative strategy to construct the 2D chiral assembled monolayer.Understanding the formation and structural transition of the two-dimensional chirality of self-assembly is a subject which still gains significant interest in surface or interface chirality studies. Here, we present the solvent-induced chiral structural transition of a 2-hydroxy-7-pentadecyloxy

  14. Lewis pair polymerization by classical and frustrated Lewis pairs: Acid, base and monomer scope and polymerization mechanism

    KAUST Repository

    Zhang, Yuetao

    2012-01-01

    Classical and frustrated Lewis pairs (LPs) of the strong Lewis acid (LA) Al(C 6F 5) 3 with several Lewis base (LB) classes have been found to exhibit exceptional activity in the Lewis pair polymerization (LPP) of conjugated polar alkenes such as methyl methacrylate (MMA) as well as renewable α-methylene-γ-butyrolactone (MBL) and γ-methyl- α-methylene-γ-butyrolactone (γ-MMBL), leading to high molecular weight polymers, often with narrow molecular weight distributions. This study has investigated a large number of LPs, consisting of 11 LAs as well as 10 achiral and 4 chiral LBs, for LPP of 12 monomers of several different types. Although some more common LAs can also be utilized for LPP, Al(C 6F 5) 3-based LPs are far more active and effective than other LA-based LPs. On the other hand, several classes of LBs, when paired with Al(C 6F 5) 3, can render highly active and effective LPP of MMA and γ-MMBL; such LBs include phosphines (e.g., P tBu 3), chiral chelating diphosphines, N-heterocyclic carbenes (NHCs), and phosphazene superbases (e.g., P 4- tBu). The P 4- tBu/Al(C 6F 5) 3 pair exhibits the highest activity of the LP series, with a remarkably high turn-over frequency of 9.6 × 10 4 h -1 (0.125 mol% catalyst, 100% MMA conversion in 30 s, M n = 2.12 × 10 5 g mol -1, PDI = 1.34). The polymers produced by LPs at RT are typically atactic (P γMMBL with ∼47% mr) or syndio-rich (PMMA with ∼70-75% rr), but highly syndiotactic PMMA with rr ∼91% can be produced by chiral or achiral LPs at -78 °C. Mechanistic studies have identified and structurally characterized zwitterionic phosphonium and imidazolium enolaluminates as the active species of the current LPP system, which are formed by the reaction of the monomer·Al(C 6F 5) 3 adduct with P tBu 3 and NHC bases, respectively. Kinetic studies have revealed that the MMA polymerization by the tBu 3P/ Al(C 6F 5) 3 pair is zero-order in monomer concentration after an initial induction period, and the polymerization

  15. Light-directing chiral liquid crystal nanostructures: from 1D to 3D.

    Science.gov (United States)

    Bisoyi, Hari Krishna; Li, Quan

    2014-10-21

    Endowing external, remote, and dynamic control to self-organized superstructures with desired functionalities is a principal driving force in the bottom-up nanofabrication of molecular devices. Light-driven chiral molecular switches or motors in liquid crystal (LC) media capable of self-organizing into optically tunable one-dimensional (1D) and three-dimensional (3D) superstructures represent such an elegant system. As a consequence, photoresponsive cholesteric LCs (CLCs), i.e., self-organized 1D helical superstructures, and LC blue phases (BPs), i.e., self-organized 3D periodic cubic lattices, are emerging as a new generation of multifunctional supramolecular 1D and 3D photonic materials in their own right because of their fundamental academic interest and technological significance. These smart stimuli-responsive materials can be facilely fabricated from achiral LC hosts by the addition of a small amount of a light-driven chiral molecular switch or motor. The photoresponsiveness of these materials is a result of both molecular interaction and geometry changes in the chiral molecular switch upon light irradiation. The doped photoresponsive CLCs undergo light-driven pitch modulation and/or helix inversion, which has many applications in color filters, polarizers, all-optical displays, optical lasers, sensors, energy-saving smart devices, and so on. Recently, we have conceptualized and rationally synthesized different light-driven chiral molecular switches that have very high helical twisting powers (HTPs) and exhibit large changes in HTP in different states, thereby enabling wide phototunability of the systems by the addition of very small amounts of the molecular switches into commercially available achiral LCs. The light-driven chiral molecular switches are based on well-recognized azobenzene, dithienylcyclopentene, and spirooxazine derivatives. We have demonstrated high-resolution and lightweight photoaddressable displays without patterned electronics on

  16. Diagnostic Approach to Disease Using Non-invasive Samples Based on Derivatization and LC-ESI-MS/MS.

    Science.gov (United States)

    Toyo'oka, Toshimasa

    2016-01-01

    The determination of biologically-active molecules is very important in order to understand biological functions. A novel approach for the highly sensitive and specific determination seems to be essential for this purpose. Based on this consideration, we synthesized various types of fluorogenic and fluorescent reagents for the derivatization of chiral and achiral molecules. The fluorescence analysis is excellent for the analysis of target molecules and generally provides good expected results. However, the trace analysis of the bioactive molecules in complex matrices, such as plasma and urine, is not always satisfactory even using high-performance fluorometry. In such a situation, mass spectrometry (MS) is another technique for the selective and sensitive determination of biological components. Therefore, various derivatization reagents for MS/MS detection were developed and used for the determination of amines and carboxyls including chiral molecules. These newly developed reagents were also adopted for the biomarker detection related to diseases using non-invasive samples (i.e., saliva, nail, hair). Although the determination of the targeted chiral molecules is relatively easy, it is very difficult to identify and/or determine the enantiomeric biomarker in real samples. To solve this difficulty, we proposed the strategy called "chiral metabolomics," which means the total analysis of the enantiomers of various chiral metabolites in complex matrices. This review paper focused on the development of various new derivatization reagents for amines and carboxyls by liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis and the detection of the biomarker candidates related to several diseases in non-invasive samples (i.e., hair, nail, saliva) using these reagents. PMID:27582321

  17. δ-Peptides from RuAAC-Derived 1,5-Disubstituted Triazole Units

    KAUST Repository

    Johansson, Johan R.

    2014-02-14

    Non-natural peptides with structures and functions similar to natural peptides have emerged lately in biomedical as well as nanotechnological contexts. They are interesting for pharmaceutical applications since they can adopt structures with new targeting potentials and because they are generally not prone to degradation by proteases. We report here a new set of peptidomimetics derived from δ-peptides, consisting of n units of a 1,5-disubstituted 1,2,3-triazole amino acid (5Tzl). The monomer was prepared using ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) chemistry using [RuCl2Cp]x as the catalyst, allowing for simpler purification and resulting in excellent yields. This achiral monomer was used to prepare peptide oligomers that are water soluble independent of peptide chain length. Conformational analysis and structural investigations of the oligomers were performed by 2D NOESY NMR experiments, and by quantum chemical calculations using the ωB97X-D functional. These data indicate that several conformations may co-exist with slight energetic differences. Together with their increased hydrophilicity, this feature of homo-5Tzl may prove essential for mimicking natural peptides composed of α-amino acids, where the various secondary structures are achieved by side chain effects and not by the rigidity of the peptide backbone. The improved synthetic method allows for facile variation of the 5Tzl amino acid side chains, further increasing the versatility of these compounds. A new set of non-natural peptides composed of 1,5-disubstituted 1,2,3-triazole amino acids is presented. These peptides benefit from: a) modular synthesis of the monomers, allowing variation of the side chains; b) increased solubility of the oligomers in water, irrespective of peptide length; c) flexibility of the backbone allowing these foldamers to adopt several conformations. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Biosynthesis of monoterpenes. Enantioselectivity in the enzymatic cyclization of (+)- and (-)-linalyl pyrophosphate to (+)- and (-)-pinene and (+)- and (-)-camphene

    Energy Technology Data Exchange (ETDEWEB)

    Croteau, R.; Satterwhite, D.M.; Cane, D.E.; Chang, C.C.

    1988-07-25

    Cyclase I from Salvia officinalis leaf catalyzes the conversion of geranyl pyrophosphate to the stereo-chemically related bicyclic monoterpenes (+)-alpha-pinene and (+)-camphene and to lesser quantities of monocyclic and acyclic olefins, whereas cyclase II from this plant tissue converts the same acyclic precursor to (-)-alpha-pinene, (-)-beta-pinene and (-)-camphene as well as to lesser amounts of monocyclics and acyclics. These antipodal cyclizations are considered to proceed by the initial isomerization of the substrate to the respective bound tertiary allylic intermediates (-)-(3R)- and (+)-(3S)-linalyl pyrophosphate. ((3R)-8,9-14C,(3RS)-1E-3H)Linalyl pyrophosphate (3H:14C = 5.14) was tested as a substrate with both cyclases to determine the configuration of the cyclizing intermediate. This substrate with cyclase I yielded alpha-pinene and camphene with 3H:14C ratios of 3.1 and 4.2, respectively, indicating preferential, but not exclusive, utilization of the (3R)-enantiomer. With cyclase II, the doubly labeled substrate gave bicyclic olefins with 3H:14C ratios of from 13 to 20, indicating preferential, but not exclusive, utilization of the (3S)-enantiomer in this case. (3R)- and (3S)-(1Z-3H)linalyl pyrophosphate were separately compared to the achiral precursors (1-3H)geranyl pyrophosphate and (1-3H)neryl pyrophosphate (cis-isomer) as substrates for the cyclizations. With cyclase I, geranyl, neryl, and (3R)-linalyl pyrophosphate gave rise exclusively to (+)-alpha-pinene and (+)-camphene, whereas (3S)-linayl pyrophosphate produced, at relatively low rates, the (-)-isomers. With cyclase II, geranyl, neryl, and (3S)-linalyl pyrophosphate yielded exclusively the (-)-isomer series, whereas (3R)-linalyl pyrophosphate afforded the (+)-isomers at low rates.

  19. Solvent-induced helical assembly and reversible chiroptical switching of chiral cyclic-dipeptide-functionalized naphthalenediimides.

    Science.gov (United States)

    Manchineella, Shivaprasad; Prathyusha, V; Priyakumar, U Deva; Govindaraju, T

    2013-12-01

    Understanding the roles of various parameters in orchestrating the preferential chiral molecular organization in supramolecular self-assembly processes is of great significance in designing novel molecular functional systems. Cyclic dipeptide (CDP) chiral auxiliary-functionalized naphthalenediimides (NCDPs 1-6) have been prepared and their chiral self-assembly properties have been investigated. Detailed photophysical and circular dichroism (CD) studies have unveiled the crucial role of the solvent in the chiral aggregation of these NCDPs. NCDPs 1-3 form supramolecular helical assemblies and exhibit remarkable chiroptical switching behaviour (M- to P-type) depending on the solvent composition of HFIP and DMSO. The strong influence of solvent composition on the supramolecular chirality of NCDPs has been further corroborated by concentration and solid-state thin-film CD studies. The chiroptical switching between supramolecular aggregates of opposite helicity (M and P) has been found to be reversible, and can be achieved through cycles of solvent removal and redissolution in solvent mixtures of specific composition. The control molecular systems (NCDPs 4-6), with an achiral or D-isomer second amino acid in the CDP auxiliary, did not show chiral aggregation properties. The substantial roles of hydrogen bonding and π-π interactions in the assembly of the NCDPs have been validated through nuclear magnetic resonance (NMR), photophysical, and computational studies. Quantum chemical calculations at the ab initio, semiempirical, and density functional theory levels have been performed on model systems to understand the stabilities of the right (P-) and left (M-) handed helical supramolecular assemblies and the nature of the intermolecular interactions. This study emphasizes the role of CDP chiral auxiliaries on the solvent-induced helical assembly and reversible chiroptical switching of naphthalenediimides. PMID:24281809

  20. Biosynthesis of monoterpenes. Enantioselectivity in the enzymatic cyclization of (+)- and (-)-linalyl pyrophosphate to (+)- and (-)-pinene and (+)- and (-)-camphene

    International Nuclear Information System (INIS)

    Cyclase I from Salvia officinalis leaf catalyzes the conversion of geranyl pyrophosphate to the stereo-chemically related bicyclic monoterpenes (+)-alpha-pinene and (+)-camphene and to lesser quantities of monocyclic and acyclic olefins, whereas cyclase II from this plant tissue converts the same acyclic precursor to (-)-alpha-pinene, (-)-beta-pinene and (-)-camphene as well as to lesser amounts of monocyclics and acyclics. These antipodal cyclizations are considered to proceed by the initial isomerization of the substrate to the respective bound tertiary allylic intermediates (-)-(3R)- and (+)-(3S)-linalyl pyrophosphate. [(3R)-8,9-14C,(3RS)-1E-3H]Linalyl pyrophosphate (3H:14C = 5.14) was tested as a substrate with both cyclases to determine the configuration of the cyclizing intermediate. This substrate with cyclase I yielded alpha-pinene and camphene with 3H:14C ratios of 3.1 and 4.2, respectively, indicating preferential, but not exclusive, utilization of the (3R)-enantiomer. With cyclase II, the doubly labeled substrate gave bicyclic olefins with 3H:14C ratios of from 13 to 20, indicating preferential, but not exclusive, utilization of the (3S)-enantiomer in this case. (3R)- and (3S)-[1Z-3H]linalyl pyrophosphate were separately compared to the achiral precursors [1-3H]geranyl pyrophosphate and [1-3H]neryl pyrophosphate (cis-isomer) as substrates for the cyclizations. With cyclase I, geranyl, neryl, and (3R)-linalyl pyrophosphate gave rise exclusively to (+)-alpha-pinene and (+)-camphene, whereas (3S)-linayl pyrophosphate produced, at relatively low rates, the (-)-isomers. With cyclase II, geranyl, neryl, and (3S)-linalyl pyrophosphate yielded exclusively the (-)-isomer series, whereas (3R)-linalyl pyrophosphate afforded the (+)-isomers at low rates

  1. Diastereo- and enantioseparation of a N(α)-Boc amino acid with a zwitterionic quinine-based stationary phase: focus on the stereorecognition mechanism.

    Science.gov (United States)

    Ianni, Federica; Carotti, Andrea; Marinozzi, Maura; Marcelli, Gloria; Di Michele, Alessandro; Sardella, Roccaldo; Lindner, Wolfgang; Natalini, Benedetto

    2015-07-23

    A chiral chromatography method enabling the simultaneous diastereo- and enantioseparation of N(α)-Boc-N(4)-(hydroorotyl)-4-aminophenylalanine [Boc-Aph(Hor)-OH, 1] was optimized with a quinine-based zwitterionic stationary phase. The polar-ionic eluent system consisting of ACN:MeOH:water-49.7:49.7:0.6 (v/v/v) with formic acid (4.0mM) and diethylamine (2.5mM), allowed the successful separation of the four acid stereoisomers: αd,d-/d,l-1=1.08; αd,l-/l,d-1=1.08; αl,d-/l,l-1=1.40. According to the in-house developed synthetic procedure and the recorded electronic circular dichroism spectra, the following stereoisomeric elution order was readily established in the optimal chromatographic conditions: d,d-1achiral sub-structural elements of the chiral stationary phase and eluent components in the overall stereorecognition mechanism.

  2. Criteria of backscattering in chiral one-way photonic crystals

    Science.gov (United States)

    Cheng, Pi-Ju; Chang, Shu-Wei

    2016-03-01

    Optical isolators are important devices in photonic circuits. To reduce the unwanted reflection in a robust manner, several setups have been realized using nonreciprocal schemes. In this study, we show that the propagating modes in a strongly-guided chiral photonic crystal (no breaking of the reciprocity) are not backscattering-immune even though they are indeed insensitive to many types of scatters. Without the protection from the nonreciprocity, the backscattering occurs under certain circumstances. We present a perturbative method to calculate the backscattering of chiral photonic crystals in the presence of chiral/achiral scatters. The model is, essentially, a simplified analogy to the first-order Born approximation. Under reasonable assumptions based on the behaviors of chiral photonic modes, we obtained the expression of reflection coefficients which provides criteria for the prominent backscattering in such chiral structures. Numerical examinations using the finite-element method were also performed and the results agree well with the theoretical prediction. From both our theory and numerical calculations, we find that the amount of backscattering critically depends on the symmetry of scatter cross sections. Strong reflection takes place when the azimuthal Fourier components of scatter cross sections have an order l of 2. Chiral scatters without these Fourier components would not efficiently reflect the chiral photonic modes. In addition, for these chiral propagating modes, disturbances at the most significant parts of field profiles do not necessarily result in the most effective backscattering. The observation also reveals what types of scatters or defects should be avoided in one-way applications of chiral structures in order to minimize the backscattering.

  3. Enantiomeric excesses induced in amino acids by ultraviolet circularly polarized light irradiation of extraterrestrial ice analogs: A possible source of asymmetry for prebiotic chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Modica, Paola; De Marcellus, Pierre; D' Hendecourt, Louis Le Sergeant [Univ. Paris-Sud, Institut d' Astrophysique Spatiale, UMR 8617, F-91405 Orsay (France); Meinert, Cornelia; Meierhenrich, Uwe J. [Univ. Nice Sophia Antipolis, Institut de Chimie de Nice, UMR 7272 CNRS, F-06108 Nice (France); Nahon, Laurent, E-mail: laurent.nahon@synchrotron-soleil.fr, E-mail: ldh@ias.u-psud.fr [Synchrotron SOLEIL, F-91192 Gif-sur-Yvette (France)

    2014-06-10

    The discovery of meteoritic amino acids with enantiomeric excesses of the L-form (ee {sub L}) has suggested that extraterrestrial organic materials may have contributed to prebiotic chemistry and directed the initial occurrence of the ee {sub L} that further led to homochirality of amino acids on Earth. A proposed mechanism for the origin of ee {sub L} in meteorites involves an asymmetric photochemistry of extraterrestrial ices by UV circularly polarized light (CPL). We have performed the asymmetric synthesis of amino acids on achiral extraterrestrial ice analogs by VUV CPL, investigating the chiral asymmetry transfer at two different evolutionary stages at which the analogs were irradiated (regular ices and/or organic residues) and at two different photon energies (6.6 and 10.2 eV). We identify 16 distinct amino acids and precisely measure the L-enantiomeric excesses using the enantioselective GC × GC-TOFMS technique in five of them: α-alanine, 2,3-diaminopropionic acid, 2-aminobutyric acid, valine, and norvaline, with values ranging from ee {sub L} = –0.20% ± 0.14% to ee {sub L} = –2.54% ± 0.28%. The sign of the induced ee {sub L} depends on the helicity and the energy of CPL, but not on the evolutionary stage of the samples, and is the same for all five considered amino acids. Our results support an astrophysical scenario in which the solar system was formed in a high-mass star-forming region where icy grains were irradiated during the protoplanetary phase by an external source of CPL of a given helicity and a dominant energy, inducing a stereo-specific photochemistry.

  4. CYP2C subfamily, primarily CYP2C9, catalyses the enantioselective demethylation of the endocrine disruptor pesticide methoxychlor in human liver microsomes: use of inhibitory monoclonal antibodies in P450 identification.

    Science.gov (United States)

    Hu, Y; Krausz, K; Gelboin, H V; Kupfer, D

    2004-02-01

    1. The endocrine disruptor pesticide methoxychlor undergoes O-demethylation by mammalian liver microsomes forming chiral mono-phenolic (1,1,1-trichloro-2-(4-hydroxyphenyl)-2-(4-methoxyphenyl)ethane, i.e. mono-OH-M) and achiral bis-phenolic oestrogenic metabolites. Human liver microsomes (HLM) generated primarily the S-mono-OH-M. 2. Inhibitory monoclonal antibodies (MAb) identified those P450s catalysing the enantioselective O-demethylation of methoxychlor. In HLM, O-demethylation was inhibited by MAb anti-2C9 (30-40%), diminishing the per cent of S-mono-OH-M from about 80 to 55-60%. MAb anti-CYP1A2, 2A6, 2B6, 2C8, 2C19, 2D6 and 3A4 did not affect the demethylation rate in HLM. Nevertheless, MAb anti-CYP1A2 decreased the formation of R-mono-OH-M from 21-23 to 10-17%, indicating that CYP1A2 exhibits a role in generating the R-enantiomer. 3. Among cDNA-expressed human P450s (supersomes), CYP2C19 was the most active in demethylation, but in HLM, CYP2C19 appeared inactive (no inhibition by MAb anti-CYP2C19). There was a substantial difference in the per cent inhibition of demethylation by MAb anti-CYP2C9 and anti-rat CYP2C (MAb inhibiting all human CYP2C forms) and in altering the enantioselectivity, suggesting that demethylation by combined CYP2C8, 2C18 and 2C19 was significant (20-30%). 4. Polymorphism of methoxychlor demethylation was examined with supersomes and HLM-expressing CYP2C9 allelic variants. CYP2C9*1 and 2C9*2 were highly active; however, CYP2C9*3 appeared inactive.

  5. Lanthanide(III) complexes of bis-semicarbazone and bis-imine-substituted phenanthroline ligands: solid-state structures, photophysical properties, and anion sensing.

    Science.gov (United States)

    Nadella, Sandeep; Selvakumar, Paulraj M; Suresh, Eringathodi; Subramanian, Palani S; Albrecht, Markus; Giese, Michael; Fröhlich, Roland

    2012-12-21

    Phenanthroline-based hexadentate ligands L(1) and L(2) bearing two achiral semicarbazone or two chiral imine moieties as well as the respective mononuclear complexes incorporating various lanthanide ions, such as La(III), Eu(III), Tb(III), Lu(III), and Y(III) metal ions, were synthesized, and the crystal structures of [ML(1)Cl(3)] (M=La(III), Eu(III), Tb(III), Lu(III), or Y(III)) complexes were determined. Solvent or water molecules act as coligands for the rare-earth metals in addition to halide anions. The big Ln(III) ion exhibits a coordination number (CN) of 10, whereas the corresponding Eu(III), Tb(III), Lu(III), and Y(III) centers with smaller ionic radii show CN=9. Complexes of L(2), namely [ML(2)Cl(3)] (M=Eu(III), Tb(III), Lu(III), or Y(III)) ions could also be prepared. Only the complex of Eu(III) showed red luminescence, whereas all the others were nonluminescent. The emission properties of the Eu derivative can be applied as a photophysical signal for sensing various anions. The addition of phosphate anions leads to a unique change in the luminescence behavior. As a case study, the quenching behavior of adenosine-5'-triphosphate (ATP) was investigated at physiological pH value in an aqueous solvent. A specificity of the sensor for ATP relative to adenosine-5'-diphosphate (ADP) and adenosine-5'-monophosphate (AMP) was found. (31)P NMR spectroscopic studies revealed the formation of a [EuL(2)(ATP)] coordination species.

  6. J-aggregates of amphiphilic cyanine dyes: Self-organization of artificial light harvesting complexes

    Directory of Open Access Journals (Sweden)

    Stefan Kirstein

    2006-01-01

    Full Text Available The simultaneous chemical linkage of cyanine dye chromophores with both hydrophobic and hydrophilic substituents leads to a new type of amphiphilic molecules with the ability of spontaneous self-organization into highly ordered aggregates of various structures and morphologies. These aggregates carry the outstanding optical properties of J-aggregates, namely, efficient exciton coupling and fast exciton energy migration, which are essential for the build up of artificial light harvesting systems. The morphology of the aggregates depends sensitively on the molecular structure of the chemical substituents of the dye chromophore. Accordingly, lamellar ribbon-like structures, vesicles , tubes, and bundles of tubes are found depending on the dyes and the structure can further be altered by addition of surfactants, alcohols, or other additives. Altogether the tubular structure is the most noticeable structural motif of these types of J-aggregates. The optical spectra are characterized in general by a complex exciton spectrum which is composed of several electronic transitions. The spectrum is red-shifted as a total with respect to the monomer absorption and exhibits resonance fluorescence from the lowest energy transition. For the tubular structures, the optical spectra can be related to a structural model. Although the molecules itself are strictly achiral, a pronounced circular dichroism (CD is observed for the tubular aggregates and explained by unequal distribution of left- and right-handed helicity of the tubes. Photo-induced electron transfer (PET reactions from the dye aggregates to electron acceptor molecules lead to superquenching which proves the delocalization of the excitation. This property is used to synthesize metal nanoparticles on the aggregate surface by photo-induced reduction of metal ions.

  7. Elongation Factor Tu Prevents Misediting of Gly-tRNA(Gly) Caused by the Design Behind the Chiral Proofreading Site of D-Aminoacyl-tRNA Deacylase

    Science.gov (United States)

    Routh, Satya Brata; Ahmad, Sadeem; Suma, Katta; Kumar, Mantu; Kuncha, Santosh Kumar; Yadav, Kranthikumar; Kruparani, Shobha P; Sankaranarayanan, Rajan

    2016-01-01

    D-aminoacyl-tRNA deacylase (DTD) removes D-amino acids mischarged on tRNAs and is thus implicated in enforcing homochirality in proteins. Previously, we proposed that selective capture of D-aminoacyl-tRNA by DTD’s invariant, cross-subunit Gly-cisPro motif forms the mechanistic basis for its enantioselectivity. We now show, using nuclear magnetic resonance (NMR) spectroscopy-based binding studies followed by biochemical assays with both bacterial and eukaryotic systems, that DTD effectively misedits Gly-tRNAGly. High-resolution crystal structure reveals that the architecture of DTD’s chiral proofreading site is completely porous to achiral glycine. Hence, L-chiral rejection is the only design principle on which DTD functions, unlike other chiral-specific enzymes such as D-amino acid oxidases, which are specific for D-enantiomers. Competition assays with elongation factor thermo unstable (EF-Tu) and DTD demonstrate that EF-Tu precludes Gly-tRNAGly misediting at normal cellular concentrations. However, even slightly higher DTD levels overcome this protection conferred by EF-Tu, thus resulting in significant depletion of Gly-tRNAGly. Our in vitro observations are substantiated by cell-based studies in Escherichia coli that show that overexpression of DTD causes cellular toxicity, which is largely rescued upon glycine supplementation. Furthermore, we provide direct evidence that DTD is an RNA-based catalyst, since it uses only the terminal 2′-OH of tRNA for catalysis without the involvement of protein side chains. The study therefore provides a unique paradigm of enzyme action for substrate selection/specificity by DTD, and thus explains the underlying cause of DTD’s activity on Gly-tRNAGly. It also gives a molecular and functional basis for the necessity and the observed tight regulation of DTD levels, thereby preventing cellular toxicity due to misediting. PMID:27224426

  8. Structural Basis for the Enzymatic Formation of the Key Strawberry Flavor Compound 4-Hydroxy-2,5-dimethyl-3(2H)-furanone

    Science.gov (United States)

    Schiefner, André; Sinz, Quirin; Neumaier, Irmgard; Schwab, Wilfried; Skerra, Arne

    2013-01-01

    The last step in the biosynthetic route to the key strawberry flavor compound 4-hydroxy-2,5-dimethyl-3(2H)-furanone (HDMF) is catalyzed by Fragaria x ananassa enone oxidoreductase (FaEO), earlier putatively assigned as quinone oxidoreductase (FaQR). The ripening-induced enzyme catalyzes the reduction of the exocyclic double bond of the highly reactive precursor 4-hydroxy-5-methyl-2-methylene-3(2H)-furanone (HMMF) in a NAD(P)H-dependent manner. To elucidate the molecular mechanism of this peculiar reaction, we determined the crystal structure of FaEO in six different states or complexes at resolutions of ≤1.6 Å, including those with HDMF as well as three distinct substrate analogs. Our crystallographic analysis revealed a monomeric enzyme whose active site is largely determined by the bound NAD(P)H cofactor, which is embedded in a Rossmann-fold. Considering that the quasi-symmetric enolic reaction product HDMF is prone to extensive tautomerization, whereas its precursor HMMF is chemically labile in aqueous solution, we used the asymmetric and more stable surrogate product 2-ethyl-4-hydroxy-5-methyl-3(2H)-furanone (EHMF) and the corresponding substrate (2E)-ethylidene-4-hydroxy-5-methyl-3(2H)-furanone (EDHMF) to study their enzyme complexes as well. Together with deuterium-labeling experiments of EDHMF reduction by [4R-2H]NADH and chiral-phase analysis of the reaction product EHMF, our data show that the 4R-hydride of NAD(P)H is transferred to the unsaturated exocyclic C6 carbon of HMMF, resulting in a cyclic achiral enolate intermediate that subsequently becomes protonated, eventually leading to HDMF. Apart from elucidating this important reaction of the plant secondary metabolism our study provides a foundation for protein engineering of enone oxidoreductases and their application in biocatalytic processes. PMID:23589283

  9. Three luminescent d10 metal coordination polymers assembled from a semirigid V-shaped ligand with high selective detecting of Cu2+ ion and nitrobenzene

    International Nuclear Information System (INIS)

    Three 2D luminescent coordination polymers with helical frameworks, [ZnL2]n (1) and ([ML2]·(H2O))n (M=Zn (2), Cd (3)) (HL=4-((2-methyl-1 H-imidazol-1-yl)methyl)benzoic acid), have been assembled under hydro(solvo)thermal conditions. Complex 1 is in chiral space group and displays a rare 2D→2D 2-fold parallel interpenetrated layer network with two types of chiral double helixes. Interestingly, the single crystal structure analyses indicate the coexistence of enantiomers la and 1b in one pot, while the bulk crystallization of 1 are racemic mixtures based on the CD measurement. 2 and 3 are isostructural, in the structure, there are two kinds of 2D chiral helical-layers which stack in an -ABAB- sequence leading to the overall structure are mesomer and achiral. All compounds display intense luminescence in solid state at room temperature with high chemical and thermal stability. More importantly, 1 has been successfully applied in the detection of Cu2+ ions in aqueous media and nitrobenzene and the probable detecting mechanism was also discussed. - Graphical abstract: Three luminescent d10 metal coordination polymers with helical-layer based on 4-((2-methyl-1H-imidazol-1-yl)methyl)benzoic acid have been obtained. Compound 1 shows high selective detecting for Cu2+ ion in aqueous and nitrobenzene. - Highlights: • Three coordination polymers with chiral helical-layer have been obtained. • 1 Can luminescent detect Cu2+ ion in aqueous media and nitrobenzene. • Racemic mixture or mesomer compounds can be obtained by controlling the reaction conditions

  10. Novel cationic polyene glycol phospholipids as DNA transfer reagents--lack of a structure-activity relationship due to uncontrolled self-assembling processes.

    Science.gov (United States)

    Øpstad, Christer L; Zeeshan, Muhammad; Zaidi, Asma; Sliwka, Hans-Richard; Partali, Vassilia; Nicholson, David G; Surve, Chinmay; Izower, Mitchell A; Bilchuk, Natalia; Lou, Howard H; Leopold, Philip L; Larsen, Helge; Liberska, Alexandra; Khalique, Nada Abdul; Raju, Liji; Flinterman, Marcella; Jubeli, Emile; Pungente, Michael D

    2014-10-01

    Cationic glycol phospholipids were synthesized introducing chromophoric, rigid polyenoic C20:5 and C30:9 chains next to saturated flexible alkyl chains of variable lengths C6-20:0. Surface properties and liposome formation of the amphiphilic compounds were determined, the properties of liposome/DNA complexes (lipoplexes) were established using three formulations (no co-lipid, DOPE as a co-lipid, or cholesterol as a co-lipid), and the microstructure of the best transfecting compounds inspected using small angle X-ray diffraction to explore details of the partially ordered structures of the systems that constitute the series. Transfection and cytotoxicity of the lipoplexes were evaluated by DNA delivery to Chinese hamster ovary (CHO-K1) cells using the cationic glycerol phospholipid 1,2-dioleoyl-sn-glycero-3-ethylphosphocholine (EPC) as a reference compound. The uncontrollable self-association of the molecules in water resulted in aggregates and liposomes of quite different sizes without a structure-property relationship. Likewise, adding DNA to the liposomes gave rise to unpredictable sized lipoplexes, which, again, transfected without a structure-activity relationship. Nevertheless, one compound among the novel lipids (C30:9 chain paired with a C20:0 chain) exhibited comparable transfection efficiency and toxicity to the control cationic lipid EPC. Thus, the presence of a rigid polyene chain in this best performing achiral glycol lipid did not have an influence on transfection compared with the chiral glycerolipid reference ethyl phosphocholine EPC with two flexible saturated C14 chains. PMID:24814958

  11. Evaluation of an organo-layered double hydroxide and two organic residues as amendments to immobilize metalaxyl enantiomers in soils: A comparative study.

    Science.gov (United States)

    López-Cabeza, Rocío; Cornejo, Juan; Celis, Rafael

    2016-10-01

    Many pollutants released into the environment as a result of human activities are chiral. Pollution control strategies generally consider chiral compounds as if they were achiral and rarely consider enantiomers separately. We compared the performance of three different materials, an organically-modified anionic clay (HT-ELA) and two organic agro-food residues (ALP and ALPc), as amendments to immobilize the chiral fungicide metalaxyl in two soils with different textures, addressing the effects of the amendments on the sorption, persistence, and leaching of each of the two enantiomers of metalaxyl (R-metalaxyl and S-metalaxyl) separately. The effects of the amendments were both soil- and amendment-dependent, as well as enantiomer-selective. The organo-clay (HT-ELA) was much more efficient in increasing the sorption capacity of the soils for the two enantiomers of metalaxyl than the agro-food residues (ALP and ALPc), even when applied at a reduced application rate. The enhanced sorption in HT-ELA-amended soils reduced the bioavailability of metalaxyl enantiomers and their leaching in the soils, mitigating the particularly high leaching potential of the more persistent S enantiomer. The immobilizing capacity of the agro-food residues was more variable, mainly because their addition did not greatly ameliorate the sorption capacity of the soils and had variable effects on the enantiomers degradation rates. HT-ELA showed potential to reduce the bioavailability and mobility of metalaxyl enantiomers in soil and to mitigate the contamination problems particularly associated with the higher leaching potential of the more persistent enantiomer. PMID:27341374

  12. Fast and high-resolution stereochemical analysis by nonuniform sampling and covariance processing of anisotropic natural abundance 2D 2H NMR datasets.

    Science.gov (United States)

    Lafon, Olivier; Hu, Bingwen; Amoureux, Jean-Paul; Lesot, Philippe

    2011-06-01

    Natural abundance deuterium (NAD) 2D NMR spectroscopy using chiral or achiral liquid crystals is an efficient analytical tool for the stereochemical analysis of enantio- or diastereomers by the virtue of proton-to-deuterium substitution. In particular, it allows the measurement of enantiopurity of organic synthetic molecules or the determination of the natural isotopic (1)H/(2)H fractionation in biological molecules, such as fatty acid methyl esters (FAME). So far, the NAD 2D spectra of solutes were acquired by using uniform sampling (US) and processed by conventional 2D Fourier transform (FT), which could result in long measurement times for medium-sized analytes or low solute concentrations. Herein, we demonstrate that this conventional approach can be advantageously replaced by nonuniform sampling (NUS) processed by covariance (Cov) transform. This original spectral reconstruction provides a significant enhancement of spectral resolution, as well as a reduction of measurement times. The application of Cov to NUS data has required the introduction of a regularization procedure in the time domain for the indirect dimension. The analytical potential of combining Cov and NUS is demonstrated by measuring the enantiomeric excess of a scalemic mixture of 2-ethyloxirane and by determining the diastereomeric excess of methyl vernoleate, a natural FAME. These two organic compounds were aligned in a polypeptide (poly(γ-benzyl-L-glutamate)) mesophase. In the case of NAD 2D NMR spectroscopy, we show that Cov and NUS methods allow a decrease in measurement time by a factor of two compared with Cov applied to US data and a factor of four compared with FT applied to US data.

  13. Elongation Factor Tu Prevents Misediting of Gly-tRNA(Gly Caused by the Design Behind the Chiral Proofreading Site of D-Aminoacyl-tRNA Deacylase.

    Directory of Open Access Journals (Sweden)

    Satya Brata Routh

    2016-05-01

    Full Text Available D-aminoacyl-tRNA deacylase (DTD removes D-amino acids mischarged on tRNAs and is thus implicated in enforcing homochirality in proteins. Previously, we proposed that selective capture of D-aminoacyl-tRNA by DTD's invariant, cross-subunit Gly-cisPro motif forms the mechanistic basis for its enantioselectivity. We now show, using nuclear magnetic resonance (NMR spectroscopy-based binding studies followed by biochemical assays with both bacterial and eukaryotic systems, that DTD effectively misedits Gly-tRNAGly. High-resolution crystal structure reveals that the architecture of DTD's chiral proofreading site is completely porous to achiral glycine. Hence, L-chiral rejection is the only design principle on which DTD functions, unlike other chiral-specific enzymes such as D-amino acid oxidases, which are specific for D-enantiomers. Competition assays with elongation factor thermo unstable (EF-Tu and DTD demonstrate that EF-Tu precludes Gly-tRNAGly misediting at normal cellular concentrations. However, even slightly higher DTD levels overcome this protection conferred by EF-Tu, thus resulting in significant depletion of Gly-tRNAGly. Our in vitro observations are substantiated by cell-based studies in Escherichia coli that show that overexpression of DTD causes cellular toxicity, which is largely rescued upon glycine supplementation. Furthermore, we provide direct evidence that DTD is an RNA-based catalyst, since it uses only the terminal 2'-OH of tRNA for catalysis without the involvement of protein side chains. The study therefore provides a unique paradigm of enzyme action for substrate selection/specificity by DTD, and thus explains the underlying cause of DTD's activity on Gly-tRNAGly. It also gives a molecular and functional basis for the necessity and the observed tight regulation of DTD levels, thereby preventing cellular toxicity due to misediting.

  14. Elongation Factor Tu Prevents Misediting of Gly-tRNA(Gly) Caused by the Design Behind the Chiral Proofreading Site of D-Aminoacyl-tRNA Deacylase.

    Science.gov (United States)

    Routh, Satya Brata; Pawar, Komal Ishwar; Ahmad, Sadeem; Singh, Swati; Suma, Katta; Kumar, Mantu; Kuncha, Santosh Kumar; Yadav, Kranthikumar; Kruparani, Shobha P; Sankaranarayanan, Rajan

    2016-05-01

    D-aminoacyl-tRNA deacylase (DTD) removes D-amino acids mischarged on tRNAs and is thus implicated in enforcing homochirality in proteins. Previously, we proposed that selective capture of D-aminoacyl-tRNA by DTD's invariant, cross-subunit Gly-cisPro motif forms the mechanistic basis for its enantioselectivity. We now show, using nuclear magnetic resonance (NMR) spectroscopy-based binding studies followed by biochemical assays with both bacterial and eukaryotic systems, that DTD effectively misedits Gly-tRNAGly. High-resolution crystal structure reveals that the architecture of DTD's chiral proofreading site is completely porous to achiral glycine. Hence, L-chiral rejection is the only design principle on which DTD functions, unlike other chiral-specific enzymes such as D-amino acid oxidases, which are specific for D-enantiomers. Competition assays with elongation factor thermo unstable (EF-Tu) and DTD demonstrate that EF-Tu precludes Gly-tRNAGly misediting at normal cellular concentrations. However, even slightly higher DTD levels overcome this protection conferred by EF-Tu, thus resulting in significant depletion of Gly-tRNAGly. Our in vitro observations are substantiated by cell-based studies in Escherichia coli that show that overexpression of DTD causes cellular toxicity, which is largely rescued upon glycine supplementation. Furthermore, we provide direct evidence that DTD is an RNA-based catalyst, since it uses only the terminal 2'-OH of tRNA for catalysis without the involvement of protein side chains. The study therefore provides a unique paradigm of enzyme action for substrate selection/specificity by DTD, and thus explains the underlying cause of DTD's activity on Gly-tRNAGly. It also gives a molecular and functional basis for the necessity and the observed tight regulation of DTD levels, thereby preventing cellular toxicity due to misediting. PMID:27224426

  15. Chiral crystal of a C2v-symmetric 1,3-diazaaulene derivative showing efficient optical second harmonic generation

    KAUST Repository

    Ma, Xiaohua

    2011-03-01

    Achiral nonlinear optical (NLO) chromophores 1,3-diazaazulene derivatives, 2-(4â€-aminophenyl)-6-nitro-1,3-diazaazulene (APNA) and 2-(4â€-N,N-diphenylaminophenyl)-6-nitro-1,3-diazaazulene (DPAPNA), were synthesized with high yield. Despite the moderate static first hyperpolarizabilities (β0) for both APNA [(136 ± 5) à - 10-30 esu] and DPAPNA [(263 ± 20) à - 10-30 esu], only APNA crystal shows a powder efficiency of second harmonic generation (SHG) of 23 times that of urea. It is shown that the APNA crystallization driven cooperatively by the strong H-bonding network and the dipolar electrostatic interactions falls into the noncentrosymmetric P2 12121 space group, and that the helical supramolecular assembly is solely responsible for the efficient SHG response. To the contrary, the DPAPNA crystal with centrosymmetric P-1 space group is packed with antiparalleling dimmers, and is therefore completely SHG-inactive. 1,3-Diazaazulene derivatives are suggested to be potent building blocks for SHG-active chiral crystals, which are advantageous in high thermal stability, excellent near-infrared transparency and high degree of designing flexibility. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011 Optical crystals based on 1,3-diazaazulene derivatives are reported as the first example of organic nonlinear optical crystal whose second harmonic generation activity is found to originate solely from the chirality of their helical supramolecular orientation. The strong H-bond network forming between adjacent choromophores is found to act cooperatively with dipolar electrostatic interactions in driving the chiral crystallization of this material. Copyright © 2011 Wiley Periodicals, Inc.

  16. Structure of the complex of [Ru(tpm)(dppz)py](2+) with a B-DNA oligonucleotide - a single-substituent binding switch for a metallo-intercalator.

    Science.gov (United States)

    Waywell, Philip; Gonzalez, Veronica; Gill, Martin R; Adams, Harry; Meijer, Anthony J H M; Williamson, Mike P; Thomas, James A

    2010-02-22

    We report the synthesis of three new complexes related to the achiral [Ru(tpm)(dppz)py](2+) cation (tpm=tripyridazole methane, dppz=dipyrido[3,2-a:2',3'-c]phenazine, py=pyridine) that contain an additional single functional group on the monodentate ancillary pyridyl ligand. Computational calculations indicate that the coordinated pyridyl rings are in a fixed orientation parallel to the dppz axis, and that the electrostatic properties of the complexes are very similar. DNA binding studies on the new complexes reveal that the nature and positioning of the functional group has a profound effect on the binding mode and affinity of these complexes. To explore the molecular and structural basis of these effects, circular dichroism and NMR studies on [Ru(tpm)(dppz)py]Cl(2) with the octanucleotides d(AGAGCTCT)(2) and d(CGAGCTCG)(2), were carried out. These studies demonstrate that the dppz ligand intercalates into the G(2)-A(3) step, with {Ru(tpm)py} in the minor groove. They also reveal that the complex intercalates into the binding site in two possible orientations with the pyridyl ligand of the major conformer making close contact with terminal base pairs. We conclude that substitution at the 2- or 3-position of the pyridine ring has little effect on binding, but that substitution at the 4-position drastically disrupts intercalative binding, particularly with a 4-amino substituent, because of steric and electronic interactions with the DNA. These results indicate that complexes derived from these systems have the potential to function as sequence-specific light-switch systems.

  17. The crystalline sponge method updated

    Science.gov (United States)

    Hoshino, Manabu; Khutia, Anupam; Xing, Hongzhu; Inokuma, Yasuhide; Fujita, Makoto

    2016-01-01

    Crystalline sponges are porous metal complexes that can absorb and orient common organic molecules in their pores and make them observable by conventional X-ray structure analysis (crystalline sponge method). In this study, all of the steps in the crystalline sponge method, including sponge crystal preparation, pore–solvent exchange, guest soaking, data collection and crystallographic analysis, are carefully examined and thoroughly optimized to provide reliable and meaningful chemical information as chemical crystallography. Major improvements in the method have been made in the guest-soaking and data-collection steps. In the soaking step, obtaining a high site occupancy of the guest is particularly important, and dominant parameters for guest soaking (e.g. temperature, time, concentration, solvents) therefore have to be optimized for every sample compound. When standard conditions do not work, a high-throughput method is useful for efficiently optimizing the soaking conditions. The X-ray experiments are also carefully re-examined. Significant improvement of the guest data quality is achieved by complete data collection at high angle regions. The appropriate disorder treatment of the most flexible ZnI2 portions of the host framework and refinement of the solvents filling the remaining void are also particularly important for obtaining better data quality. A benchmark test for the crystalline sponge method toward an achiral molecule is proposed with a guaiazulene guest, in which the guest structure (with ∼ 100% site occupancy) is refined without applying any restraints or constraints. The obtained data quality with R int = 0.0279 and R 1 = 0.0379 is comparable with that of current conventional crystallographic analysis for small molecules. Another benchmark test for this method toward a chiral molecule is also proposed with a santonin guest. The crystallographic data obtained [R int = 0.0421, R 1 = 0.0312, Flack (Parsons) = −0.0071 (11)] represents the

  18. Polar Order and Symmetry Breaking at the Boundary between Bent-Core and Rodlike Molecular Forms: When 4-Cyanoresorcinol Meets the Carbosilane End Group.

    Science.gov (United States)

    Westphal, Eduard; Gallardo, Hugo; Caramori, Giovanni Finoto; Sebastián, Nerea; Tamba, Maria-Gabriela; Eremin, Alexey; Kawauchi, Susumu; Prehm, Marko; Tschierske, Carsten

    2016-06-01

    Two isomeric achiral bent-core liquid crystals involving a 4-cyanoresorcinol core and containing a carbosilane unit as nanosegregating segment were synthesized and were shown to form ferroelectric liquid-crystalline phases. Inversion of the direction of one of the COO groups in these molecules leads to a distinct distribution of the electrostatic potential along the surface of the molecule and to a strong change of the molecular dipole moments. Thus, a distinct degree of segregation of the carbosilane units and consequent modification of the phase structure and coherence length of polar order result. For the compound with larger dipole moment (CN1) segregation of the carbosilane units is suppressed, and this compound forms paraelectric SmA and SmC phases; polar order is only achieved after transition to a new LC phase, namely, the ferroelectric leaning phase (SmCLs PS ) with the unique feature that tilt direction and polar direction coincide. The isomeric compound CN2 with a smaller dipole moment forms separate layers of the carbosilane groups and shows a randomized polar SmA phase (SmAPAR ) and ferroelectric polydomain SmCs PS phases with orthogonal combination of tilt and polar direction and much higher polarizations. Thus, surprisingly, the compound with the smaller molecular dipole moment shows increased polar order in the LC phases. Besides ferroelectricity, mirror-symmetry breaking with formation of a conglomerate of macroscopic chiral domains was observed in one of the SmC phases of CN1. These investigations contribute to the general understanding of the development of polar order and chirality in soft matter.

  19. The crystalline sponge method updated

    Directory of Open Access Journals (Sweden)

    Manabu Hoshino

    2016-03-01

    Full Text Available Crystalline sponges are porous metal complexes that can absorb and orient common organic molecules in their pores and make them observable by conventional X-ray structure analysis (crystalline sponge method. In this study, all of the steps in the crystalline sponge method, including sponge crystal preparation, pore–solvent exchange, guest soaking, data collection and crystallographic analysis, are carefully examined and thoroughly optimized to provide reliable and meaningful chemical information as chemical crystallography. Major improvements in the method have been made in the guest-soaking and data-collection steps. In the soaking step, obtaining a high site occupancy of the guest is particularly important, and dominant parameters for guest soaking (e.g. temperature, time, concentration, solvents therefore have to be optimized for every sample compound. When standard conditions do not work, a high-throughput method is useful for efficiently optimizing the soaking conditions. The X-ray experiments are also carefully re-examined. Significant improvement of the guest data quality is achieved by complete data collection at high angle regions. The appropriate disorder treatment of the most flexible ZnI2 portions of the host framework and refinement of the solvents filling the remaining void are also particularly important for obtaining better data quality. A benchmark test for the crystalline sponge method toward an achiral molecule is proposed with a guaiazulene guest, in which the guest structure (with ∼ 100% site occupancy is refined without applying any restraints or constraints. The obtained data quality with Rint = 0.0279 and R1 = 0.0379 is comparable with that of current conventional crystallographic analysis for small molecules. Another benchmark test for this method toward a chiral molecule is also proposed with a santonin guest. The crystallographic data obtained [Rint = 0.0421, R1 = 0.0312, Flack (Parsons = −0.0071 (11

  20. The crystalline sponge method updated.

    Science.gov (United States)

    Hoshino, Manabu; Khutia, Anupam; Xing, Hongzhu; Inokuma, Yasuhide; Fujita, Makoto

    2016-03-01

    Crystalline sponges are porous metal complexes that can absorb and orient common organic molecules in their pores and make them observable by conventional X-ray structure analysis (crystalline sponge method). In this study, all of the steps in the crystalline sponge method, including sponge crystal preparation, pore-solvent exchange, guest soaking, data collection and crystallographic analysis, are carefully examined and thoroughly optimized to provide reliable and meaningful chemical information as chemical crystallography. Major improvements in the method have been made in the guest-soaking and data-collection steps. In the soaking step, obtaining a high site occupancy of the guest is particularly important, and dominant parameters for guest soaking (e.g. temperature, time, concentration, solvents) therefore have to be optimized for every sample compound. When standard conditions do not work, a high-throughput method is useful for efficiently optimizing the soaking conditions. The X-ray experiments are also carefully re-examined. Significant improvement of the guest data quality is achieved by complete data collection at high angle regions. The appropriate disorder treatment of the most flexible ZnI2 portions of the host framework and refinement of the solvents filling the remaining void are also particularly important for obtaining better data quality. A benchmark test for the crystalline sponge method toward an achiral molecule is proposed with a guaiazulene guest, in which the guest structure (with ∼ 100% site occupancy) is refined without applying any restraints or constraints. The obtained data quality with R int = 0.0279 and R 1 = 0.0379 is comparable with that of current conventional crystallographic analysis for small molecules. Another benchmark test for this method toward a chiral molecule is also proposed with a santonin guest. The crystallographic data obtained [R int = 0.0421, R 1 = 0.0312, Flack (Parsons) = -0.0071 (11)] represents the

  1. Three luminescent d{sup 10} metal coordination polymers assembled from a semirigid V-shaped ligand with high selective detecting of Cu{sup 2+} ion and nitrobenzene

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Wei-Ping [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorg. Chem., College of Chemistry & Materials Science, Northwest University, Xi’an 710069 (China); Institute of Functional Materials, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science & Engineering, Zigong 643000 (China); Liu, Ping; Liang, Yu-Tong; Cui, Lin; Xi, Zheng-Ping [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorg. Chem., College of Chemistry & Materials Science, Northwest University, Xi’an 710069 (China); Wang, Yao-Yu, E-mail: wyaoyu@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorg. Chem., College of Chemistry & Materials Science, Northwest University, Xi’an 710069 (China)

    2015-08-15

    Three 2D luminescent coordination polymers with helical frameworks, [ZnL{sub 2}]{sub n} (1) and ([ML{sub 2}]·(H{sub 2}O)){sub n} (M=Zn (2), Cd (3)) (HL=4-((2-methyl-1 H-imidazol-1-yl)methyl)benzoic acid), have been assembled under hydro(solvo)thermal conditions. Complex 1 is in chiral space group and displays a rare 2D→2D 2-fold parallel interpenetrated layer network with two types of chiral double helixes. Interestingly, the single crystal structure analyses indicate the coexistence of enantiomers la and 1b in one pot, while the bulk crystallization of 1 are racemic mixtures based on the CD measurement. 2 and 3 are isostructural, in the structure, there are two kinds of 2D chiral helical-layers which stack in an -ABAB- sequence leading to the overall structure are mesomer and achiral. All compounds display intense luminescence in solid state at room temperature with high chemical and thermal stability. More importantly, 1 has been successfully applied in the detection of Cu{sup 2+} ions in aqueous media and nitrobenzene and the probable detecting mechanism was also discussed. - Graphical abstract: Three luminescent d{sup 10} metal coordination polymers with helical-layer based on 4-((2-methyl-1H-imidazol-1-yl)methyl)benzoic acid have been obtained. Compound 1 shows high selective detecting for Cu{sup 2+} ion in aqueous and nitrobenzene. - Highlights: • Three coordination polymers with chiral helical-layer have been obtained. • 1 Can luminescent detect Cu{sup 2+} ion in aqueous media and nitrobenzene. • Racemic mixture or mesomer compounds can be obtained by controlling the reaction conditions.

  2. Exploring the substructural space of indole-3-carboxamide derivatives binding to renin: a novel active-site spatial partitioning approach.

    Science.gov (United States)

    Jing, Tao; Feng, Jian; Zuo, Yumei; Ran, Boli; Liu, Jianping; He, Guoxiang

    2012-09-01

    Renin has recently attracted much attention in the antihypertensive community, since this enzyme starts the angiotensin-converting cascade and forms the rate-limiting step in this cascade. In the present study, we describe a new method called active-site spatial partitioning (ASSP) for quantitatively characterizing the nonbonding interaction profile between renin and the substructures of indole-3-carboxamide derivatives-a novel class of achiral renin inhibitors that exhibit both high affinity and strong specificity for renin, thus blocking its active state-on the basis of structural models of protein-ligand complexes. It is shown that the ASSP-derived potential parameters are highly correlated with the experimentally measured activities of indole-3-carboxamides; the statistical models linking the parameters and activities using a sophisticated partial least squares regression technique show much promise as an effective and powerful tool for generalizing and predicting the pharmaceutical potencies and the physicochemical properties of other modified derivatives. Furthermore, by visually examining substructure-color plots generated by the ASSP procedure, it is found that the relative importance of nonbonding contributions to the recognition and binding of a ligand by renin is as follows: steric < hydrophobic < electrostatic. The polar and charged moieties that float on the surface of the ligand molecule play a critical role in conferring electrostatic stability and specificity to renin-ligand complexes, whereas the aromatic rings embedded in the core region of the ligand are the main source of hydrophobic and steric potentials that lead to substantial stabilization of the complex architecture. PMID:22588582

  3. Investigation of Solute-Fiber Affinity and Orientational Ordering of Norbornadiene Interacting with Two-Polypeptide Chiral Liquid Crystalline Solvents by Natural Abundance Deuterium (NAD) NMR.

    Science.gov (United States)

    Serhan, Zeinab; Aroulanda, Christie; Lesot, Philippe

    2016-08-01

    A prochiral bridged compound of C2v symmetry, the norbornadiene (NBD), oriented in a chiral liquid crystal composed of various mixtures of poly-γ-benzyl-l-glutamate (PBLG) and poly-ε-carboxy-l-lysine (PCBLL), two chiral homopolypeptides, is investigated using natural abundance deuterium 2D-NMR (NAD 2D-NMR) spectroscopy. In such chiral oriented solvents, enantiotopic directions are spectrally nonequivalent, and two distinct (2)H quadrupolar doublets associated with enantioisotopomeric pairs of NBD are detected. As the two homopolypeptides have the same absolute configuration but distinct chemical functions in their side chains, the variation of residual quadrupolar couplings (RQC's) allows the determination of the relative solute-fiber affinities toward the two polypeptides in these lyotropic bipolymeric systems. Besides the experimental measurement of RQC's and the determination of their signs at each inequivalent (2)H site, the elements of the second-rank order tensor, Sαβ, are calculated by assuming a modeled structure. The variations of RQC's and diagonalized order parameters, Sα'α', are followed versus the relative proportion of two polypeptides in the chiral oriented mixture. The influence of the solute mass fraction in the two-homopolypeptide oriented samples is also examined as well as the case of homogeneous and uniform achiral mesophases "PBG-PCBL" made of two pairs of mirror-image homopolypeptides (PBLG/PBDG and PCBLL/PCBDL). In the latter, the solute ordering is modulated by the proportion of each type of homopolypeptide (chemical nature and absolute configuration), leading to eliminate the enantiodiscrimination mechanisms on the average. In the frame of a model, new insights on the solute-homopolypeptide fiber interactions are discussed. PMID:27383731

  4. Evaluation of an organo-layered double hydroxide and two organic residues as amendments to immobilize metalaxyl enantiomers in soils: A comparative study.

    Science.gov (United States)

    López-Cabeza, Rocío; Cornejo, Juan; Celis, Rafael

    2016-10-01

    Many pollutants released into the environment as a result of human activities are chiral. Pollution control strategies generally consider chiral compounds as if they were achiral and rarely consider enantiomers separately. We compared the performance of three different materials, an organically-modified anionic clay (HT-ELA) and two organic agro-food residues (ALP and ALPc), as amendments to immobilize the chiral fungicide metalaxyl in two soils with different textures, addressing the effects of the amendments on the sorption, persistence, and leaching of each of the two enantiomers of metalaxyl (R-metalaxyl and S-metalaxyl) separately. The effects of the amendments were both soil- and amendment-dependent, as well as enantiomer-selective. The organo-clay (HT-ELA) was much more efficient in increasing the sorption capacity of the soils for the two enantiomers of metalaxyl than the agro-food residues (ALP and ALPc), even when applied at a reduced application rate. The enhanced sorption in HT-ELA-amended soils reduced the bioavailability of metalaxyl enantiomers and their leaching in the soils, mitigating the particularly high leaching potential of the more persistent S enantiomer. The immobilizing capacity of the agro-food residues was more variable, mainly because their addition did not greatly ameliorate the sorption capacity of the soils and had variable effects on the enantiomers degradation rates. HT-ELA showed potential to reduce the bioavailability and mobility of metalaxyl enantiomers in soil and to mitigate the contamination problems particularly associated with the higher leaching potential of the more persistent enantiomer.

  5. Enantiomeric excesses induced in amino acids by ultraviolet circularly polarized light irradiation of extraterrestrial ice analogs: A possible source of asymmetry for prebiotic chemistry

    International Nuclear Information System (INIS)

    The discovery of meteoritic amino acids with enantiomeric excesses of the L-form (ee L) has suggested that extraterrestrial organic materials may have contributed to prebiotic chemistry and directed the initial occurrence of the ee L that further led to homochirality of amino acids on Earth. A proposed mechanism for the origin of ee L in meteorites involves an asymmetric photochemistry of extraterrestrial ices by UV circularly polarized light (CPL). We have performed the asymmetric synthesis of amino acids on achiral extraterrestrial ice analogs by VUV CPL, investigating the chiral asymmetry transfer at two different evolutionary stages at which the analogs were irradiated (regular ices and/or organic residues) and at two different photon energies (6.6 and 10.2 eV). We identify 16 distinct amino acids and precisely measure the L-enantiomeric excesses using the enantioselective GC × GC-TOFMS technique in five of them: α-alanine, 2,3-diaminopropionic acid, 2-aminobutyric acid, valine, and norvaline, with values ranging from ee L = –0.20% ± 0.14% to ee L = –2.54% ± 0.28%. The sign of the induced ee L depends on the helicity and the energy of CPL, but not on the evolutionary stage of the samples, and is the same for all five considered amino acids. Our results support an astrophysical scenario in which the solar system was formed in a high-mass star-forming region where icy grains were irradiated during the protoplanetary phase by an external source of CPL of a given helicity and a dominant energy, inducing a stereo-specific photochemistry.

  6. Complex organic molecules at metal surfaces: bonding, organisation and chirality [review article

    Science.gov (United States)

    Barlow, S. M.; Raval, R.

    2003-08-01

    Surface science techniques have now reached a stage of maturity that has enabled their successful deployment in the study of complex adsorption systems. A particular example of this success has been the understanding that has been gained regarding the behaviour of multi-functional organic molecules at metal surfaces. These organic-metal systems show enormous diversity, starting from their local description which can vary in terms of chemical structure, orientation and bonding. Additionally, in many cases, these complex organic molecules self-organise into beautiful, ordered superstructures held together by networks of intermolecular bonds. Both these aspects enable a single organic molecule-metal system to exhibit a wide-ranging and flexible approach to its environment, leading to a variety of adsorption phases, according to the prevailing temperature and coverage conditions. In this review we have attempted to capture this complexity by constructing adsorption phase diagrams from the available literature for complex carboxylic acids, amino acids, anhydrides and ring systems, all deposited under controlled conditions onto defined metal surfaces. These provide an accessible, pictorial basis of the adsorption phases which are then discussed further in the text of the review. Finally, interest has recently focused on the property of chirality that can be bestowed at an achiral metal surface by the adsorption of these complex organic molecules. The creation of such architectures offers the opportunity for ultimate stereocontrol of reactions and responses at surfaces. We have, therefore, specifically examined the various ways in which chirality can be expressed at a surface and provide a framework for classifying chiral hierarchies that are manifested at surfaces, with particular attention being paid to the progression of chirality from a local to a global level.

  7. Transfer of noncovalent chiral information along an optically inactive helical peptide chain: allosteric control of asymmetry of the C-terminal site by external molecule that binds to the N-terminal site.

    Science.gov (United States)

    Ousaka, Naoki; Inai, Yoshihito

    2009-02-20

    This study aims at demonstrating end-to-end transfer of noncovalent chiral information along a peptide chain. The domino-type induction of helical sense is proven by using achiral peptides 1-m of bis-chromophoric sequence with different chain lengths: H-(Aib-Delta(Z)Phe)(m)-(Aib-Delta(Z)Bip)(2)-Aib-OCH(3) [m = 2, 4, and 6; Aib = alpha-aminoisobutyric acid; Delta(Z)Phe = (Z)-alpha,beta-didehydrophenylalanine; Delta(Z)Bip = (Z)-beta-(4,4'-biphenyl)-alpha,beta-didehydroalanine]. They all showed the tendency to adopt a 3(10)-helix. Whereas peptide 1-m originally shows no circular dichroism (CD) signals, marked CD signals were induced at around 270-320 nm based on both the beta-aryl didehydroresidues by chiral Boc-proline (Boc = tert-butoxycarbonyl). The observed CD spectra were interpreted on the basis of the exciton chirality method and theoretical CD simulation of several helical conformations that were energy-minimized. The experimental and theoretical CD analysis reveals that Boc-l-proline induces the preference for a right-handed helicity in the whole chain of 1-m. Such noncovalent chiral induction was not observed in the corresponding N-terminally protected 1-m. Obviously, helicity induction in 1-m originates from the binding of Boc-proline to the N-terminal site. In the 17-mer (1-6), the information of helix sense reaches the 16th residue from the N-terminus. We have monitored precise transfer of noncovalent chiral stimulus along a helical peptide chain. The present study also proposes a primitive allosteric model of a single protein-mimicking backbone. Here chiral molecule binding the N-terminal site of 1-6 controls the chiroptical signals and helical sense of the C-terminal site about 30 A away.

  8. Chiral Pesticides in Soil and Water and Exchange with the Atmosphere

    Directory of Open Access Journals (Sweden)

    Terry F. Bidleman

    2002-01-01

    enantiomer fractions (EFs and mass balance in the water column. Apparent pseudo first-order rate constants in the eastern Arctic Ocean are 0.12 year-1 for (+α-HCH, 0.030 year-1 for (–α-HCH, and 0.037 year-1 for achiral Υ-HCH. These rate constants are 3–10 times greater than those for basic hydrolysis in seawater. Microbial breakdown may compete with advective outflow for long-term removal of HCHs from the Arctic Ocean. Rate constants estimated for the arctic lake are about 3–8 times greater than those in the ocean.

  9. Chiral pesticides in soil and water and exchange with the atmosphere.

    Science.gov (United States)

    Bidleman, Terry F; Leone, Andi D; Falconer, Renee L; Harner, Tom; Jantunen, Liisa M M; Wiberg, Karin; Helm, Paul A; Diamond, Miriam L; Loo, Binh

    2002-02-01

    enantiomer fractions (EFs) and mass balance in the water column. Apparent pseudo first-order rate constants in the eastern Arctic Ocean are 0.12 year(-1) for (+)alpha-HCH, 0.030 year(-1) for (-)alpha-HCH, and 0.037 year(-1) for achiral gamma-HCH. These rate constants are 3-10 times greater than those for basic hydrolysis in seawater. Microbial breakdown may compete with advective outflow for long-term removal of HCHs from the Arctic Ocean. Rate constants estimated for the arctic lake are about 3-8 times greater than those in the ocean. PMID:12806022

  10. 苄醚型树枝化碳水化合物的合成与液晶性%Benzyl ether type of dendronized carbohydrates:Synthesis and liquid crystallinity

    Institute of Scientific and Technical Information of China (English)

    杨柳林; 曹擎; 董炎明; 胡晓兰; 刘安华; 赵雅青

    2012-01-01

    Most of traditional carbohydrate liquid crystals are composed of sugar moiety substituted by n-alkyl chains. There are still quite limited categories in this liquid crystal library. In this study, dendronized carbohydrate liquid crystals were synthesized with N-acetylglucosamine as core unit, and wedge or taper shaped benzyl ether type dendrons as branches. Liquid crystallinity of dendronized carbohydrates was studied by POM, DSC, XRD, CD/UV spectroscopy. Molecules contain wedge shaped dendrons can self-organize into chiral columnar hexagonal phase or achiral nematic phase, while molecules contain taper shaped dendrons still self-organize into chiral columnar hexagonal phase, not however cubic phase as suspected. Supramolecular chirality is most probably derived from a helical arrangement of dendrimers around the cylinder axis, driven by a collaborative self-assembly of carbohydrate core and dendron branches, and the chiral carbohydrate center plays the primary role of selecting the handedness of the helix so as not to be racemization. This novel dendronized carbohydrate liquid crystal may provide inspiration in the study of chiral supramolecular aggregates induced by carbohydrates.%选取3种不同结构的苄醚型树枝状分子为分枝,以N-乙酰氨基葡萄糖为内核,合成出一类树枝化碳水化物;利用DSC、热台偏光显微镜、XRD和CD/UV光谱等手段研究该类化合物的液晶性,并命名为树状碳水化合物液晶.研究表明,连接有楔形树枝状单元的化合物形成手性柱状六方相或者向列相,连接有锥形树枝状单元的化合物未能如预期形成立方相,而仍然形成手性柱状六方相.超分子手性很可能源于树枝状单元与糖内核的协同自组装,使得树状分子沿着柱轴螺旋式堆砌;而糖环内核则对超分子柱的手性起调控作用,从而避免了外消旋的发生.该类化合物为研究碳水化合物诱导手性超分子聚集体提供了新的思路.

  11. Two multidimensional chromatographic methods for enantiomeric analysis of o,p'-DDT and o,p'-DDD in contaminated soil and air in a malaria area of South Africa.

    Science.gov (United States)

    Naudé, Yvette; Rohwer, Egmont R

    2012-06-12

    In rural parts of South Africa the organochlorine insecticide DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane) is still used for malaria vector control where traditional dwellings are sprayed on the inside with small quantities of technical DDT. Since o,p'-DDT may show enantioselective oestrogenicity and biodegradability, it is important to analyse enantiomers of o,p'-DDT and its chiral degradation product, o,p'-DDD, for both health and environmental-forensic considerations. Generally, chiral analysis is performed using heart-cut multidimensional gas chromatography (MDGC) and, more recently, comprehensive two-dimensional gas chromatography (GC×GC). We developed an off-line gas chromatographic fraction collection (heart-cut) procedure for the selective capturing of the appropriate isomers from a first apolar column, followed by reinjection and separation on a second chiral column. Only the o,p'-isomers of DDT and DDD fractions from the first dimension complex chromatogram (achiral apolar GC column separation) were selectively collected onto a polydimethylsiloxane (PDMS) multichannel open tubular silicone rubber trap by simply placing the latter device on the flame tip of an inactivated flame ionisation detector (FID). The multichannel trap containing the o,p'-heart-cuts was then thermally desorbed into a GC with time-of-flight mass spectrometry detection (GC-TOFMS) for second dimension enantioselective separation on a chiral column (β-cyclodextrin-based). By selectively capturing only the o,p'-isomers from the complex sample chromatogram, (1)D separation of ultra-trace level enantiomers could be achieved on the second chiral column without matrix interference. Here, we present solventless concentration techniques for extraction of DDT from contaminated soil and air, and report enantiomeric fraction (EF) values of o,p'-DDT and o,p'-DDD obtained by a new multidimensional approach for heart-cut gas chromatographic fraction collection for off-line second dimension

  12. Thioamides: versatile bonds to induce directional and cooperative hydrogen bonding in supramolecular polymers.

    Science.gov (United States)

    Mes, Tristan; Cantekin, Seda; Balkenende, Dirk W R; Frissen, Martijn M M; Gillissen, Martijn A J; De Waal, Bas F M; Voets, Ilja K; Meijer, E W; Palmans, Anja R A

    2013-06-24

    The amide bond is a versatile functional group and its directional hydrogen-bonding capabilities are widely applied in, for example, supramolecular chemistry. The potential of the thioamide bond, in contrast, is virtually unexplored as a structuring moiety in hydrogen-bonding-based self-assembling systems. We report herein the synthesis and characterisation of a new self-assembling motif comprising thioamides to induce directional hydrogen bonding. N,N',N''-Trialkylbenzene-1,3,5-tris(carbothioamide)s (thioBTAs) with either achiral or chiral side-chains have been readily obtained by treating their amide-based precursors with P2S5. The thioBTAs showed thermotropic liquid crystalline behaviour and a columnar mesophase was assigned. IR spectroscopy revealed that strong, three-fold, intermolecular hydrogen-bonding interactions stabilise the columnar structures. In apolar alkane solutions, thioBTAs self-assemble into one-dimensional, helical supramolecular polymers stabilised by three-fold hydrogen bonding. Concentration- and temperature-dependent self-assembly studies performed by using a combination of UV and CD spectroscopy demonstrated a cooperative supramolecular polymerisation mechanism and a strong amplification of supramolecular chirality. The high dipole moment of the thioamide bond in combination with the anisotropic shape of the resulting cylindrical aggregate gives rise to sufficiently strong depolarised light scattering to enable depolarised dynamic light scattering (DDLS) experiments in dilute alkane solution. The rotational and translational diffusion coefficients, D(trans) and D(rot), were obtained from the DDLS measurements, and the average length, L, and diameter, d, of the thioBTA aggregates were derived (L = 490 nm and d = 3.6 nm). These measured values are in good agreement with the value L(w) = 755 nm obtained from fitting the temperature-dependent CD data by using a recently developed equilibrium model. This experimental verification

  13. Molecular-Level Design of Heterogeneous Chiral Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Francisco Zaera

    2012-03-21

    , and the development of ways to imprint chiral centers on achiral solid surfaces. Chiral catalysis is not only a problem of great importance in its own right, but also the ultimate test of how to control selectivity in catalysis. The time is ripe for fundamental work in heterogeneous chiral catalysis to provide the U.S. with a leadership role in developing the next generation of catalytic processes for medicinal and agrochemical manufacturing. Our team provides the required expertise for a synergistic and comprehensive integration of physical and chemical experimentation with solid state and molecular reactivity theories to solve this problem.

  14. Account of helical and rotational symmetries in the linear augmented cylindrical wave method for calculating the electronic structure of nanotubes: Towards the ab initio determination of the band structure of a (100, 99) tubule

    Science.gov (United States)

    D'Yachkov, P. N.; Makaev, D. V.

    2007-11-01

    Every carbon single-walled nanotube (SWNT) can be generated by first mapping only two nearest-neighbor C atoms onto a surface of a cylinder and then using the rotational and helical symmetry operators to determine the remainder of the tubule [C. T. White , Phys. Rev. B 47, 5485 (1993)]. With account of these symmetries, we developed a symmetry-adapted version of a linear augmented cylindrical wave method. In this case, the cells contain only two carbon atoms, and the ab initio theory becomes applicable to any SWNT independent of the number of atoms in a translational unit cell. The approximations are made in the sense of muffin-tin (MT) potentials and local-density-functional theory only. An electronic potential is suggested to be spherically symmetrical in the regions of atoms and constant in an interspherical region up to the two essentially impenetrable cylinder-shaped potential barriers. To construct the basis wave functions, the solutions of the Schrödinger equation for the interspherical and MT regions of the tubule were sewn together using a theorem of addition for cylindrical functions, the resulting basis functions being continuous and differentiable anywhere in the system. With account of analytical equations for these functions, the overlap and Hamiltonian integrals are calculated, which permits determination of electronic structure of nanotube. We have calculated the total band structures and densities of states of the chiral and achiral, semiconducting, semimetallic, and metallic carbon SWNTs (13, 0), (12, 2), (11, 3), (10, 5), (9, 6), (8, 7), (7, 7), (12, 4), and (100, 99) containing up to the 118 804 atoms per translational unit cell. Even for the (100, 99) system with huge unit cell, the band structure can be easily calculated and the results can be presented in the standard form of four curves for the valence band plus one curve for the low-energy states of conduction band. About 150 functions produce convergence of the band structures better then

  15. Controllable synthesis of Zn/Cd(ii) coordination polymers: dual-emissive luminescent properties, and tailoring emission tendency under varying excitation energies.

    Science.gov (United States)

    Xing, Kai; Fan, Ruiqing; Gao, Song; Wang, Xinming; Du, Xi; Wang, Ping; Fang, Ru; Yang, Yulin

    2016-03-21

    Based on a new asymmetric semi-rigid V-shaped tricarboxylate ligand 3-(2',3'-dicarboxylphenoxy)benzoic acid (H3dpob), a series of zinc/cadmium(ii) coordination polymers, {[Cd(Hdpob)(H2O)3]·H2O}n (1), [Cd(Hdpob)(bib)]n (2), [Zn(Hdpob)(bib)0.5]n (3), {[Cd1.5(dpob)(2,2'-bipy)]·0.5H2O}2n (4) and {[Cd3(dpob)2(4,4'-bipy)2]·3H2O}n (5) [bib = 1,4-bis(1-imidazolyl)benzene; 2,2'-bipy = 2,2'-bipyridine; 4,4'-bipy = 4,4'-bipyridine], have been successfully synthesized via hydro(solvo)thermal reactions. 1 forms a three dimensional (3D) supramolecular structure linked by two types of intermolecular hydrogen bonds based on zig-zag 1D chains, whereas 2 and 3 are obtained with a similar 2D layer structure by the same ligands and further connected into a 3D structure through hydrogen bonds. 4 displays a homochiral 2D structure though two achiral ligands 2,2'-bipy and H3dpob, which contains right-handed helical infinite chains. 5 is a 3D structure containing 2D metal-pyridine layer motifs, which are further pillared by beaded dpob(3-) ligands to complete the structure and form a 6-connected pcu (primitive cubic) net. In DMSO solvent, 1-5 illustrate dual-emission properties but have different low-energy emission (LE) intensities relatively. Extraordinarily, the difference resulting from central metals between 2 and 3 makes the intensity of LE dramatically enhanced and quenched. In this regard, the luminescence of 2 and 3 can be tuned between blue and green regions by varying the excitation light, and the tuning tendency can be tailored with inverse directions. Comparing their tunable-sensitivity to energy quantitatively, the theoretical calculation displays that 3 (4.29%) is little higher than 2 (3.59%) in a relative lower excitation wavelength zone. Meanwhile, five coordination polymers show distinct luminescence thermochromism in the solid state. When the temperature decreases from 298 K to 77 K, the red-shift from blue/green to the pure yellow light region is highlighted. The

  16. Infrared optical activity: electric field approaches in time domain.

    Science.gov (United States)

    Rhee, Hanju; Choi, Jun-Ho; Cho, Minhaeng

    2010-12-21

    Vibrational circular dichroism (VCD) spectroscopy provides detailed information about the absolute configurations of chiral molecules including biomolecules and synthetic drugs. This method is the infrared (IR) analogue of the more popular electronic CD spectroscopy that uses the ultraviolet and visible ranges of the electromagnetic spectrum. Because conventional electronic CD spectroscopy measures the difference in signal intensity, problems such as weak signal and low time-resolution can limit its utility. To overcome the difficulties associated with that approach, we have recently developed femtosecond IR optical activity (IOA) spectrometry, which directly measures the IOA free-induction-decay (FID), the impulsive chiroptical IR response that occurs over time. In this Account, we review the time-domain electric field measurement and calculation methods used to simultaneously characterize VCD and related vibrational optical rotatory dispersion (VORD) spectra. Although conventional methods measure the electric field intensity, this vibrational technique is based on a direct phase-and-amplitude measurement of the electric field of the chiroptical signal over time. This method uses a cross-polarization analyzer to carry out heterodyned spectral interferometry. The cross-polarization scheme enables us to selectively remove the achiral background signal, which is the dominant noise component present in differential intensity measurement techniques. Because we can detect the IOA FID signal in a phase-amplitude-sensitive manner, we can directly characterize the time-dependent electric dipole/magnetic dipole response function and the complex chiral susceptibility that contain information about the angular oscillations of charged particles. These parameters yield information about the VCD and VORD spectra. In parallel with such experimental developments, we have also calculated the IOA FID signal and the resulting VCD spectrum. These simulations use a quantum mechanical

  17. Infrared laser induced population transfer and parity selection in {sup 14}NH{sub 3}: A proof of principle experiment towards detecting parity violation in chiral molecules

    Energy Technology Data Exchange (ETDEWEB)

    Dietiker, P.; Miloglyadov, E.; Quack, M., E-mail: Martin@Quack.ch; Schneider, A.; Seyfang, G. [Physical Chemistry, ETH Zürich, CH-8093 Zürich (Switzerland)

    2015-12-28

    We have set up an experiment for the efficient population transfer by a sequential two photon—absorption and stimulated emission—process in a molecular beam to prepare quantum states of well defined parity and their subsequent sensitive detection. This provides a proof of principle for an experiment which would allow for parity selection and measurement of the time evolution of parity in chiral molecules, resulting in a measurement of the parity violating energy difference Δ{sub pv}E between enantiomers of chiral molecules. Here, we present first results on a simple achiral molecule demonstrating efficient population transfer (about 80% on the average for each step) and unperturbed persistence of a selected excited parity level over flight times of about 1.3 ms in the beam. In agreement with model calculations with and without including nuclear hyperfine structure, efficient population transfer can be achieved by a rather simple implementation of the rapid adiabatic passage method of Reuss and coworkers and considering also the stimulated Raman adiabatic passage technique of Bergmann and coworkers as an alternative. The preparation step uses two powerful single mode continuous wave optical parametric oscillators of high frequency stability and accuracy. The detection uses a sensitive resonantly enhanced multiphoton ionization method after free flight lengths of up to 0.8 m in the molecular beam. Using this technique, we were able to also resolve the nuclear hyperfine structure in the rovibrational levels of the ν{sub 1} and ν{sub 3} fundamentals as well as the 2ν{sub 4} overtone of {sup 14}NH{sub 3}, for which no previous data with hyperfine resolution were available. We present our new results on the quadrupole coupling constants for the ν{sub 1}, ν{sub 3}, and 2ν{sub 4} levels in the context of previously known data for ν{sub 2} and its overtone, as well as ν{sub 4}, and the ground state. Thus, now, {sup 14}N quadrupole coupling constants for all

  18. Infrared laser induced population transfer and parity selection in 14NH3: A proof of principle experiment towards detecting parity violation in chiral molecules

    International Nuclear Information System (INIS)

    We have set up an experiment for the efficient population transfer by a sequential two photon—absorption and stimulated emission—process in a molecular beam to prepare quantum states of well defined parity and their subsequent sensitive detection. This provides a proof of principle for an experiment which would allow for parity selection and measurement of the time evolution of parity in chiral molecules, resulting in a measurement of the parity violating energy difference ΔpvE between enantiomers of chiral molecules. Here, we present first results on a simple achiral molecule demonstrating efficient population transfer (about 80% on the average for each step) and unperturbed persistence of a selected excited parity level over flight times of about 1.3 ms in the beam. In agreement with model calculations with and without including nuclear hyperfine structure, efficient population transfer can be achieved by a rather simple implementation of the rapid adiabatic passage method of Reuss and coworkers and considering also the stimulated Raman adiabatic passage technique of Bergmann and coworkers as an alternative. The preparation step uses two powerful single mode continuous wave optical parametric oscillators of high frequency stability and accuracy. The detection uses a sensitive resonantly enhanced multiphoton ionization method after free flight lengths of up to 0.8 m in the molecular beam. Using this technique, we were able to also resolve the nuclear hyperfine structure in the rovibrational levels of the ν1 and ν3 fundamentals as well as the 2ν4 overtone of 14NH3, for which no previous data with hyperfine resolution were available. We present our new results on the quadrupole coupling constants for the ν1, ν3, and 2ν4 levels in the context of previously known data for ν2 and its overtone, as well as ν4, and the ground state. Thus, now, 14N quadrupole coupling constants for all fundamentals and some overtones of 14NH3 are known and can be used for

  19. Evaluation of a series of prolylamidepyridines as the chiral derivatization reagents for enantioseparation of carboxylic acids by LC-ESI-MS/MS and the application to human saliva.

    Science.gov (United States)

    Kuwabara, Tomohiro; Takayama, Takahiro; Todoroki, Kenichiro; Inoue, Koichi; Min, Jun Zhe; Toyo'oka, Toshimasa

    2014-04-01

    biological carboxylic acids, such as lactic acid (LA), 3-hydroxybutylic acid, maric acid, succinic acid, α-ketoglutalic acid, and citric acid, were clearly identified in the saliva of healthy persons and diabetic patients. Furthermore, the ratio of D-LA in diabetic patients was higher than that in normal subjects. Judging from these results, PCP2 seems to be a useful chiral derivatization reagent for the determination not only of chiral, but also achiral, carboxylic acids in real samples. PMID:24500756

  20. Optical and resonant X-ray diffraction studies of molecular arrangements in several liquid crystals

    Science.gov (United States)

    Wang, Suntao

    Using optical and x-ray techniques, we have studied several selected liquid crystal compounds formed by three types of molecules: rod-like; hockey-stick-shaped and bent-core-shaped molecules. This thesis describes four research projects. The first one is a study of the molecular arrangements in freestanding films of three chiral compounds showing no-layer-shrinkage behavior above their bulk SmA-SmC* transition temperatures. Upon cooling under a proper electric field, novel nonplanar-anticlinic-synclinic and nonplanar-synclinic transitions have been observed in two compounds. Increasing electric field can induce a rare transition from a synclinic to an anticlinic structure. Results from both x-ray diffraction and optical studies indicate that different molecular packing arrangements exist within the Sm A phase window. The second project is to investigate three achiral meta-substituted three-ring compounds. These compounds exhibit two different tilted smectic phases, Sm C1 and SmC2. A recent paper has reported that mirror symmetry is broken in one of these compounds. However, no mirror symmetry breaking has been observed in our studies of the same compound. Our studies of another two compounds confirmed previous results that the Sm C1 and SmC2 phases are Sm C and SmCA, respectively. Thirdly, we confirmed the SM C*FI2 -SmC* phase sequence reversal in one liquid crystal compound and specially prepared binary mixtures. This phase sequence reversal was predicted by a recent phenomenological model. Moreover, the temperature range for the SM C*FI2 phase increases significantly in the mixture suggesting that such a phase sequence may exist in other compounds. The last project is to study the B2 phase formed by bent-core molecules using polarization-analyzed resonant x-ray diffraction. The B2 phase has three possible arrangements which show a two-layer unit cell. We analyzed the polarization of the resonant peaks at different Bragg orders. By comparing a theoretical

  1. Investigating the orientational order in smectic liquid crystals

    Science.gov (United States)

    Wang, Shun

    This thesis is composed of two projects. The first one is the investigation of a reversed phase sequence, which subsequently leads to the discovery of a novel Smectic-C liquid crystal phase. The 10OHFBBB1M7 (10OHF) compound shows a reversed phase sequence with the SmC*d4 phase occurring at a higher temperature than the SmC* phase. This phase sequence is stabilized by moderate doping of 9OTBBB1M7 (C9) or 11OTBBB1M7 (C11). To further study this unique phase sequence, the mixtures of 10OHFBBB1M7 and its homologs have been characterized by optical techniques. In order to perform the resonant X-ray diffraction experiment, we have added C9 and C11 compounds to the binary mixtures and pure 10OHF. In two of the studied mixtures, a new smectic-C* liquid crystal phase with six-layer periodicity has been discovered. Upon cooling, the new phase appears between the SmC*a phase having a helical structure and the SmC*d4 phase with four-layer periodicity. The SmC*d6 phase shows a distorted clock structure. Three theoretical models have predicted the existence of a six-layer phase. However, our experimental findings are not consistent with the theories. The second project involves the mixtures of liquid crystals with different shapes. The role of different interactions in stabilizing the antiferroelectric smectic liquid crystal phases have been a long-standing questions in the community. By mixing the antiferroelectric smectic liquid crystal with achiral liquid crystal molecules with rod and hockey-stick shapes, distinct different behaviors are obtained. In the case of the mixtures of chiral smectic liquid crystals with rod-like molecules, all the smectic-C* variant phases vanish with a small amount of doping. However, the hockey-stick molecule is much less destructive compared to the rod-like molecule. This suggests that the antiferroelectric smectic liquid crystal molecules may have a shape closer to a hockey-stick rather than a rod.

  2. Infrared laser induced population transfer and parity selection in 14NH3: A proof of principle experiment towards detecting parity violation in chiral molecules

    Science.gov (United States)

    Dietiker, P.; Miloglyadov, E.; Quack, M.; Schneider, A.; Seyfang, G.

    2015-12-01

    We have set up an experiment for the efficient population transfer by a sequential two photon—absorption and stimulated emission—process in a molecular beam to prepare quantum states of well defined parity and their subsequent sensitive detection. This provides a proof of principle for an experiment which would allow for parity selection and measurement of the time evolution of parity in chiral molecules, resulting in a measurement of the parity violating energy difference ΔpvE between enantiomers of chiral molecules. Here, we present first results on a simple achiral molecule demonstrating efficient population transfer (about 80% on the average for each step) and unperturbed persistence of a selected excited parity level over flight times of about 1.3 ms in the beam. In agreement with model calculations with and without including nuclear hyperfine structure, efficient population transfer can be achieved by a rather simple implementation of the rapid adiabatic passage method of Reuss and coworkers and considering also the stimulated Raman adiabatic passage technique of Bergmann and coworkers as an alternative. The preparation step uses two powerful single mode continuous wave optical parametric oscillators of high frequency stability and accuracy. The detection uses a sensitive resonantly enhanced multiphoton ionization method after free flight lengths of up to 0.8 m in the molecular beam. Using this technique, we were able to also resolve the nuclear hyperfine structure in the rovibrational levels of the ν1 and ν3 fundamentals as well as the 2ν4 overtone of 14NH3, for which no previous data with hyperfine resolution were available. We present our new results on the quadrupole coupling constants for the ν1, ν3, and 2ν4 levels in the context of previously known data for ν2 and its overtone, as well as ν4, and the ground state. Thus, now, 14N quadrupole coupling constants for all fundamentals and some overtones of 14NH3 are known and can be used for

  3. Infrared laser induced population transfer and parity selection in (14)NH3: A proof of principle experiment towards detecting parity violation in chiral molecules.

    Science.gov (United States)

    Dietiker, P; Miloglyadov, E; Quack, M; Schneider, A; Seyfang, G

    2015-12-28

    We have set up an experiment for the efficient population transfer by a sequential two photon-absorption and stimulated emission-process in a molecular beam to prepare quantum states of well defined parity and their subsequent sensitive detection. This provides a proof of principle for an experiment which would allow for parity selection and measurement of the time evolution of parity in chiral molecules, resulting in a measurement of the parity violating energy difference ΔpvE between enantiomers of chiral molecules. Here, we present first results on a simple achiral molecule demonstrating efficient population transfer (about 80% on the average for each step) and unperturbed persistence of a selected excited parity level over flight times of about 1.3 ms in the beam. In agreement with model calculations with and without including nuclear hyperfine structure, efficient population transfer can be achieved by a rather simple implementation of the rapid adiabatic passage method of Reuss and coworkers and considering also the stimulated Raman adiabatic passage technique of Bergmann and coworkers as an alternative. The preparation step uses two powerful single mode continuous wave optical parametric oscillators of high frequency stability and accuracy. The detection uses a sensitive resonantly enhanced multiphoton ionization method after free flight lengths of up to 0.8 m in the molecular beam. Using this technique, we were able to also resolve the nuclear hyperfine structure in the rovibrational levels of the ν1 and ν3 fundamentals as well as the 2ν4 overtone of (14)NH3, for which no previous data with hyperfine resolution were available. We present our new results on the quadrupole coupling constants for the ν1, ν3, and 2ν4 levels in the context of previously known data for ν2 and its overtone, as well as ν4, and the ground state. Thus, now, (14)N quadrupole coupling constants for all fundamentals and some overtones of (14)NH3 are known and can be used for

  4. Tetrahedral Order in Liquid Crystals

    Science.gov (United States)

    Pleiner, Harald; Brand, Helmut R.

    2016-10-01

    We review the impact of tetrahedral order on the macroscopic dynamics of bent-core liquid crystals. We discuss tetrahedral order comparing with other types of orientational order, like nematic, polar nematic, polar smectic, and active polar order. In particular, we present hydrodynamic equations for phases, where only tetrahedral order exists or tetrahedral order is combined with nematic order. Among the latter, we discriminate between three cases, where the nematic director (a) orients along a fourfold, (b) along a threefold symmetry axis of the tetrahedral structure, or (c) is homogeneously uncorrelated with the tetrahedron. For the optically isotropic T d phase, which only has tetrahedral order, we focus on the coupling of flow with, e.g., temperature gradients and on the specific orientation behavior in external electric fields. For the transition to the nematic phase, electric fields lead to a temperature shift that is linear in the field strength. Electric fields induce nematic order, again linear in the field strength. If strong enough, electric fields can change the tetrahedral structure and symmetry leading to a polar phase. We briefly deal with the T phase that arises when tetrahedral order occurs in a system of chiral molecules. To case (a), defined above, belong (i) the non-polar, achiral, optically uniaxial D2d phase with ambidextrous helicity (due to a linear gradient free energy contribution) and with orientational frustration in external fields, (ii) the non-polar tetragonal S4 phase, (iii) the non-polar, orthorhombic D2 phase that is structurally chiral featuring ambidextrous chirality, (iv) the polar orthorhombic C2v phase, and (v) the polar, structurally chiral, monoclinic C2 phase. Case (b) results in a trigonal C3v phase that behaves like a biaxial polar nematic phase. An example for case (c) is a splay bend phase, where the ground state is inhomogeneous due to a linear gradient free energy contribution. Finally, we discuss some experiments

  5. Origin of nucleic acids

    International Nuclear Information System (INIS)

    The appearance of nucleic acids is the first event after the birth of membranes which made it possible to assure the perenniality of information. The complexity of these molecules has led some scientists to propose that they were not prebiotic but rather derived a more simple and achiral primitive ancestor. This hypothesis suggests that ribose possesses properties that allowed the formation of certain polysaccharides which evolved to RNA. The first step of the hypothesis is the selection and concentration of ribofuranose. This sugar has chelating properties and its alpha-ribofuranose is favoured in the chelating position. The density of the sugar with a heavy cation is greater than water and thus the complex can escape the UV radiation at the surface of the ocean. The particularity of ribose is to be able to form a homochiral regular array of these basic chelating structures with pyrophosphite. These arrays evolve towards the formation of polysaccharides (poly ribose phosphate) which have a very organized structure. These polysaccharides in turn evolve to RNA by binding of adenine and deoxyguanine which are HCN derivatives that can react with the polysaccharides. The primitive RNA is methylated and oxidized to form prebiotic RNA with adenosine, cytidine, 7methyl-guanosine and ribothymidine as nucleic bases. The pathway of biosynthesis of DNA form RNA will be studied. I suggest that the appearance of DNA results form the interaction between prebiotic double stranded RNA and proteins. DNA could be a product of RNA degradation by proteins. The catabolism of RNA to DNA requires a source of free radicals, protons and hydrides. RNA cannot produce free radicals, which are provided by the phenol group of the amino acid tyrosien. Protons are provided by the medium and hydrides are provided by 7-methyl-guanosine which can fix hydrides coming from hydrogen gas and donate them for the transformation of a riboside to a deoxyriboside. This pathway suggests that DNA appeared at

  6. Kiralnost - ususret 160. obljetnici Pasteurova otkrića

    Directory of Open Access Journals (Sweden)

    Kojić-Prodić, B.

    2007-05-01

    guide our life processes. The synthesis of various dynamically chiral supramolecules from achiral molecules and preparations of conjugated homochiral polymers will offer new types of biosensors, artificial enzymes and some sophisticated materials. Theresearch of isotopic chirality by quantum-chemical methods reveals some parity-violating effects and shed more light on the physical bases of molecular chirality.

  7. Transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates: Catalysts for asymmetric olefin hydroamination and acceptorless alcohol decarbonylation

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Kuntal [Ames Lab., Ames, IA (United States)

    2012-12-17

    The research presented and discussed in this dissertation involves the synthesis of transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates, and their application in catalytic enantioselective olefin hydroamination and acceptorless alcohol decarbonylation. Neutral oxazolinylboranes are excellent synthetic intermediates for preparing new borate ligands and also developing organometallic complexes. Achiral and optically active bis(oxazolinyl)phenylboranes are synthesized by reaction of 2-lithio-2-oxazolide and 0.50 equiv of dichlorophenylborane. These bis(oxazolinyl)phenylboranes are oligomeric species in solid state resulting from the coordination of an oxazoline to the boron center of another borane monomer. The treatment of chiral bis(oxazolinyl)phenylboranes with sodium cyclopentadienide provide optically active cyclopentadienyl-bis(oxazolinyl)borates H[PhB(C5H5)(OxR)2] [OxR = Ox4S-iPr,Me2, Ox4R-iPr,Me2, Ox4S-tBu]. These optically active proligands react with an equivalent of M(NMe2)4 (M = Ti, Zr, Hf) to afford corresponding cyclopentadienyl-bis(oxazolinyl)borato group 4 complexes {PhB(C5H4)(OxR)2}M(NMe2)2 in high yields. These group 4 compounds catalyze cyclization of aminoalkenes at room temperature or below, providing pyrrolidine, piperidine, and azepane with enantiomeric excesses up to 99%. Our mechanistic investigations suggest a non-insertive mechanism involving concerted C-N/C-H bond formation in the turnover limiting step of the catalytic cycle. Among cyclopentadienyl-bis(oxazolinyl)borato group 4 catalysts, the zirconium complex {PhB(C5H4)(Ox4S-iPr,Me2)2}Zr(NMe2)2 ({S-2}Zr(NMe2)2) displays highest activity and enantioselectivity. Interestingly, S-2

  8. Synthesis, Characterization and Application of Water-soluble Gold and Silver Nanoclusters

    Science.gov (United States)

    Kumar, Santosh

    The term `nanotechnology' has emerged as a buzzword since the last few decades. It has found widespread applications across disciplines, from medicine to energy. The synthesis of gold and silver nanoclusters has found much excitement, due to their novel material properties. Seminal work by various groups, including ours, has shown that the size of these clusters can be controlled with atomic precision. This control gives access to tuning the optical and electronic properties. The majority of nanoclusters reported thus far are not water soluble, which limit their applications in biology that requires water-solubility. Going from organic to aqueous phase is by no means a simple task, as it is associated with many challenges. Their stability in the presence of oxygen, difficulty in characterization, and separation of pure nanoclusters are some of the major bottlenecks associated with the synthesis of water-soluble gold nanoclusters. Water-soluble gold nanoclusters hold great potential in biological labeling, bio-catalysis and nano-bioconjugates. To overcome this problem, a new ligand with structural rigidity is needed. After considering various possibilities, we chose Captopril as a candidate ligand. In my thesis research, the synthesis of Au25 nanocluster capped with captopril has been reported. Captopril-protected Au25 nanocluster showed significantly higher thermal stability and enhanced chiroptical properties than the Glutathione-capped cluster, which confirms our initial rationale, that the ligand is critical in protecting the nanocluster. The optical absorption properties of these Au25 nanoclusters are studied and compared to the plasmonic nanoparticles. The high thermal stability and solubility of Au25 cluster capped with Captopril motivated us to explore this ligand for the synthesis of other gold clusters. Captopril is a chiral molecule with two chiral centers. The chiral ligand can induce chirality to the overall cluster, even if the core is achiral

  9. Binuclear trans-bis(β-iminoaryloxy)palladium(II) complexes doubly linked with pentamethylene spacers: structure-dependent flapping motion and heterochiral association behavior of the clothespin-shaped molecules.

    Science.gov (United States)

    Naito, Masaya; Souda, Hiroyuki; Koori, Hiroshi; Komiya, Naruyoshi; Naota, Takeshi

    2014-06-01

    The synthesis, structure, and solution-state behavior of clothespin-shaped binuclear trans-bis(β-iminoaryloxy)palladium(II) complexes doubly linked with pentamethylene spacers are described. Achiral syn and racemic anti isomers of complexes 1-3 were prepared by treating Pd(OAc)2 with the corresponding N,N'-bis(β-hydroxyarylmethylene)-1,5-pentanediamine and then subjecting the mixture to chromatographic separation. Optically pure (100 % ee) complexes, (+)-anti-1, (+)-anti-2, and (+)-anti-3, were obtained from the racemic mixture by employing a preparative HPLC system with a chiral column. The trans coordination and clothespin-shaped structures with syn and anti conformations of these complexes have been unequivocally established by X-ray diffraction studies. (1)H NMR analysis showed that (±)-anti-1, (±)-anti-2, syn-2, and (±)-anti-3 display a flapping motion by consecutive stacking association/dissociation between cofacial coordination planes in [D8]toluene, whereas syn-1 and syn-3 are static under the same conditions. The activation parameters for the flapping motion (ΔH(≠) and ΔS(≠)) were determined from variable-temperature NMR analyses as 50.4 kJ mol(-1) and 60.1 J mol(-1)  K(-1) for (±)-anti-1, 31.0 kJ mol(-1) and -22.7 J mol(-1)  K(-1) for (±)-anti-2, 29.6 kJ mol(-1) and -57.7 J mol(-1)  K(-1) for syn-2, and 35.0 kJ mol(-1) and 0.5 J mol(-1)  K(-1) for (±)-anti-3, respectively. The molecular structure and kinetic parameters demonstrate that all of the anti complexes flap with a twisting motion in [D8]toluene, although (±)-anti-1 bearing dilated Z-shaped blades moves more dynamically than I-shaped (±)-anti-2 or the smaller (±)-anti-3. Highly symmetrical syn-2 displays a much more static flapping motion, that is, in a see-saw-like manner. In CDCl3, (±)-anti-1 exhibits an extraordinary upfield shift of the (1)H NMR signals with increasing concentration, whereas solutions of (+)-anti-1 and the other

  10. Obituary for Moshe Shapiro

    Science.gov (United States)

    Grant, Edward R.

    2014-04-01

    induced symmetry breaking to form chiral products from achiral precursors, and showed how to use phase-coherent laser excitation to launch directional currents in semiconductors, in the absence of bias voltage. He has also contributed to important advances in laser catalysis, quantum computing and decoherence, transition state spectroscopy, potential inversion and wavefunction imaging, the theory of strong field phenomena in atoms and molecules, quantum theory of elementary exchange reactions and foundations of quantum mechanics. His most recent research focused on the control of molecular, atomic, and photonic processes with coherent light, quantum pattern recognition, coherent chiral separation and the coherent suppression of spontaneous emission, decoherence and other decay processes. At UBC, Moshe is remembered for his perceptiveness, broad vision and collegiality. 'One day he came to a group meeting with the idea of a solar-pumped living laser,' said physics colleague, Valery Milner. 'After thinking about this for two months, we designed an experiment using a random laser cavity that produced gain with milliwatts of pumping power applied to a fluorescent protein. We have now only to get lasing with the bacterium we engineered to express this protein.' Moshe studied for his PhD guided by Professor Raphael D Levine, in theoretical chemistry at the Hebrew University, focusing on photodissociation and molecular collisions. In 1970, he moved to Harvard University as a postdoctoral fellow, where he worked in reaction dynamics with Martin Karplus, a 2013 Nobel laureate in chemistry. In 1972, Moshe joined the faculty of the Department of Chemical Physics at the Weizmann Institute. There, he served as a department chair and was named the Jacques Mimran Professor of Chemical Physics. In 2002, he was appointed to a Canada Research Chair in Quantum Control in the Department of Chemistry at UBC. He won the Willis E Lamb Medal for achievements in the Physics of Quantum Electronics

  11. Molecular-level Design of Heterogeneous Chiral Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gellman, Andrew John [Carnegie Mellon University; Sholl, David S. [Georgia Institute of Technology; Tysoe, Wilfred T. [University of Wisconsin - Milwaukee; Zaera, Francisco [University of California at Riverside

    2013-04-28

    Understanding and controlling selectivity is one of the key challenges in heterogeneous catalysis. Among problems in catalytic selectivity enantioselectivity is perhaps the most the most challenging. The primary goal of the project on “Molecular-level Design of Heterogeneous Chiral Catalysts” is to understand the origins of enantioselectivity on chiral heterogeneous surfaces and catalysts. The efforts of the project team include preparation of chiral surfaces, characterization of chiral surfaces, experimental detection of enantioselectivity on such surfaces and computational modeling of the interactions of chiral probe molecules with chiral surfaces. Over the course of the project period the team of PI’s has made some of the most detailed and insightful studies of enantioselective chemistry on chiral surfaces. This includes the measurement of fundamental interactions and reaction mechanisms of chiral molecules on chiral surfaces and leads all the way to rationale design and synthesis of chiral surfaces and materials for enantioselective surface chemistry. The PI’s have designed and prepared new materials for enantioselective adsorption and catalysis. Naturally Chiral Surfaces • Completion of a systematic study of the enantiospecific desorption kinetics of R-3-methylcyclohexanone (R-3-MCHO) on 9 achiral and 7 enantiomeric pairs of chiral Cu surfaces with orientations that span the stereographic triangle. • Discovery of super-enantioselective tartaric acid (TA) and aspartic acid (Asp) decomposition as a result of a surface explosion mechanism on Cu(643)R&S. Systematic study of super-enantiospecific TA and Asp decomposition on five enantiomeric pairs of chiral Cu surfaces. • Initial observation of the enantiospecific desorption of R- and S-propylene oxide (PO) from Cu(100) imprinted with {3,1,17} facets by L-lysine adsorption. Templated Chiral Surfaces • Initial observation of the enantiospecific desorption of R- and S-PO from Pt(111) and Pd(111

  12. Enantioselective stable isotope analysis (ESIA) of polar Herbicides

    Science.gov (United States)

    Maier, Michael; Qiu, Shiran; Elsner, Martin

    2013-04-01

    preference was rate determining. Our findings are in contrast to previously reported results for the degradation of α-hexachlorocyclohexane (Badea et al., 2012), where isotope fractionation, but no enantiomeric fractionation was observed. Hence the two lines of evidence seem to be independent of each other. Enhanced insight maybe provided when both effects appear simultaneously, as shown downstream of a landfill site under anaerobic conditions for the chiral herbicide 4-CPP (Milosevic et al., 2013). Buser HR, Muller MD (1998): Occurrence and transformation reactions of chiral and achiral phenoxyalkanoic acid herbicides in lakes and rivers in Switzerland. Environmental Science & Technology 32 (5):626-633. Badea S-L, Vogt C, Gehre M, Fischer A, Danet A-F, Richnow H-H (2011): Development of an enantiomer-specific stable carbon isotope analysis (ESIA) method for assessing the fate of alpha-hexachlorocyclohexane in the environment. Rapid Communications in Mass Spectrometry 25 (10):1363-1372. Milosevic N, Qiu S, Elsner M, Einsiedl F, Maier MP, Bensch HKV, Albrechtsen HJ, Bjerg PL (2013): Combined isotope and enantiomer analysis to assess the fate of phenoxy acids in a eterogeneous geologic setting at an old landfill. Water Research 47 (2): 637-649.

  13. Organic Reactions in Aqueous Media (by Chao-Jun Li and Tak-Hang Chan)

    Science.gov (United States)

    Rosan, Reviewed Alan M.

    2000-06-01

    the index. The text does not explicitly include a discussion of what has come to be broadly termed biphasic reaction conditions. Understandably, enzymatic reactions are beyond the scope of the presentation. This book has a decidedly applied character with an understated environmental theme, and the authors succinctly present the extraordinary effects of water on the kinetics, efficiency, and stereoselectivity of a large number of diverse reactions. In addition to their emphasis on the historically significant aqueous Diels-Alder reaction, discovered in 1980, and the literature regarding reactions of various nucleophilic organometals, the authors are to be commended for gathering together a wide and diverse body of information: it is clear that many of the examples shown are gems buried among larger bodies of work. Thus the book does an excellent job of culling and surveying a vast amount of data. There is, however, less emphasis on organizing the mechanistic bases underlying these often dramatic effects. For example, the apparent lack of generality of the effect of water on rate and selectivity in pericyclic reactions calls for some theoretical foundation. The singularly effective use of aqueous TlOH in the Suzuki reaction is cited without comment. On the other hand, the authors' concept of a mechanistic triad that incorporates to various degrees anion, radical, or covalent character in the carbon-carbon bond-forming step between various organometals and carbonyl substrates is appealing and suggests the need for future sophisticated experimental design. The most interesting sections are those dealing with synthesis and industrial applications. Unfortunately the latter is also the shortest chapter. The synthetic examples are timely and well chosen and include water-promoted Heck, Stille, Suzuki, and aldol reactions. There is an extensive, highly informative listing and survey of the use of water-soluble phosphines (both achiral and chiral) and an excellent discussion