Poly-proline-based chiral stationary phases: a molecular dynamics study of triproline, tetraproline, pentaproline and hexaproline interfaces.

PubMed

Ashtari, M; Cann, N M

2012-11-23

Poly-proline chains and derivatives have been recently examined as the basis for new chiral stationary phases in high performance liquid chromatography. The selectivity of poly-proline has been measured for peptides with up to ten proline units. In this article, we employ molecular dynamics simulations to examine the interfacial structure and solvation of surface-bound poly-proline chiral selectors. Specifically, we study the interfacial structure of trimethylacetyl-terminated poly-proline chains with three-to-six prolines. The surface includes silanol groups and end-caps, to better capture the characteristics of the stationary phase, and the solvent is either a polar water/methanol or a relatively apolar n-hexane/2-propanol mixture. We begin with a comprehensive ab initio study of the conformers, their energies, and an assessment of conformer flexibility. Force fields have been developed for each poly-proline selector. Molecular dynamics simulations are employed to study the preferred backbone conformations and solvent hydrogen bonding for different poly-proline/solvent interfaces. For triproline, the effect of two different terminal groups, trimethylacetyl and t-butyl carbamate are compared. Copyright © 2012 Elsevier B.V. All rights reserved.

Chemical synthesis of water-soluble, chiral conducting-polymer complexes

DOEpatents

Wang, Hsing-Lin; McCarthy, Patrick A.; Yang, Sze Cheng

2003-01-01

The template-guided synthesis of water-soluble, chiral conducting polymer complexes is described. Synthesis of water-soluble polyaniline complexes is achieved by carefully controlling the experimental parameters such as; acid concentration, ionic strength, monomer/template ratio, total reagent concentration, and order of reagent addition. Chiral (helical) polyaniline complexes can be synthesized by addition of a chiral inducing agent (chiral acid) prior to polymerization, and the polyaniline helix can be controlled by the addition of the (+) or (-) form of the chiral acid. Moreover the quantity of chiral acid and the salt content has a significant impact on the degree of chirality in the final polymer complexes. The polyaniline and the template have been found to be mixed at the molecular level which results in chiral complexes that are robust through repeated doping and dedoping cycles.

Pharmacokinetics of Chiral Dendrimer-Triamine-Coordinated Gd-MRI Contrast Agents Evaluated by in Vivo MRI and Estimated by in Vitro QCM.

PubMed

Miyake, Yuka; Ishikawa, Syungo; Kimura, Yu; Son, Aoi; Imai, Hirohiko; Matsuda, Tetsuya; Yamada, Hisatsugu; Toshimitsu, Akio; Kondo, Teruyuki

2015-12-18

Recently, we developed novel chiral dendrimer-triamine-coordinated Gd-MRI contrast agents (Gd-MRI CAs), which showed longitudinal relaxivity (r₁) values about four times higher than that of clinically used Gd-DTPA (Magnevist(®), Bayer). In our continuing study of pharmacokinetic differences derived from both the chirality and generation of Gd-MRI CAs, we found that the ability of chiral dendrimer Gd-MRI CAs to circulate within the body can be directly evaluated by in vitro MRI (7 T). In this study, the association constants (K(a)) of chiral dendrimer Gd-MRI CAs to bovine serum albumin (BSA), measured and calculated with a quartz crystal microbalance (QCM) in vitro, were found to be an extremely easy means for evaluating the body-circulation ability of chiral dendrimer Gd-MRI CAs. The K(a) values of S-isomeric dendrimer Gd-MRI CAs were generally greater than those of R-isomeric dendrimer Gd-MRI CAs, which is consistent with the results of our previous MRI study in vivo.

Chromatographic Studies of Protein-Based Chiral Separations

PubMed Central

Bi, Cong; Zheng, Xiwei; Azaria, Shiden; Beeram, Sandya; Li, Zhao; Hage, David S.

2016-01-01

The development of separation methods for the analysis and resolution of chiral drugs and solutes has been an area of ongoing interest in pharmaceutical research. The use of proteins as chiral binding agents in high-performance liquid chromatography (HPLC) has been an approach that has received particular attention in such work. This report provides an overview of proteins that have been used as binding agents to create chiral stationary phases (CSPs) and in the use of chromatographic methods to study these materials and protein-based chiral separations. The supports and methods that have been employed to prepare protein-based CSPs will also be discussed and compared. Specific types of CSPs that are considered include those that employ serum transport proteins (e.g., human serum albumin, bovine serum albumin, and alpha1-acid glycoprotein), enzymes (e.g., penicillin G acylase, cellobiohydrolases, and α-chymotrypsin) or other types of proteins (e.g., ovomucoid, antibodies, and avidin or streptavidin). The properties and applications for each type of protein and CSP will also be discussed in terms of their use in chromatography and chiral separations. PMID:28344977

Pharmacokinetics of Chiral Dendrimer-Triamine-Coordinated Gd-MRI Contrast Agents Evaluated by in Vivo MRI and Estimated by in Vitro QCM

PubMed Central

Miyake, Yuka; Ishikawa, Syungo; Kimura, Yu; Son, Aoi; Imai, Hirohiko; Matsuda, Tetsuya; Yamada, Hisatsugu; Toshimitsu, Akio; Kondo, Teruyuki

2015-01-01

Recently, we developed novel chiral dendrimer-triamine-coordinated Gd-MRI contrast agents (Gd-MRI CAs), which showed longitudinal relaxivity (r1) values about four times higher than that of clinically used Gd-DTPA (Magnevist®, Bayer). In our continuing study of pharmacokinetic differences derived from both the chirality and generation of Gd-MRI CAs, we found that the ability of chiral dendrimer Gd-MRI CAs to circulate within the body can be directly evaluated by in vitro MRI (7 T). In this study, the association constants (Ka) of chiral dendrimer Gd-MRI CAs to bovine serum albumin (BSA), measured and calculated with a quartz crystal microbalance (QCM) in vitro, were found to be an extremely easy means for evaluating the body-circulation ability of chiral dendrimer Gd-MRI CAs. The Ka values of S-isomeric dendrimer Gd-MRI CAs were generally greater than those of R-isomeric dendrimer Gd-MRI CAs, which is consistent with the results of our previous MRI study in vivo. PMID:26694418

Chiral ionic liquids in chromatographic and electrophoretic separations.

PubMed

Kapnissi-Christodoulou, Constantina P; Stavrou, Ioannis J; Mavroudi, Maria C

2014-10-10

This report provides an overview of the application of chiral ionic liquids (CILs) in separation technology, and particularly in capillary electrophoresis and both gas and liquid chromatography. There is a large number of CILs that have been synthesized and designed as chiral agents. However, only a few have successfully been applied in separation technology. Even though this application of CILs is still in its early stages, the scientific interest is increasing dramatically. This article is focused on the use of CILs as chiral selectors, background electrolyte additives, chiral ligands and chiral stationary phases in electrophoretic and chromatographic techniques. Different examples of CILs, which contain either a chiral cation, a chiral anion or both, are presented in this review article, and their major advantages along with their potential applications in chiral electrophoretic and chromatographic recognition are discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

Annual Report 2013-2014: Theoretical Studies of Nerve Agents Adsorbed on Surfaces

DTIC Science & Technology

2014-07-08

of the solvation of sarin by water are underway. The results should clarify how water affects desorption properties and the extent of solvation of...platinum activated nanocrystalline ZnO thick films. Sensors and Actuators B-Chemical 2012, 161, 372- 380. 5. Bermudez, V. M., Computational Study of...Rauk, A.; Shishkov, I. F.; Vilkov, L. V.; Koehler, K. F.; Kostyanovsky, R. G., DETERMINATION OF THE STRUCTURE AND CHIROPTICAL PROPERTIES OF THE

Chiral Separation of G-type Chemical Warfare Nerve Agents via Analytical Supercritical Fluid Chromatography

PubMed Central

Kasten, Shane A; Zulli, Steven; Jones, Jonathan L; Dephillipo, Thomas; Cerasoli, Douglas M

2014-01-01

Chemical warfare nerve agents (CWNAs) are extremely toxic organophosphorus compounds that contain a chiral phosphorus center. Undirected synthesis of G-type CWNAs produces stereoisomers of tabun, sarin, soman, and cyclosarin (GA, GB, GD, and GF, respectively). Analytical-scale methods were developed using a supercritical fluid chromatography (SFC) system in tandem with a mass spectrometer for the separation, quantitation, and isolation of individual stereoisomers of GA, GB, GD, and GF. Screening various chiral stationary phases (CSPs) for the capacity to provide full baseline separation of the CWNAs revealed that a Regis WhelkO1 (SS) column was capable of separating the enantiomers of GA, GB, and GF, with elution of the P(+) enantiomer preceding elution of the corresponding P(–) enantiomer; two WhelkO1 (SS) columns had to be connected in series to achieve complete baseline resolution. The four diastereomers of GD were also resolved using two tandem WhelkO1 (SS) columns, with complete baseline separation of the two P(+) epimers. A single WhelkO1 (RR) column with inverse stereochemistry resulted in baseline separation of the GD P(–) epimers. The analytical methods described can be scaled to allow isolation of individual stereoisomers to assist in screening and development of countermeasures to organophosphorus nerve agents. Chirality 26:817–824, 2014. © 2014 The Authors. Chirality published by John Wiley Periodicals, Inc. PMID:25298066

Hydrolysis of Nerve Agents by Model Nucleophiles: A Computational Study

PubMed Central

Beck, Jeremy M.

2008-01-01

Density functional theory calculations were employed to study the reaction of five nerve agents with model nucleophiles, including EtX− and EtXH (X = O, S, Se) for serine, cysteine and selenocysteine, respectively. Calculations at the B3LYP/6-311++G(2d,p) level of theory predict an exothermic reaction between ethoxide and all of the nerve agents studied. As compared to EtO− as a nucleophile, these reactions become ~30 kcal/mol more endothermic for EtS−, and by ~40 kcal/mol for EtSe−. The equivalent reactions with the neutral nucleophiles (EtXH) were more endothermic. The effect of solvation on the reaction thermochemistry was determined using a polarizable continuum model simulating the dielectric constant of chloroform. While there was a large exothermic shift for reactions involving charged nucleophiles with solvation modeling, the corresponding shift was minimal for the reaction with neutral nucleophiles. PMID:18538754

Crystallization processes in pharmaceutical technology and drug delivery design

NASA Astrophysics Data System (ADS)

Shekunov, B. Yu; York, P.

2000-04-01

Crystallization is a major technological process for particle formation in pharmaceutical industry and, in addition, plays an important role in defining the stability and drug release properties of the final dosage forms. Industrial and regulatory aspects of crystallization are briefly reviewed with reference to solid-state properties of pharmaceuticals. Crystallization, incorporating wider definition to include precipitation and solid-state transitions, is considered in terms of preparation of materials for direct compression, formation of amorphous, solvated and polymorphic forms, chiral separation of drugs, production of materials for inhalation drug delivery and injections. Finally, recent developments in supercritical fluid particle technology is considered in relationship to the areas discussed.

Chiral separation of G-type chemical warfare nerve agents via analytical supercritical fluid chromatography.

PubMed

Kasten, Shane A; Zulli, Steven; Jones, Jonathan L; Dephillipo, Thomas; Cerasoli, Douglas M

2014-12-01

Chemical warfare nerve agents (CWNAs) are extremely toxic organophosphorus compounds that contain a chiral phosphorus center. Undirected synthesis of G-type CWNAs produces stereoisomers of tabun, sarin, soman, and cyclosarin (GA, GB, GD, and GF, respectively). Analytical-scale methods were developed using a supercritical fluid chromatography (SFC) system in tandem with a mass spectrometer for the separation, quantitation, and isolation of individual stereoisomers of GA, GB, GD, and GF. Screening various chiral stationary phases (CSPs) for the capacity to provide full baseline separation of the CWNAs revealed that a Regis WhelkO1 (SS) column was capable of separating the enantiomers of GA, GB, and GF, with elution of the P(+) enantiomer preceding elution of the corresponding P(-) enantiomer; two WhelkO1 (SS) columns had to be connected in series to achieve complete baseline resolution. The four diastereomers of GD were also resolved using two tandem WhelkO1 (SS) columns, with complete baseline separation of the two P(+) epimers. A single WhelkO1 (RR) column with inverse stereochemistry resulted in baseline separation of the GD P(-) epimers. The analytical methods described can be scaled to allow isolation of individual stereoisomers to assist in screening and development of countermeasures to organophosphorus nerve agents. © 2014 The Authors. Chirality published by John Wiley Periodicals, Inc.

EFFECT OF AN ADDITIONAL HYDROPHILIC VERSUS HYDROPHOBIC COAT ON THE QUALITY OF DENTINAL SEALING PROVIDED BY TWO-STEP ETCH-AND-RINSE ADHESIVES

PubMed Central

Silva, Safira Marques de Andrade; Carrilho, Marcela Rocha de Oliveira; Marquezini, Luiz; Garcia, Fernanda Cristina Pimentel; Manso, Adriana Pigozzo; Alves, Marcelo Corrêa; de Carvalho, Ricardo Marins

2009-01-01

Objective: To test the hypothesis that the quality of the dentinal sealing provided by two-step etch-and-rinse adhesives cannot be altered by the addition of an extra layer of the respective adhesive or the application of a more hydrophobic, non-solvated resin. Material and Methods: full-crown preparations were acid-etched with phosphoric acid for 15 s and bonded with Adper Single Bond (3M ESPE), Excite DSC (Ivoclar/Vivadent) or Prime & Bond NT (Dentsply). The adhesives were used according to the manufacturers' instructions (control groups) or after application to dentin they were a) covered with an extra coat of each respective system or b) coated with a non-solvated bonding agent (Adper Scotchbond Multi-Purpose Adhesive, 3M ESPE). Fluid flow rate was measured before and after dentin surfaces were acid-etched and bonded with adhesives. Results: None of the adhesives or experimental treatments was capable to block completely the fluid transudation across the treated dentin. Application of an extra coat of the adhesive did not reduce the fluid flow rate of adhesive-bonded dentin (p>0.05). Conversely, the application of a more hydrophobic non-solvated resin resulted in significant reductions in the fluid flow rate (p<0.05) for all tested adhesives. Conclusions: The quality of the dentinal sealing provided by etch-and-rinse adhesives can be significantly improved by the application of a more hydrophobic, non-solvated bonding agent. PMID:19466248

On the origin of biological chirality via natural beta-decay

NASA Technical Reports Server (NTRS)

Noyes, H. P.; Bonner, W. A.; Tomlin, J. A.

1977-01-01

An hypothesis to account for the chirality (handedness) of some biological molecules is given. Experimental evidence suggests that longitudinally polarized electrons having the chirality of terrestrial beta-decay electrons remove dextro-leucine from a racemic mixture. If, by a similar mechanism, the terrestrial environment provided more levo- than dextro-amino acids, that would account for the chirality now observed in organic molecules. An isotope of potassium has been proposed as the natural beta-emitter responsible for biomolecular chirality; however, Carbon 14 may be an even more plausible candidate. Ready availability of the carbon isotope in the terrestrial environment of 4.5 aeons ago, and the role of leucine in protein synthesis indicate that these two agents may have been chief factors in the evolution of biomolecular chirality. Suggestions for further research in this area are made.

Synthesis of Enantiomerically Pure Anthracyclinones

NASA Astrophysics Data System (ADS)

Achmatowicz, Osman; Szechner, Barbara

The anthracycline antibiotics are among the most important clinical drugs used in the treatment of human cancer. The search for new agents with improved therapeutic efficacy and reduced cardiotoxicity stimulated considerable efforts in the synthesis of new analogues. Since the biological activity of anthracyclines depends on their natural absolute configuration, various strategies for the synthesis of enantiomerically pure anthracyclinones (aglycones) have been developed. They comprise: resolution of racemic intermediate, incorporation of a chiral fragment derived from natural and non-natural chiral pools, asymmetric synthesis with the use of a chiral auxiliary or a chiral reagent, and enantioselective catalysis. Synthetic advances towards enantiopure anthracyclinones reported over the last 17 years are reviewed.

Method for the synthesis of chiral allylic alcohols utilizing selone based chiral derivatizing agents

DOEpatents

Silks, III, Louis A.

2002-01-01

Molecules containing a chiral 1,2-diol unit are synthesized from reactions between aldehydes and N-acyl selones. A chilled N-acyl selone is reacted with a Lewis acid such as TiCl.sub.4 and mixed with a tertiary amine such as diisopropylethylamine to generate an enolate solution. Upon further chilling of the enolate solution a desired aldehyde is added and after an acceptable reaction period a quencher is introduced and the product isolated.

Chirality in adsorption on solid surfaces.

PubMed

Zaera, Francisco

2017-12-07

In the present review we survey the main advances made in recent years on the understanding of chemical chirality at solid surfaces. Chirality is an important topic, made particularly relevant by the homochiral nature of the biochemistry of life on Earth, and many chiral chemical reactions involve solid surfaces. Here we start our discussion with a description of surface chirality and of the different ways that chirality can be bestowed on solid surfaces. We then expand on the studies carried out to date to understand the adsorption of chiral compounds at a molecular level. We summarize the work published on the adsorption of pure enantiomers, of enantiomeric mixtures, and of prochiral molecules on chiral and achiral model surfaces, especially on well-defined metal single crystals but also on other flat substrates such as highly ordered pyrolytic graphite. Several phenomena are identified, including surface reconstruction and chiral imprinting upon adsorption of chiral agents, and the enhancement or suppression of enantioselectivity seen in some cases upon adsorption of enantiomixtures of chiral compounds. The possibility of enhancing the enantiopurity of adsorbed layers upon the addition of chiral seeds and the so-called "sergeants and soldiers" phenomenon are presented. Examples are provided where the chiral behavior has been associated with either thermodynamic or kinetic driving forces. Two main approaches to the creation of enantioselective surface sites are discussed, namely, via the formation of supramolecular chiral ensembles made out of small chiral adsorbates, and by adsorption of more complex chiral molecules capable of providing suitable chiral environments for reactants by themselves, via the formation of individual adsorbate:modifier adducts on the surface. Finally, a discussion is offered on the additional effects generated by the presence of the liquid phase often required in practical applications such as enantioselective crystallization, chiral chromatography, and enantioselective catalysis.

New insights into the coordination chemistry of Schiff bases derived from amino acids: Planar [Ni4] complexes with tyrosine side-chains

NASA Astrophysics Data System (ADS)

Muche, Simon; Hołyńska, Małgorzata

2017-08-01

Structure and properties of a rare metal complex of the chiral Schiff base ligand derived from ortho-vanillin and L-tyrosine are presented. This study is a continuation of research on ligands containing biologically compatible moieties. The ligand is also fully characterized in form of a sodium salt, in particular in solution, for the first time. The metal complex contains a unique bowl-shaped [Ni4] core. Its structure is investigated both in solution (ESI-MS, NMR) and in solid state (X-ray diffraction studies). Under certain conditions the complex can be isolated as crystalline DMF solvate which is studied in solid state.

Anti-cancer agents based on 6-trifluoromethoxybenzimidazole derivatives and method of making

DOEpatents

Gakh, Andrei A.; Vovk, Mykhaylo V.; Mel'nychenko, Nina V.; Sukach, Volodymyr A.

2012-08-14

The present disclosure relates to novel compounds having the structural Formulas (1a,1b), stereoisomers, tautomers, racemics, prodrugs, metabolites thereof, or pharmaceutically acceptable salt and/or solvate thereof as chemotherapy agents for treating of cancer, particularly androgen-independent prostate cancer. The disclosure also relates to methods for preparing said compounds, and to pharmaceutical compositions comprising said compounds.

Anti-cancer agents based on 6-trifluoromethoxybenzimidazole derivatives and method of making

DOEpatents

Gakh, Andrei A; Vovk, Mykhaylo V; Mel& #x27; nychenko, Nina V; Sukach, Volodymyr A

2012-10-23

The present disclosure relates to novel compounds having the structural Formulas (1a,1b), stereoisomers, tautomers, racemics, prodrugs, metabolites thereof, or pharmaceutically acceptable salt and/or solvate thereof as chemotherapy agents for treating of cancer, particularly androgen-independent prostate cancer. The disclosure also relates to methods for preparing said compounds, and to pharmaceutical compositions comprising said compounds.

In search of a viable reaction pathway in the chelation of a metallo-protein

NASA Astrophysics Data System (ADS)

Rose, Frisco; Hodak, Miroslav; Bernholc, Jerry

2010-03-01

Misfolded metallo-proteins are potential causal agents in the onset of neuro-degenerative diseases, such as Alzheimer's and Parkinson's Diseases (PD). Experimental results involving metal chelation have shown significant promise in symptom reduction and misfolding reversal. We explore, through atomistic simulations, potential reaction pathways for the chelation of Cu^2+ from the metal binding site in our representation of a partially misfolded α-synuclein, the protein implicated in PD. Our ab initio simulations use Density Functional Theory (DFT) and nudged elastic band to obtain the minimized energy coordinates of this reaction. Our simulations include ab initio water at the interaction site and in its first solvation shells, while the remainder is fully solvated with orbital-free DFT water representation [1]. Our ongoing studies of viable chelation agents include nicotine, caffeine and other potential reagents, we will review the best case agents in this presentation. [4pt] [1] Hodak M, Lu W, Bernholc J. Hybrid ab initio Kohn-Sham density functional theory/frozen-density orbital-free density functional theory simulation method suitable for biological systems. J. Chem. Phys. 2008 Jan;128(1):014101-9.

Antiviral agents of plant origin. III. Scopadulin, a novel tetracyclic diterpene from Scoparia dulcis L.

PubMed

Hayashi, T; Kawasaki, M; Miwa, Y; Taga, T; Morita, N

1990-04-01

The structure and stereochemistry of scopadulin, a novel aphidicolane-type diterpene isolated from Scoparia dulcis L. have been established from spectral data and single-crystal X-ray analysis of its acetone solvate.

Solvent, Temperature And Concentration Effects on the Optical Activity of Chiral FIVE-And-SIX Membered Ring Ketones Conformers

NASA Astrophysics Data System (ADS)

Al-Basheer, Watheq

2017-06-01

Chiral five-and-six membered ring ketones are important molecules that are found in many biological systems and can exist in many possible conformers. In this talk, experimental and computational investigation of solvent, temperature and concentration effects on the circular dichroism (CD) and optical rotation (OR) of (R)-3 -methylcyclohexanone (R3MCH), (R)-3-methylcyclopentanone (R3MCP) and carvone conformers will be discussed. CD and OR measurements of these ketones gaseous samples and in ten common solvents of wide polarity range for different concentrations and sample temperatures were recorded and related to molecular conformation. Density functional theoretical calculations were performed using Gaussian09 at B3LYP functions with aug-cc-pVDZ level of theory. Also, CD and OR spectra for the optimized geometries of the ketones dominant conformers were computed over the ultraviolet and visible region in the gas phase as well as in ten solvents of varying polarity range, and under the umbrella of the polarizable continuum model (PCM). By comparing theoretical and experimental results, few thermodynamic parameters were deduced for the individual equatorial and axial conformers of each molecule in gas phase and in solvation.

A C–H oxidation approach for streamlining synthesis of chiral polyoxygenated motifs

PubMed Central

Covell, Dustin J.; White, M. Christina

2013-01-01

Chiral oxygenated molecules are pervasive in natural products and medicinal agents; however, their chemical syntheses often necessitate numerous, wasteful steps involving functional group and oxidation state manipulations. Herein a strategy for synthesizing a readily diversifiable class of chiral building blocks, allylic alcohols, through sequential asymmetric C—H activation/resolution is evaluated against the state-of-the-art. The C—H oxidation routes’ capacity to strategically introduce oxygen into a sequence and thereby minimize non-productive manipulations is demonstrated to effect significant decreases in overall step-count and increases in yield and synthetic flexibility. PMID:25013239

Effect of a Polymercaptan Material on the Electro-Optical Properties of Polymer-Dispersed Liquid Crystal Films.

PubMed

Sun, Yujian; Zhang, Cuihong; Zhou, Le; Fang, Hua; Huang, Jianhua; Ma, Haipeng; Zhang, Yi; Yang, Jie; Zhang, Lan-Ying; Song, Ping; Gao, Yanzi; Xiao, Jiumei; Li, Fasheng; Li, Kexuan

2016-12-30

Polymer-dispersed liquid crystal (PDLC) films were prepared by the ultraviolet-light-induced polymerization of photopolymerizable monomers in nematic liquid crystal/chiral dopant/thiol-acrylate reaction monomer composites. The effects of the chiral dopant and crosslinking agents on the electro-optical properties of the PDLC films were systematically investigate. While added the chiral dopant S811 into the PDLC films, the initial off-state transmittance of the films was decreased. It was found that the weight ratio among acrylate monomers, thiol monomer PETMP and the polymercaptan Capcure 3-800 showed great influence on the properties of the fabricated PDLC films because of the existence of competition between thiol-acrylate reaction and acrylate monomer polymerization reaction. While adding polymercaptans curing agent Capcure 3-800 with appropriate concentration into the PDLC system, lower driven voltage and higher contrast ratio were achieved. This made the polymer network and electro-optical properties of the PDLC films easily tunable by the introduction of the thiol monomers.

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

PubMed

Tschierske, Carsten; Ungar, Goran

2016-01-04

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Readily Available Chiral Benzimidazoles-Derived Guanidines as Organocatalysts in the Asymmetric α-Amination of 1,3-Dicarbonyl Compounds.

PubMed

Benavent, Llorenç; Puccetti, Francesco; Baeza, Alejandro; Gómez-Martínez, Melania

2017-08-11

The synthesis and the evaluation as organocatalysts of new chiral guanidines derived from benzimidazoles in the enantioselective α-amination of 1,3-dicarbonyl compounds using di- t -butylazodicarboxylate as aminating agent is herein disclosed. The catalysts are readily synthesized through the reaction of 2-chlorobezimidazole and a chiral amine in moderate-to-good yields. Among all of them, those derived from ( R )-1-phenylethan-1-amine ( 1 ) and ( S )-1-(2-naphthyl)ethan-1-amine ( 3 ) turned out to be the most efficient for such asymmetric transformation, rendering good-to-high yields and moderate-to-good enantioselectivities for the amination products.

Chiral metabonomics: 1H NMR-based enantiospecific differentiation of metabolites in human urine via direct cosolvation with β-cyclodextrin.

PubMed

Pérez-Trujillo, Míriam; Lindon, John C; Parella, Teodor; Keun, Hector C; Nicholson, Jeremy K; Athersuch, Toby J

2012-03-20

Differences in molecular chirality remain an important issue in drug metabolism and pharmacokinetics for the pharmaceutical industry and regulatory authorities, and chirality is an important feature of many endogenous metabolites. We present a method for the rapid, direct differentiation and identification of chiral drug enantiomers in human urine without pretreatment of any kind. Using the well-known anti-inflammatory chemical ibuprofen as one example, we demonstrate that the enantiomers of ibuprofen and the diastereoisomers of one of its main metabolites, the glucuronidated carboxylate derivative, can be resolved by (1)H NMR spectroscopy as a consequence of direct addition of the chiral cosolvating agent (CSA) β-cyclodextrin (βCD). This approach is simple, rapid, and robust, involves minimal sample manipulation, and does not require derivatization or purification of the sample. In addition, the method should allow the enantiodifferentiation of endogenous chiral metabolites, and this has potential value for differentiating metabolites from mammalian and microbial sources in biofluids. From these initial findings, we propose that more extensive and detailed enantiospecific metabolic profiling could be possible using CSA-NMR spectroscopy than has been previously reported.

Molecular-Level Design of Heterogeneous Chiral Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Francisco Zaera

2012-03-21

The following is a proposal to continue our multi-institutional research on heterogeneous chiral catalysis. Our team combines the use of surface-sensitive analytical techniques for the characterization of model systems with quantum and statistical mechanical calculations to interpret experimental data and guide the design of future research. Our investigation focuses on the interrelation among the three main mechanisms by which enantioselectivity can be bestowed to heterogeneous catalysts, namely: (1) by templating chirality via the adsorption of chiral supramolecular assemblies, (2) by using chiral modifiers capable of forming chiral complexes with the reactant and force enantioselective surface reactions, and (3) by formingmore » naturally chiral surfaces using imprinting chiral agents. Individually, the members of our team are leaders in these various aspects of chiral catalysis, but the present program provides the vehicle to generate and exploit the synergies necessary to address the problem in a comprehensive manner. Our initial work has advanced the methodology needed for these studies, including an enantioselective titration procedure to identify surface chiral sites, infrared spectroscopy in situ at the interface between gases or liquids and solids to mimic realistic catalytic conditions, and DFT and Monte Carlo algorithms to simulate and understand chirality on surfaces. The next step, to be funded by the monies requested in this proposal, is to apply those methods to specific problems in chiral catalysis, including the identification of the requirements for the formation of supramolecular surface structures with enantioselective behavior, the search for better molecules to probe the chiral nature of the modified surfaces, the exploration of the transition from supramolecular to one-to-one chiral modification, the correlation of the adsorption characteristics of one-to-one chiral modifiers with their physical properties, in particular with their configuration, 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.« less

Impact of pyrrolidine-bispyrrole DNA minor groove binding agents and chirality on global proteomic profile in Escherichia Coli.

PubMed

Yang, Ya-Ting; Lin, Chun-Yu; Jeng, Jingyueh; Ong, Chi-Wi

2013-05-23

There is great interest in the design of small molecules that selectively target minor grooves of duplex DNA for controlling specific gene expression implicated in a disease. The design of chiral small molecules for rational drug design has attracted increasing attention due to the chirality of DNA. Yet, there is limited research on the chirality effect of minor groove binders on DNA interaction, especially at the protein expression level. This paper is an attempt to illustrate that DNA binding affinity might not provide a full picture on the biological activities. Drug interacting at the genomic level can be translated to the proteomic level. Here we have illustrated that although the chiral bispyrrole-pyrrolidine-oligoamides, PySSPy and PyRSPy, showed low binding affinity to DNA, their influence at the proteomic level is significant. More importantly, the chirality also plays a role. Two-dimensional proteomic profile to identify the differentially expressed protein in Escherichia coli DH5α (E coli DH5α) were investigated. E coli DH5α incubated with the chiral PySSPy and PyRSPy, diastereomeric at the pyrrolidine ring, showed differential expression of eighteen proteins as observed through two dimensional proteomic profiling. These eighteen proteins identified by MALDI_TOF/TOF MS include antioxidant defense, DNA protection, protein synthesis, chaperone, and stress response proteins. No statistically significant toxicity was observed at the tested drug concentrations as measured via MTT assay. The current results showed that the chiral PySSPy and PyRSPy impact on the proteomic profiling of E coli DH5α, implicating the importance of drug chirality on biological activities at the molecular level.

Chiral lactic hydrazone derivatives as potential bioactive antibacterial agents: Synthesis, spectroscopic, structural and molecular docking studies

NASA Astrophysics Data System (ADS)

Noshiranzadeh, Nader; Heidari, Azam; Haghi, Fakhri; Bikas, Rahman; Lis, Tadeusz

2017-01-01

A series of novel chiral lactic-hydrazone derivatives were synthesized by condensation of (S)-lactic acid hydrazide with salicylaldehyde derivatives and characterized by elemental analysis and spectroscopic studies (FT-IR, 1H NMR and 13C NMR spectroscopy). The structure of one compound was determined by single crystal X-ray analysis. Antibacterial activity of the synthesized compounds was studied against Staphylococcus aureus, Streptococcus pneumonia, Escherichia coli and Pseudomonas aeruginosa as bacterial cultures by broth microdilution method. All of the synthesized compounds showed good antibacterial activity with MIC range of 64-512 μg/mL. Compounds (S,E)-2-hydroxy-N-(2-hydroxy-5-nitrobenzylidene)propanehydrazide (5) and (S,E)-2-hydroxy-N-((3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl)propanehydrazide (7) were the most effective antibacterial derivatives against S. aureus and E. coli respectively with a MIC value of 64 μg/mL. Bacterial biofilm formation assay showed that these compounds significantly inhibited biofilm formation of P. aeruginosa. Also, in silico molecular docking studies were performed to show lipoteichoic acid synthase (LtaS) inhibitory effect of lactic hydrazone derivatives. The association between electronic and structural effects of some substituents on the benzylidene moiety and the biological activity of these chiral compounds were studied. Structural studies show that compound with higher hydrogen bonding interactions show higher antibacterial activity. The results show chiral hydrazone derivatives based on lactic acid hydrazide could be used as potential lead compounds for developing novel antibacterial agents.

Investigation of intermolecular interactions in finasteride drug crystals in view of X-ray and Hirshfeld surface analysis

NASA Astrophysics Data System (ADS)

Bojarska, Joanna; Maniukiewicz, Waldemar

2015-11-01

The N,N-dimethylformamide (DMF) solvate hemihydrate (1) of finasteride, has been structurally characterized by single-crystal X-ray diffraction at 100 K and compared with previously reported finasteride crystalline forms. In addition, in order to resolve ambiguity concerning H-bond interactions, the crystal structure of finasteride hemihydrate, (2), originally reported by Schultheiss et al. in 2009, has been redetermined with higher precision. The (1) and (2) pseudopolymorphs of finasteride crystallize as orthorhombic in chiral P212121 space group with two very similar host molecules in the asymmetric unit. The conformation of fused 6-membered rings are screw-boat, chair and chair for both molecules, while 5-membered rings assume chair in (1), and half-chair in (2). There is a fairly close resemblance of the molecular geometry for all analyzed compounds, arising due to the rigid host molecule. Inter- and intramolecular host-host, host-guest strong O-H⋯O, N-H⋯O hydrogen bonds and weak C-H⋯O interactions form 3D net conferring stability to the crystal packing. Finasterides can be classified as synthon pseudopolymorphs. Isostructural solvates crystallizing in the orthorhombic space group P212121, with Z‧ = 2, exhibit R22(8) C22(15) network, monoclinic solvate (Z‧ = 1) possess D11(2), while both orthorhombic and monoclinic polymorphs have C(4) motifs, respectively. The structural similarities and subtle differences have been interpreted in view of the 3D Hirshfeld surface analysis and associated 2D fingerprint plots, which enabled detailed qualitative and quantitative insight into the intermolecular interactions. The 97-100% of Hirshfeld surface areas are due to H···H, O···H/H⋯O, C···H/H⋯C and N⋯H/H⋯N contacts. Furthermore, the electrostatic potential has been mapped over the Hirshfeld surfaces to decode the electrostatic complementarities, which exist in the crystal packing.

Computations of the chirality-sensitive effect induced by an antisymmetric indirect spin–spin coupling

NASA Astrophysics Data System (ADS)

Garbacz, Piotr

2018-05-01

Results of quantum mechanical computations of the antisymmetric part of the indirect spin-spin coupling tensor, ?, performed using the coupled-cluster method, the second-order polarisation propagator approximation, and the density functional theory for 25 molecules and nearly 100 spin-spin couplings are reported. These results are used for an estimation of the magnitude of the recently proposed liquid-state nuclear magnetic resonance chirality-sensitive effect, which allows to determine the molecular chirality directly, i.e. without the need for the application of any chiral agent. The following were found: (i) the antisymmetry J⋆ is usually larger for the coupling between spins separated by two chemical bonds in comparison with the coupling through one bond, (ii) promising samples are those which contain fluorine, and (iii) the antisymmetry of the spin-spin coupling tensor is of the order of a few hertz for commercially available chemical compounds. Therefore, the relevant property of the experiment, the pseudoscalar Jc, for them is of the order of 1 nHz m/V.

Catalytic enantioselective synthesis of atropisomeric biaryls by a cation-directed O-alkylation

NASA Astrophysics Data System (ADS)

Jolliffe, John D.; Armstrong, Roly J.; Smith, Martin D.

2017-06-01

Axially chiral biaryls, as exemplified by 1,1‧-bi-2-naphthol (BINOL), are key components of catalysts, natural products and medicines. These materials are synthesized conventionally in enantioenriched form through metal-mediated cross coupling, de novo construction of an aromatic ring, point-to-axial chirality transfer or an atropselective transformation of an existing biaryl. Here, we report a highly enantioselective organocatalytic method for the synthesis of atropisomeric biaryls by a cation-directed O-alkylation. Treatment of racemic 1-aryl-2-tetralones with a chiral quinidine-derived ammonium salt under basic conditions in the presence of an alkylating agent leads to atropselective O-alkylation with e.r. up to 98:2. Oxidation with DDQ gives access to C2-symmetric and non-symmetric BINOL derivatives without compromising e.r. We propose that the chiral ammonium counterion differentiates between rapidly equilibrating atropisomeric enolates, leading to highly atropselective O-alkylation. This dynamic kinetic resolution process offers a general approach to the synthesis of enantioenriched atropisomeric materials.

Methodology for the Absolute Configuration Determination of Epoxythymols Using the Constituents of Ageratina glabrata.

PubMed

Arreaga-González, Héctor M; Pardo-Novoa, Julio C; Del Río, Rosa E; Rodríguez-García, Gabriela; Torres-Valencia, J Martín; Manríquez-Torres, J Jesús; Cerda-García-Rojas, Carlos M; Joseph-Nathan, Pedro; Gómez-Hurtado, Mario A

2018-01-26

A methodology to determine the enantiomeric excess and the absolute configuration (AC) of natural epoxythymols was developed and tested using five constituents of Ageratina glabrata. The methodology is based on enantiomeric purity determination employing 1,1'-bi-2-naphthol (BINOL) as a chiral solvating agent combined with vibrational circular dichroism (VCD) measurements and calculations. The conformational searching included an extensive Monte Carlo protocol that considered the rotational barriers to cover the whole conformational spaces. (+)-(8S)-10-Benzoyloxy-6-hydroxy-8,9-epoxythymol isobutyrate (1), (+)-(8S)-10-acetoxy-6-methoxy-8,9-epoxythymol isobutyrate (4), and (+)-(8S)-10-benzoyloxy-6-methoxy-8,9-epoxythymol isobutyrate (5) were isolated as enantiomerically pure constituents, while 10-isobutyryloxy-8,9-epoxythymol isobutyrate (2) was obtained as a 75:25 (8S)/(8R) scalemic mixture. In the case of 10-benzoyloxy-8,9-epoxythymol isobutyrate (3), the BINOL methodology revealed a 56:44 scalemic mixture and the VCD measurement was beyond the limit of sensitivity since the enantiomeric excess is only 12%. The racemization process of epoxythymol derivatives was studied using compound 1 and allowed the clarification of some stereochemical aspects of epoxythymol derivatives since their ACs have been scarcely analyzed and a particular behavior in their specific rotations was detected. In more than 30 oxygenated thymol derivatives, including some epoxythymols, the reported specific rotation values fluctuate from -1.6 to +1.4 passing through zero, suggesting the presence of scalemic and close to racemic mixtures, since enantiomerically pure natural constituents showed positive or negative specific rotations greater than 10 units.

Efficient synthesis, structural characterization and anti-microbial activity of chiral aryl boronate esters of 1,2-O-isopropylidene-α-D-xylofuranose.

PubMed

Trivedi, Rajiv; Rami Reddy, E; Kiran Kumar, Ch; Sridhar, B; Pranay Kumar, K; Srinivasa Rao, M

2011-07-01

A simple and efficient synthetic approach toward a series of chiral aryl boronate esters, starting from D-xylose, as anti-microbial agents, is described herein. Minimum inhibitory concentration and zone of inhibition revealed that these derivatives exhibit potent anti-bacterial and anti-fungal properties. Herein, we report the first anti-microbial activity of this class of compounds. All products have been characterized by NMR ((1)H, (13)C and (11)B), IR, elemental and mass spectral study. Copyright © 2011 Elsevier Ltd. All rights reserved.

Formation of helical organic-inorganic hybrid silica nanotubes using a chiral anionic gelator.

PubMed

Wang, Liwen; Wang, Hairui; Li, Yi; Zhuang, Wei; Zhu, Zhaoyong; Chen, Yuanli; Li, Baozong; Yang, Yonggang

2011-03-01

Right-handed helical organic-inorganic hybrid silica nanotubes were prepared using a chiral anionic gelator with 3-aminopropyltrimethoxysilane as a co-structure-directing agent and 1,4-bis(triethoxysilyl)benzene, 4,4'-bis(triethoxysilyl)-1,1'-biphenyl, bis(triethoxysilyl)methane, 1,2-bis(triethoxysilyl)ethane, and 1,2-bis(triethoxysilyl)ethene as the precursors. The sol-gel reactions were carried out in a mixture of water and ethanol at the volume ratio of 2.2:1.8. The nanostructures were studied using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). For 4,4'-biphenylene-silica nanotube, the circular dichroism spectrum indicates at least some of the biphenyl rings within the walls stack in chiral form. The TEM images taken after different reaction time reveal a cooperative mechanism. The growth of the organic self-assemblies and the adsorption of the hybrid silica oligomers occurred at the same time.

Optical Rotatory Dispersion: New Twists on AN Old Topic

NASA Astrophysics Data System (ADS)

Vaccaro, Patrick

2017-06-01

Among the many physicochemical properties used to distinguish chiral molecules, perhaps none has had as profound and sustained an impact in the realm of chemistry as the characteristic interactions that take place with polarized light. Of special note is the dispersive (non-resonant) phenomenon of circular birefringence (CB), the manifestation of which first was reported over two centuries ago and which still is employed routinely - in the more familiar guise of specific optical rotation - to gauge the enantiomeric purity of the products emerging from asymmetric syntheses. Concerted experimental and theoretical efforts designed to probe such electronic optical activity in isolated chiral molecules will be presented, with special emphasis directed towards the marked influence that intramolecular (vibrational and conformational) dynamics and intermolecular (environmental) perturbations can exert upon the intrinsic chiroptical response. Requisite isolated-molecule measurements have been made possible by our continuing development of cavity ring-down polarimetry (CRDP), an ultrasensitive polarimetric scheme that has permitted the first quantitative analyses of optical rotatory dispersion (ORD or wavelength-resolved CB) to be performed in rarefied (gaseous) media. Various technical aspects of CRDP will be discussed to illustrate the unique capabilities and practical limitations afforded by this novel methodology. Comparison of specific rotation values acquired for a broad spectrum of rigid and flexible chiral species under complementary isolated and solvated conditions will highlight the intimate coupling that exists among electronic and nuclear degrees of freedom as well as the pronounced, yet oftentimes counterintuitive, effects incurred by subtle solute-solvent interactions. The disparate nature of optical activity extracted from different surroundings will be demonstrated, with quantum-chemical calculations serving to elucidate the structural, electronic, and environmental provenance of observed behavior. In addition to unraveling basic processes that mediate chiroptical response in condensed media, the vapor-phase ORD benchmarks resulting from these studies afford a critical assessment for computational predictions of dispersive optical activity and for their burgeoning ability to assist in the assignment of absolute stereochemical configuration.

Preparation and physicochemical characterization of 5 niclosamide solvates and 1 hemisolvate.

PubMed

van Tonder, Elsa C; Mahlatji, Mabatane D; Malan, Sarel F; Liebenberg, Wilna; Caira, Mino R; Song, Mingna; de Villiers, Melgardt M

2004-02-23

The purpose of the study was to characterize the physicochemical, structural, and spectral properties of the 1:1 niclosamide and methanol, diethyl ether, dimethyl sulfoxide, N,N' dimethylformamide, and tetrahydrofuran solvates and the 2:1 niclosamide and tetraethylene glycol hemisolvate prepared by recrystallization from these organic solvents. Structural, spectral, and thermal analysis results confirmed the presence of the solvents and differences in the structural properties of these solvates. In addition, differences in the activation energy of desolvation, batch solution calorimetry, and the aqueous solubility at 25 degrees C, 24 hours, showed the stability of the solvates to be in the order: anhydrate > diethyl ether solvate > tetraethylene glycol hemisolvate > methanol solvate > dimethyl sulfoxide solvate > N,N' dimethylformamide solvate. The intrinsic and powder dissolution rates of the solvates were in the order: anhydrate > diethyl ether solvate > tetraethylene glycol hemisolvate > N,N' dimethylformamide solvate > methanol solvate > dimethyl sulfoxide solvate. Although these nonaqueous solvates had higher solubility and dissolution rates than the monohydrous forms, they were unstable in aqueous media and rapidly transformed to one of the monohydrous forms.

Optically active red-emitting Cu nanoclusters originating from complexation and redox reaction between copper(ii) and d/l-penicillamine

NASA Astrophysics Data System (ADS)

Long, Tengfei; Guo, Yanjia; Lin, Min; Yuan, Mengke; Liu, Zhongde; Huang, Chengzhi

2016-05-01

Despite a significant surge in the number of investigations into both optically active Au and Ag nanostructures, there is currently only limited knowledge about optically active Cu nanoclusters (CuNCs) and their potential applications. Here, we have succeeded in preparing a pair of optically active red-emitting CuNCs on the basis of complexation and redox reaction between copper(ii) and penicillamine (Pen) enantiomers, in which Pen serves as both a reducing agent and a stabilizing ligand. Significantly, the CuNCs feature unique aggregation induced emission (AIE) characteristics and therefore can serve as pH stimuli-responsive functional materials. Impressively, the ligand chirality plays a dramatic role for the creation of brightly emissive CuNCs, attributed to the conformation of racemic Pen being unfavorable for the electrostatic interaction, and thus suppressing the formation of cluster aggregates. In addition, the clusters display potential toward cytoplasmic staining and labelling due to the high photoluminescence (PL) quantum yields (QYs) and remarkable cellular uptake, in spite that no chirality-dependent effects in autophagy and subcellular localization are observed in the application of chiral cluster enantiomer-based cell imaging.Despite a significant surge in the number of investigations into both optically active Au and Ag nanostructures, there is currently only limited knowledge about optically active Cu nanoclusters (CuNCs) and their potential applications. Here, we have succeeded in preparing a pair of optically active red-emitting CuNCs on the basis of complexation and redox reaction between copper(ii) and penicillamine (Pen) enantiomers, in which Pen serves as both a reducing agent and a stabilizing ligand. Significantly, the CuNCs feature unique aggregation induced emission (AIE) characteristics and therefore can serve as pH stimuli-responsive functional materials. Impressively, the ligand chirality plays a dramatic role for the creation of brightly emissive CuNCs, attributed to the conformation of racemic Pen being unfavorable for the electrostatic interaction, and thus suppressing the formation of cluster aggregates. In addition, the clusters display potential toward cytoplasmic staining and labelling due to the high photoluminescence (PL) quantum yields (QYs) and remarkable cellular uptake, in spite that no chirality-dependent effects in autophagy and subcellular localization are observed in the application of chiral cluster enantiomer-based cell imaging. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01492e

Organocatalytic Transfer Hydrogenation and Hydrosilylation Reactions.

PubMed

Herrera, Raquel P

2016-06-01

The reduction of different carbon-carbon or carbon-heteroatom double bonds is a powerful tool that generates in many cases new stereogenic centers. In the last decade, the organocatalytic version of these transformations has attracted more attention, and remarkable progress has been made in this way. Organocatalysts such as chiral Brønsted acids, thioureas, chiral secondary amines or Lewis bases have been successfully used for this purpose. In this context, this chapter will cover pioneering and seminal examples using Hantzsch dihydropyridines 1 and trichlorosilane 2 as reducing agents. More recent examples will be also cited in order to cover as much as possible the complete research in this field.

Method and apparatus for low temperature destruction of halogenated hydrocarbons

DOEpatents

Reagen, William Kevin; Janikowski, Stuart Kevin

1999-01-01

A method and apparatus for decomposing halogenated hydrocarbons are provided. The halogenated hydrocarbon is mixed with solvating agents and maintained in a predetermined atmosphere and at a predetermined temperature. The mixture is contacted with recyclable reactive material for chemically reacting with the recyclable material to create dehalogenated hydrocarbons and halogenated inorganic compounds. A feature of the invention is that the process enables low temperature destruction of halogenated hydrocarbons.

Anti-cancer agents based on 4-(hetero)Ary1-1,2,5-oxadiazol-3-yl Amino derivatives and a method of making

DOEpatents

Gakh, Andrei A.; Krasavin, Mikhail; Karapetian, Ruben; Rufanov, Konstantin A.; Konstantinov, Igor; Godovykh, Elena; Soldatkina, Olga; Sosnov, Andrey V.

2013-01-29

The present disclosure relates to novel compounds that can be used as anti-cancer agents in the prostate cancer therapy. ##STR00001## In particular, the invention relates N-substituted derivatives of 4-(hetero)aryl-1,2,5-oxadiazol-3-yl amines having the structural Formula (I) and (II), stereoisomers, tautomers, racemics, prodrugs, metabolites thereof, or pharmaceutically acceptable salt and/or solvate thereof. Meaning of R1 and R2 in the Formula (I) and (II) are defined in claim 1. The invention also relates to methods for preparing said compounds, and to pharmaceutical compositions comprising said compounds.

Handedness inversion in preparing chiral 4, 4'-biphenylene-silica nanostructures

NASA Astrophysics Data System (ADS)

Li, Yi; Wang, Hairui; Wang, Liwen; Zhou, Feng; Chen, Yuanli; Li, Baozong; Yang, Yonggang

2011-04-01

An anionic gelator, D-C12ValC10COONa, derived from D-valine can cause physical gels in water and organic solvents. Helical 4, 4'-biphenylene-silica nanotubes and nanoribbons were prepared using it with 3-aminopropyltrimethoxysilane as a co-structure-directing agent and 4, 4'-bis(triethoxysilyl)-1, 1'-biphenyl (BTESB) as precursor. It was found that the handedness of the hybrid silica nanotubes/nanoribbons is sensitive to the pH value and the concentration of the reaction mixtures. However, handedness inversion was not found by changing the reaction temperature. Circular dichroism spectra of the 4, 4'-biphenylene-silica nanotubes indicated that the chirality of the organic self-assemblies were successfully transferred to the twist of the biphenylene rings through the co-structure-directing agent. The handedness of the 4, 4'-biphenylene rings was also tunable by changing the pH value and the concentration of the reaction mixtures. The FESEM images and CD spectra taken after different reaction times indicated that the handedness inversion occurred after adding BTESB.

Covalently functionalized carbon nanostructures and methods for their separation

DOEpatents

Wang, YuHuang; Brozena, Alexandra H; Deng, Shunliu; Zhang, Yin

2015-03-17

The present invention is directed to carbon nanostructures, e.g., carbon nanotubes, methods of covalently functionalizing carbon nanostructures, and methods of separating and isolating covalently functionalized carbon. In some embodiments, carbon nanotubes are reacted with alkylating agents to provide water soluble covalently functionalized carbon nanotubes. In other embodiments, carbon nanotubes are reacted with a thermally-responsive agent and exposed to light in order to separate carbon nanotubes of a specific chirality from a mixture of carbon nanotubes.

X-ray diffraction and infrared spectroscopy of N,N-dimethylformamide and dimethyl sulfoxide solvatomorphs of betulonic acid.

PubMed

Boryczka, Stanisław; Jastrzebska, Maria; Bębenek, Ewa; Kusz, Joachim; Zubko, Maciej; Kadela, Monika; Michalik, Ewa

2012-12-01

X-ray diffraction and infrared spectroscopy measurements for the N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) solvatomorphs of betulonic acid (BA) were investigated. BA [3-oxolup-20(29)-en-28-oic acid, C(30)H(46)O(3)] exhibits a wide spectrum of biological activities and is considered to be a promising natural agent for the treatment of various cancer diseases. BA as a noncrystalline substance was obtained by oxidation of betulin. Crystal structures and the spectral data allowed analysis of hydrogen bonding (H-bonding), molecular conformation, and crystal packing differences in the solvatomorphs. Crystals of BA solvates were grown from the DMF-acetone (1:10, v/v) and DMSO-water (9:1, v/v) solutions. BA-DMF (1:1) solvate crystallizes in the monoclinic P2(1) space group, Z = 2. The unit cell parameters are as follows: cell lengths a = 13.2458(5) Å, b = 6.6501(2) Å, c = 17.9766(7) Å, and β = 110.513(4)°. BA-DMSO (1:1) solvate crystallizes in the orthorhombic P2(1)2(1)2(1) (Z = 4) space group with the following unit cell parameters: a = 6.6484(4) Å, b = 13.3279(8) Å, and c = 32.6821(19) Å. Conformational analysis of the six-membered rings, cyclopentane ring, and isopropenyl group showed differences in comparison with other betulin derivatives examined earlier. For both solvates, the intermolecular packing arrangement was governed mainly by H-bonds. The shortest H-bonds with D···A distances of 2.604 and 2.657 Å, and almost linear DH···A connection occurred between OH of carboxylic group of BA and oxygen atoms from O=C and O=S groups of DMF and DMSO, respectively. Copyright © 2012 Wiley Periodicals, Inc.

Self-doped molecular composite battery electrolytes

DOEpatents

Harrup, Mason K.; Wertsching, Alan K.; Stewart, Frederick F.

2003-04-08

This invention is in solid polymer-based electrolytes for battery applications. It uses molecular composite technology, coupled with unique preparation techniques to render a self-doped, stabilized electrolyte material suitable for inclusion in both primary and secondary batteries. In particular, a salt is incorporated in a nano-composite material formed by the in situ catalyzed condensation of a ceramic precursor in the presence of a solvated polymer material, utilizing a condensation agent comprised of at least one cation amenable to SPE applications. As such, the counterion in the condensation agent used in the formation of the molecular composite is already present as the electrolyte matrix develops. This procedure effectively decouples the cation loading levels required for maximum ionic conductivity from electrolyte physical properties associated with condensation agent loading levels by utilizing the inverse relationship discovered between condensation agent loading and the time domain of the aging step.

Preferential solvation of lithium cations and impacts on oxygen reduction in lithium–air batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Dong; Qu, Deyu; Yang, Xiao -Qing

2015-09-16

The solvation of Li⁺ with eleven non-aqueous solvents commonly used as the electrolytes for Li batteries were studied. The solvation preferences of different solvents were compared by means of electrospray mass spectrometry and collision-induced dissociation. The relative strength of the solvent for the solvation of Li⁺ was determined. The Lewis acidity of the solvated Li⁺ cations was determined by the preferential solvation of the solvent in the solvation shell. The kinetics of the catalytic disproportionation of the O₂⁻ depends on the relative Lewis acidity of the solvated Li⁺ ion. The impact of the solvated Li⁺ cation on the O₂ redoxmore » reaction was also investigated.« less

A first-principles examination of the asymmetric induction model in the binap/Rh(I)-catalysed 1,4-addition of phenylboronic acid to cyclic enones by density functional theory calculations.

PubMed

Qin, Hua-Li; Chen, Xiao-Qing; Huang, Yi-Zhen; Kantchev, Eric Assen B

2014-09-26

First-principles modelling of the diastereomeric transition states in the enantiodiscrimination stage of the catalytic cycle can reveal intimate details about the mechanism of enantioselection. This information can be invaluable for further improvement of the catalytic protocols by rational design. Herein, we present a density functional theory (IEFPCM/PBE0/DGDZVP level of theory) modelling of the carborhodation step for the asymmetric 1,4-arylation of cyclic α,β-unsaturated ketones mediated by a [(binap)Rh(I)] catalyst. The calculations completely support the older, qualitative, pictorial model predicting the sense of the asymmetric induction for both the chelating diphosphane (binap) and the more recent chiral diene (Phbod) ligands, while also permitting quantification of the enantiomeric excess (ee). The effect of dispersion interaction correction and basis sets has been also investigated. Dispersion-corrected functionals and solvation models significantly improve the predicted ee values. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the Basicity of 8-Phenylsulfanyl Quipazine Derivatives: New Potential Serotonergic Agents.

PubMed

Pieńko, T; Taciak, P P; Mazurek, A P

2015-07-09

A protonation state of serotonergic ligands plays a crucial role in their pharmacological activity. In this research, the basicity of 8-phenylsulfanyl quipazine derivatives as new potential serotonergic agents was studied. The most favorable protonation sites were determined in the gas and aqueous phases. In water, a solvation effect promoting the protonation of the N3 atom overcomes a positive charge delocalization phenomenon favoring a N1 atom protonation. The most stable conformations of neutral and protonated molecules in gas and water were found. It was demonstrated that a diprotonation reaction may occur. The most favorable among the diprotonated structures is the molecule with the N1 and N3 atoms protonated. A calculation of the pKa and pKa2 in water of a set of monosubstituted 8-phenylsulfanyl quipazine derivatives was performed using B3LYP/6-31G(d) and the SMD continuum solvation model. Enthalpic and entropic contributions to the pKa and pKa2 in gas and water were separated for a rationalization of a substituent effect on values of the pKa and pKa2. The relationship of the proton affinity and the solvation enthalpy in water with some reactivity descriptors, such as the Fukui function, the molecular electrostatic potential (MEP), and the global softness, was investigated. The order of the pKa values is the most controlled by the entropy. The diprotonation reaction, despite having an unfavorable enthalpy in water, is driven entropically. Final state effects in the diprotonated species were analyzed with the triadic formula. Results of a calculation of the theoretical basicity of the 8-phenylsulfanyl quipazines indicate that they should be monoprotonated on the N3 atom in the CNS environment. Diprotonation of the studied compounds may occur in very acidic body fluids such as the gastric juice.

Resolution of 2-chloromandelic acid with (R)-(+)-N-benzyl-1-phenylethylamine: chiral discrimination mechanism.

PubMed

Peng, Yangfeng; He, Quan; Rohani, Sohrab; Jenkins, Hilary

2012-05-01

During the resolution of 2-chloromandelic acid with (R)-(+)-N-benzyl-1-phenylethylamine, the crystals of the less soluble salt were grown, and their structure were determined and presented. The chiral discrimination mechanism was investigated by examining the weak intermolecular interactions (such as hydrogen bond, CH/π, and van der Waals interactions) and molecular packing mode in crystal structure of the less soluble diastereomeric salt. A one-dimensional double-chain hydrogen-bonding network and a "lock-and-key" supramolecular packing mode are disclosed. The investigation demonstrates that hydrophobic layers with corrugated surfaces can fit into the grooves of one another to realize a compact packing, when the molecular structure of resolving agent is much larger than that of the racemate. This "lock-and-key" assembly is recognized to be another characteristic of molecular packing contributing to the chiral discrimination, in addition to the well-known sandwich-like packing by hydrophobic layers with planar boundary surfaces. Copyright © 2012 Wiley Periodicals, Inc.

Enantioselective inhibition of microbial lipolytic enzymes by nonracemic monocyclic enolphosphonate analogues of cyclophostin.

PubMed

Point, Vanessa; Malla, Raj K; Carrière, Frederic; Canaan, Stéphane; Spilling, Christopher D; Cavalier, Jean-François

2013-06-13

Four nonracemic enolphosphonate analogues of Cyclophostin were obtained by asymmetric synthesis, and their absolute configurations at both phosphorus and C-5 carbon chiral centers were unambiguously assigned. The influence of chirality was studied by testing the inhibitory effects of these four stereoisomers toward the lipolytic activity of three microbial lipases: Fusarium solani cutinase, Rv0183, and LipY from Mycobacterium tuberculosis . Cutinase was highly diastereoselective for the (Sp) configuration using (Sc) inhibitors, whereas no obvious stereopreference at phosphorus was observed with (Rc) compounds. Conversely, Rv0183 exhibited strong enantioselective discrimination for (Sp) configuration regardless of the chirality at the asymmetric carbon atom. Lastly, LipY discriminated only the unusual diastereoisomeric configuration (Rc, Rp) leading to the most potent inhibitor. This work, which provides a fundamental premise for the understanding of the stereoselective relationships between nonracemic enolphosphonates and their inhibitory activity, also opens new prospects on the design and synthesis of highly specific enantioselective antimicrobial agents.

Synthesis and anti-cancer activity of chiral tetrahydropyrazolo[1,5-a]pyridine-fused steroids.

PubMed

Lopes, Susana M M; Sousa, Emanuel P; Barreira, Luísa; Marques, Cátia; Rodrigues, Maria João; Pinho E Melo, Teresa M V D

2017-06-01

Regio- and stereoselective synthesis of novel chiral 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-fused steroids via [8π+2π] cycloaddition of diazafulvenium methides with steroidal scaffolds is reported. The biological evaluation of the new family of hexacyclic steroids as anti-cancer agents was also carried out. Hexacyclic steroids bearing a benzyl group at C-22, derived from 16-dehydropregnenolone and 16-dehydroprogesterone, show considerable cytotoxicity against EL4 (murine T-lymphoma) in contrast with the corresponding C-22-unsubstituted derivatives showing low cytotoxicity. Thus, results indicate that the presence of the benzyl group is important to ensure cytotoxicity. Copyright © 2017 Elsevier Inc. All rights reserved.

Effects of Electronic-State-Dependent Solute Polarizability: Application to Solute-Pump/Solvent-Probe Spectra.

PubMed

Sun, Xiang; Ladanyi, Branka M; Stratt, Richard M

2015-07-23

Experimental studies of solvation dynamics in liquids invariably ask how changing a solute from its electronic ground state to an electronically excited state affects a solution's dynamics. With traditional time-dependent-fluorescence experiments, that means looking for the dynamical consequences of the concomitant change in solute-solvent potential energy. But if one follows the shift in the dynamics through its effects on the macroscopic polarizability, as recent solute-pump/solvent-probe spectra do, there is another effect of the electronic excitation that should be considered: the jump in the solute's own polarizability. We examine the spectroscopic consequences of this solute polarizability change in the classic example of the solvation dye coumarin 153 dissolved in acetonitrile. After demonstrating that standard quantum chemical methods can be used to construct accurate multisite models for the polarizabilities of ground- and excited-state solvation dyes, we show via simulation that this polarizability change acts as a contrast agent, significantly enhancing the observable differences in optical-Kerr spectra between ground- and excited-state solutions. A comparison of our results with experimental solute-pump/solvent-probe spectra supports our interpretation and modeling of this spectroscopy. We predict, in particular, that solute-pump/solvent-probe spectra should be sensitive to changes in both the solvent dynamics near the solute and the electronic-state-dependence of the solute's own rotational dynamics.

On the nature of the solvated electron in ice Ih.

PubMed

de Koning, Maurice; Fazzio, Adalberto; da Silva, Antônio José Roque; Antonelli, Alex

2016-02-14

The water-solvated excess electron (EE) is a key chemical agent whose hallmark signature, its asymmetric optical absorption spectrum, continues to be a topic of debate. While nearly all investigation has focused on the liquid-water solvent, the fact that the crystalline-water solvated EE shows a very similar visible absorption pattern has remained largely unexplored. Here, we present spin-polarized density-functional theory calculations subject to periodic boundary conditions of the interplay between an EE and a number of intrinsic lattice defects in ice Ih. Our results show that the optical absorption signatures in the presence of three unsaturated hydrogen bonds (HB) are very similar to those observed experimentally. Its low-energy side can be attributed to transitions between the EE ground state and a single localized excited level, in a picture that is different from that for the liquid solvent, where this portion has been associated with hydrogen-like s → p excitations. The blue tail, on the other hand, relates to transitions between the EE ground state and delocalized excited states, which is in line with the bound-to-continuum transition interpretations for the EE in liquid water. Finally, we find that, depending on the number of dangling HBs participating in the EE trap, its charge density may spontaneously break the spin degeneracy through exchange interactions with the surrounding electrons, displaying the many-electron quantum nature of the EE problem in ice Ih.

Synthesis and bio-inspired optimization of drimenal: Discovery of chiral drimane fused oxazinones as promising antifungal and antibacterial candidates.

PubMed

Li, Dangdang; Zhang, Shasha; Song, Zehua; Li, Wei; Zhu, Feng; Zhang, Jiwen; Li, Shengkun

2018-01-01

The synthesis of antifungal natural product drimenal was accomplished. Bio-inspired optimization protruded chiral 8-(R)-drimane fused oxazinone D as a lead, considering favorable physicochemical profiles for novel pesticides. The improved scalable synthesis of scaffold D was implemented by Hofmann rearrangment under mild conditions. Detailed structural optimization was discussed for both antifungal and antibacterial exploration. Substituted groups (SGs) with C 3 ∼C 5 hydrocarbon chain are recommended for exploration of antifungal agents, while substituents with C 4 ∼C 6 carbon length are preferred for antibacterial ingredients. The chiral drimane fused oxazinone D8 was selected as a promising antifungal candidate against Botrytis cirerea, with an EC 50 value of 1.18 mg/L, with the enhancement of up to >25 folds and >80 folds than the mother compound D, and acyclic counterpart AB5, respectively. The in vivo bioassay confirmed much better preservative effect of D8 than that of Carbendazim. The chiral oxazinone variant D10 possessed prominent antibacterial activity, with MIC values of 8 mg/L against both Bacillus subtilis and Ralstonia solanacearum, showing advantages over the positive control streptomycin sulfate. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Solvation structure of the halides from x-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Antalek, Matthew; Hedman, Britt; Sarangi, Ritimukta, E-mail: ritis@slac.stanford.edu

2016-07-28

Three-dimensional models for the aqueous solvation structures of chloride, bromide, and iodide are reported. K-edge extended X-ray absorption fine structure (EXAFS) and Minuit X-ray absorption near edge (MXAN) analyses found well-defined single shell solvation spheres for bromide and iodide. However, dissolved chloride proved structurally distinct, with two solvation shells needed to explain its strikingly different X-ray absorption near edge structure (XANES) spectrum. Final solvation models were as follows: iodide, 8 water molecules at 3.60 ± 0.13 Å and bromide, 8 water molecules at 3.40 ± 0.14 Å, while chloride solvation included 7 water molecules at 3.15 ± 0.10 Å, andmore » a second shell of 7 water molecules at 4.14 ± 0.30 Å. Each of the three derived solvation shells is approximately uniformly disposed about the halides, with no global asymmetry. Time-dependent density functional theory calculations simulating the chloride XANES spectra following from alternative solvation spheres revealed surprising sensitivity of the electronic state to 6-, 7-, or 8-coordination, implying a strongly bounded phase space for the correct structure during an MXAN fit. MXAN analysis further showed that the asymmetric solvation predicted from molecular dynamics simulations using halide polarization can play no significant part in bulk solvation. Classical molecular dynamics used to explore chloride solvation found a 7-water solvation shell at 3.12 (−0.04/+0.3) Å, supporting the experimental result. These experiments provide the first fully three-dimensional structures presenting to atomic resolution the aqueous solvation spheres of the larger halide ions.« less

The Metolachlor Herbicide: An Exercise in Today's Stereochemistry

ERIC Educational Resources Information Center

Mannschreck, Albrecht; von Angerer, Erwin

2009-01-01

Metolachlor is one of the most widely used agents registered for the protection of many cultivated plants against weeds. Because of axial and central chirality, this molecule forms four stereoisomers, the investigation of which by [superscript 1]H NMR and chromatography is described. It is shown that the isomers do not interconvert at room…

Examination of the formation process of pre-solvated and solvated electron in n-alcohol using femtosecond pulse radiolysis

NASA Astrophysics Data System (ADS)

Toigawa, Tomohiro; Gohdo, Masao; Norizawa, Kimihiro; Kondoh, Takafumi; Kan, Koichi; Yang, Jinfeng; Yoshida, Yoichi

2016-06-01

The formation process of pre-solvated and solvated electron in methanol (MeOH), ethanol (EtOH), n-butanol (BuOH), and n-octanol (OcOH) were investigated using a fs-pulse radiolysis technique by observing the pre-solvated electron at 1400 nm. The formation time constants of the pre-solvated electrons were determined to be 1.2, 2.2, 3.1, and 6.3 ps for MeOH, EtOH, BuOH, and OcOH, respectively. The formation time constants of the solvated electrons were determined to be 6.7, 13.6, 22.2, and 32.9 ps for MeOH, EtOH, BuOH, and OcOH, respectively. The formation dynamics and structure of the pre-solvated and solvated electrons in n-alcohols were discussed based on relation between the obtained time constant and dielectric relaxation time constant from the view point of kinetics. The observed formation time constants of the solvated electrons seemed to be strongly correlated with the second component of the dielectric relaxation time constants, which are related to single molecule motion. On the other hand, the observed formation time constants of the pre-solvated electrons seemed to be strongly correlated with the third component of the dielectric relaxation time constants, which are related to dynamics of hydrogen bonds.

Chiral 2-Aminobenzimidazole as Bifunctional Catalyst in the Asymmetric Electrophilic Amination of Unprotected 3-Substituted Oxindoles.

PubMed

Benavent, Llorenç; Baeza, Alejandro; Freckleton, Megan

2018-06-06

The use of readily available chiral trans -cyclohexanediamine-benzimidazole derivatives as bifunctional organocatalysts in the asymmetric electrophilic amination of unprotected 3-substituted oxindoles is presented. Different organocatalysts were evaluated; the most successful one contained a dimethylamino moiety ( 5 ). With this catalyst under optimized conditions, different oxindoles containing a wide variety of substituents at the 3-position were aminated in good yields and with good to excellent enantioselectivities using di- tert -butylazodicarboxylate as the aminating agent. The procedure proved to be also efficient for the amination of 3-substituted benzofuranones, although with moderate results. A bifunctional role of the catalyst, acting as Brønsted base and hydrogen bond donor, is proposed according to the experimental results observed.

Outer-sphere interaction of aluminum and gallium solvates with competitive anions in 1,2-propanediol solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrosyants, S.P.; Buslaeva, E.R.

1986-04-01

The interaction of aluminum and gallium solvates with ..pi..-acid ligand in 1,2-propanediol solutions has been investigated. The formation of associates of hexacoordinate aluminum solvates depends on the solvation of the anions in the bulk of the solution or on the faces of the solvento complexes. In the case of gallium the association of the solvates with the anions is determined by two factors: the existence of a configurational equilibrium for the solvento complexes and the preferential solvation of the competitive ..pi..-acid ligands.

Estimation of Solvation Quantities from Experimental Thermodynamic Data: Development of the Comprehensive CompSol Databank for Pure and Mixed Solutes

NASA Astrophysics Data System (ADS)

Moine, Edouard; Privat, Romain; Sirjean, Baptiste; Jaubert, Jean-Noël

2017-09-01

The Gibbs energy of solvation measures the affinity of a solute for its solvent and is thus a key property for the selection of an appropriate solvent for a chemical synthesis or a separation process. More fundamentally, Gibbs energies of solvation are choice data for developing and benchmarking molecular models predicting solvation effects. The Comprehensive Solvation—CompSol—database was developed with the ambition to propose very large sets of new experimental solvation chemical-potential, solvation entropy, and solvation enthalpy data of pure and mixed components, covering extended temperature ranges. For mixed compounds, the solvation quantities were generated in infinite-dilution conditions by combining experimental values of pure-component and binary-mixture thermodynamic properties. Three types of binary-mixture properties were considered: partition coefficients, activity coefficients at infinite dilution, and Henry's-law constants. A rigorous methodology was implemented with the aim to select data at appropriate conditions of temperature, pressure, and concentration for the estimation of solvation data. Finally, our comprehensive CompSol database contains 21 671 data associated with 1969 pure species and 70 062 data associated with 14 102 binary mixtures (including 760 solvation data related to the ionic-liquid class of solvents). On the basis of the very large amount of experimental data contained in the CompSol database, it is finally discussed how solvation energies are influenced by hydrogen-bonding association effects.

Crystal structures of human group-VIIA phospholipase A2 inhibited by organophosphorus nerve agents exhibit non-aged complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samanta, Uttamkumar; Kirby, Stephen D.; Srinivasan, Prabhavathi

The enzyme group-VIIA phospholipase A2 (gVIIA-PLA2) is bound to lipoproteins in human blood and hydrolyzes the ester bond at the sn-2 position of phospholipid substrates with a short sn-2 chain. The enzyme belongs to a serine hydrolase superfamily of enzymes, which react with organophosphorus (OP) nerve agents. OPs ultimately exert their toxicity by inhibiting human acetycholinesterase at nerve synapses, but may additionally have detrimental effects through inhibition of other serine hydrolases. We have solved the crystal structures of gVIIA-PLA2 following inhibition with the OPs diisopropylfluorophosphate, sarin, soman and tabun. The sarin and soman complexes displayed a racemic mix of P{submore » R} and P{sub S} stereoisomers at the P-chiral center. The tabun complex displayed only the P{sub R} stereoisomer in the crystal. In all cases, the crystal structures contained intact OP adducts that had not aged. Aging refers to a secondary process OP complexes can go through, which dealkylates the nerve agent adduct and results in a form that is highly resistant to either spontaneous or oxime-mediated reactivation. Non-aged OP complexes of the enzyme were corroborated by trypsin digest and matrix-assisted laser desorption ionization mass spectrometry of OP-enzyme complexes. The lack of stereoselectivity of sarin reaction was confirmed by gas chromatography/mass spectrometry using a chiral column to separate and quantitate the unbound stereoisomers of sarin following incubation with enzyme. The structural details and characterization of nascent reactivity of several toxic nerve agents is discussed with a long-term goal of developing gVIIA-PLA2 as a catalytic bioscavenger of OP nerve agents.« less

Crystal structures of human group-VIIA phospholipase A2 inhibited by organophosphorus nerve agents exhibit non-aged complexes.

PubMed

Samanta, Uttamkumar; Kirby, Stephen D; Srinivasan, Prabhavathi; Cerasoli, Douglas M; Bahnson, Brian J

2009-08-15

The enzyme group-VIIA phospholipase A2 (gVIIA-PLA2) is bound to lipoproteins in human blood and hydrolyzes the ester bond at the sn-2 position of phospholipid substrates with a short sn-2 chain. The enzyme belongs to a serine hydrolase superfamily of enzymes, which react with organophosphorus (OP) nerve agents. OPs ultimately exert their toxicity by inhibiting human acetycholinesterase at nerve synapses, but may additionally have detrimental effects through inhibition of other serine hydrolases. We have solved the crystal structures of gVIIA-PLA2 following inhibition with the OPs diisopropylfluorophosphate, sarin, soman and tabun. The sarin and soman complexes displayed a racemic mix of P(R) and P(S) stereoisomers at the P-chiral center. The tabun complex displayed only the P(R) stereoisomer in the crystal. In all cases, the crystal structures contained intact OP adducts that had not aged. Aging refers to a secondary process OP complexes can go through, which dealkylates the nerve agent adduct and results in a form that is highly resistant to either spontaneous or oxime-mediated reactivation. Non-aged OP complexes of the enzyme were corroborated by trypsin digest and matrix-assisted laser desorption ionization mass spectrometry of OP-enzyme complexes. The lack of stereoselectivity of sarin reaction was confirmed by gas chromatography/mass spectrometry using a chiral column to separate and quantitate the unbound stereoisomers of sarin following incubation with enzyme. The structural details and characterization of nascent reactivity of several toxic nerve agents is discussed with a long-term goal of developing gVIIA-PLA2 as a catalytic bioscavenger of OP nerve agents.

KECSA-Movable Type Implicit Solvation Model (KMTISM)

PubMed Central

2015-01-01

Computation of the solvation free energy for chemical and biological processes has long been of significant interest. The key challenges to effective solvation modeling center on the choice of potential function and configurational sampling. Herein, an energy sampling approach termed the “Movable Type” (MT) method, and a statistical energy function for solvation modeling, “Knowledge-based and Empirical Combined Scoring Algorithm” (KECSA) are developed and utilized to create an implicit solvation model: KECSA-Movable Type Implicit Solvation Model (KMTISM) suitable for the study of chemical and biological systems. KMTISM is an implicit solvation model, but the MT method performs energy sampling at the atom pairwise level. For a specific molecular system, the MT method collects energies from prebuilt databases for the requisite atom pairs at all relevant distance ranges, which by its very construction encodes all possible molecular configurations simultaneously. Unlike traditional statistical energy functions, KECSA converts structural statistical information into categorized atom pairwise interaction energies as a function of the radial distance instead of a mean force energy function. Within the implicit solvent model approximation, aqueous solvation free energies are then obtained from the NVT ensemble partition function generated by the MT method. Validation is performed against several subsets selected from the Minnesota Solvation Database v2012. Results are compared with several solvation free energy calculation methods, including a one-to-one comparison against two commonly used classical implicit solvation models: MM-GBSA and MM-PBSA. Comparison against a quantum mechanics based polarizable continuum model is also discussed (Cramer and Truhlar’s Solvation Model 12). PMID:25691832

Solvation thermodynamics and the physical-chemical meaning of the constant in Abraham solvation equations.

PubMed

van Noort, Paul C M

2012-04-01

Abraham solvation equations find widespread use in environmental chemistry. Until now, the intercept in these equations was determined by fitting experimental data. To simplify the determination of the coefficients in Abraham solvation equations, this study derives theoretical expressions for the value of the intercept for various partition processes. To that end, a modification of the description of the Ben-Naim standard state into the van der Waals volume is proposed. Differences between predicted and fitted values of the Abraham solvation equation intercept for the enthalpy of solvation, the entropy of solvation, solvent-water partitioning, air-solvent partitioning, partitioning into micelles, partitioning into lipid membranes and lipids, and chromatographic retention indices are comparable to experimental uncertainties in these values. Copyright © 2011 Elsevier Ltd. All rights reserved.

Unusual dynamic properties of water near the ice-binding plane of hyperactive antifreeze protein

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuffel, Anna; Czapiewski, Dariusz; Zielkiewicz, Jan, E-mail: jaz@chem.pg.gda.pl

2015-10-07

The dynamical properties of solvation water of hyperactive antifreeze protein from Choristoneura fumiferana (CfAFP) are analyzed and discussed in context of its antifreeze activity. The protein comprises of three well-defined planes and one of them binds to the surface of ice. The dynamical properties of solvation water around each of these planes were analyzed separately; the results are compared with the dynamical properties of solvation water of ice around its two crystallographic planes: basal and prism. Three main conclusions are inferred from our investigations. The first one is that the solvation shell of CfAFP does not seem to be particularlymore » far-ranged, at least not beyond what is usually observed for proteins that do not interact with ice. Therefore, it does not appear to us that the antifreeze activity is enhanced by a long-ranged retardation of water mobility. Also the correlation between the collective mobility of water and the collective mobility of protein atoms highly resembles the one measured for the protein that does not interact with ice. Our second conclusion is that the dynamical properties of solvation water of CfAFP are non-uniform. The dynamics of solvation water of ice-binding plane is, in some respects, different from the dynamics of solvation water of the two remaining planes. The feature that distinguishes the dynamics of solvation water of the three planes is the activation energy of diffusion process. The third conclusion is that—from the three analyzed solvation shells of CfAFP—the dynamical properties of solvation water of the ice-binding plane resemble the most the properties of solvation water of ice; note, however, that these properties still clearly differ from the dynamic properties of solvation water of ice.« less

Thermodynamic-ensemble independence of solvation free energy.

PubMed

Chong, Song-Ho; Ham, Sihyun

2015-02-10

Solvation free energy is the fundamental thermodynamic quantity in solution chemistry. Recently, it has been suggested that the partial molar volume correction is necessary to convert the solvation free energy determined in different thermodynamic ensembles. Here, we demonstrate ensemble-independence of the solvation free energy on general thermodynamic grounds. Theoretical estimates of the solvation free energy based on the canonical or grand-canonical ensemble are pertinent to experiments carried out under constant pressure without any conversion.

Explicitly Representing the Solvation Shell in Continuum Solvent Calculations

PubMed Central

Svendsen, Hallvard F.; Merz, Kenneth M.

2009-01-01

A method is presented to explicitly represent the first solvation shell in continuum solvation calculations. Initial solvation shell geometries were generated with classical molecular dynamics simulations. Clusters consisting of solute and 5 solvent molecules were fully relaxed in quantum mechanical calculations. The free energy of solvation of the solute was calculated from the free energy of formation of the cluster and the solvation free energy of the cluster calculated with continuum solvation models. The method has been implemented with two continuum solvation models, a Poisson-Boltzmann model and the IEF-PCM model. Calculations were carried out for a set of 60 ionic species. Implemented with the Poisson-Boltzmann model the method gave an unsigned average error of 2.1 kcal/mol and a RMSD of 2.6 kcal/mol for anions, for cations the unsigned average error was 2.8 kcal/mol and the RMSD 3.9 kcal/mol. Similar results were obtained with the IEF-PCM model. PMID:19425558

Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide

PubMed Central

Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.

2008-01-01

The division of thermodynamic solvation free energies of electrolytes into ionic constituents is conventionally accomplished by using the single-ion solvation free energy of one reference ion, conventionally the proton, to set the single-ion scales. Thus the determination of the free energy of solvation of the proton in various solvents is a fundamental issue of central importance in solution chemistry. In the present article, relative solvation free energies of ions and ion-solvent clusters in methanol, acetonitrile, and dimethyl sulfoxide (DMSO) have been determined using a combination of experimental and theoretical gas-phase free energies of formation, solution-phase reduction potentials and acid dissociation constants, and gas-phase clustering free energies. Applying the cluster pair approximation to differences between these relative solvation free energies leads to values of −263.5, −260.2, and −273.3 kcal/mol for the absolute solvation free energy of the proton in methanol, acetonitrile, and DMSO, respectively. The final absolute proton solvation free energies are used to assign absolute values for the normal hydrogen electrode potential and the solvation free energies of other single ions in the above solvents. PMID:17214493

Stereochemical inversion of a cyano-stabilized grignard reagent: remarkable effects of the ethereal solvent structure and concentration.

PubMed

Gao, Ming; Patwardhan, Neeraj N; Carlier, Paul R

2013-09-25

Chiral organometallic reagents are useful in asymmetric synthesis, and configurational stability of these species is critical to success. In this study we followed the epimerization of a chiral Grignard reagent, prepared by Mg/Br exchange of bromonitrile trans-2b. This compound underwent highly retentive Mg/Br exchange in Et2O; less retention was observed in 2-MeTHF and THF. Epimerization rate constants k(tc) were determined at 195 K by measuring the diastereomer ratio of deuteration product d1-3b as a function of the delay time before quench. Studies were also performed at varying concentrations of Et2O in toluene. Remarkable dynamic range in k(tc) was seen: relative to reaction at 0.12 M Et2O in toluene, epimerization was 26-, 800-, and 1300-fold faster in Et2O, 2-MeTHF, and THF, respectively. Thus, the identity and concentration of an ethereal solvent can dramatically affect configurational stability. Reaction stoichiometry experiments suggested that, in Et2O, the Grignard reagent derived from trans-2b exists as an i-PrMgCl heterodimer; the invariance of k(tc) over a 20-fold range in [Mg]total ruled out mandatory deaggregation (or aggregation) on the epimerization path. Analysis of the dependency of k(tc) on [Et2O] and temperature in Et2O/toluene solution at 195, 212, and 231 K indicated fast incremental solvation before rate-limiting ion-pair separation and provided an estimate of the entropic cost of capturing a solvent ligand (-13 ± 3 eu). Calculations at the MP2/6-31G*(PCM)//B3LYP/6-31G* level provide support for these conclusions and map out a possible "ionogenic conducted tour" pathway for epimerization.

A unified perspective on preferential solvation and adsorption based on inhomogeneous solvation theory

NASA Astrophysics Data System (ADS)

Shimizu, Seishi; Matubayasi, Nobuyuki

2018-02-01

How cosolvents affects solvation has been revealed through the independent determination of solute-solvent and solute-cosolvent interactions guaranteed by the phase rule. Based on the first principles of inhomogeneous solvation theory, we present here a general matrix theory encompassing both preferential solvation and surface adsorption. The central role of the stability conditions, that govern how many excess numbers (surface excesses) are independently determinable, have been clarified from the first principles. The advantage of the inhomogeneous approach has been demonstrated to be in its ease in treating solvation and adsorption in a unified manner, while its disadvantage, for example in membrane dialysis experiments, can be overcome by the inhomogeneous-homogeneous conversion.

Ligand solvation in molecular docking.

PubMed

Shoichet, B K; Leach, A R; Kuntz, I D

1999-01-01

Solvation plays an important role in ligand-protein association and has a strong impact on comparisons of binding energies for dissimilar molecules. When databases of such molecules are screened for complementarity to receptors of known structure, as often occurs in structure-based inhibitor discovery, failure to consider ligand solvation often leads to putative ligands that are too highly charged or too large. To correct for the different charge states and sizes of the ligands, we calculated electrostatic and non-polar solvation free energies for molecules in a widely used molecular database, the Available Chemicals Directory (ACD). A modified Born equation treatment was used to calculate the electrostatic component of ligand solvation. The non-polar component of ligand solvation was calculated based on the surface area of the ligand and parameters derived from the hydration energies of apolar ligands. These solvation energies were subtracted from the ligand-receptor interaction energies. We tested the usefulness of these corrections by screening the ACD for molecules that complemented three proteins of known structure, using a molecular docking program. Correcting for ligand solvation improved the rankings of known ligands and discriminated against molecules with inappropriate charge states and sizes.

Lithium ion solvation and diffusion in bulk organic electrolytes from first-principles and classical reactive molecular dynamics.

PubMed

Ong, Mitchell T; Verners, Osvalds; Draeger, Erik W; van Duin, Adri C T; Lordi, Vincenzo; Pask, John E

2015-01-29

Lithium-ion battery performance is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact both the solvation and diffusivity of Li ions. In this work, we used first-principles molecular dynamics to examine the solvation and diffusion of Li ions in the bulk organic solvents ethylene carbonate (EC), ethyl methyl carbonate (EMC), and a mixture of EC and EMC. We found that Li ions are solvated by either carbonyl or ether oxygen atoms of the solvents and sometimes by the PF6(-) anion. Li(+) prefers a tetrahedrally coordinated first solvation shell regardless of which species are involved, with the specific preferred solvation structure dependent on the organic solvent. In addition, we calculated Li diffusion coefficients in each electrolyte, finding slightly larger diffusivities in the linear carbonate EMC compared to the cyclic carbonate EC. The magnitude of the diffusion coefficient correlates with the strength of Li(+) solvation. Corresponding analysis for the PF6(-) anion shows greater diffusivity associated with a weakly bound, poorly defined first solvation shell. These results can be used to aid in the design of new electrolytes to improve Li-ion battery performance.

Cluster-continuum quasichemical theory calculation of the lithium ion solvation in water, acetonitrile and dimethyl sulfoxide: an absolute single-ion solvation free energy scale.

PubMed

Carvalho, Nathalia F; Pliego, Josefredo R

2015-10-28

Absolute single-ion solvation free energy is a very useful property for understanding solution phase chemistry. The real solvation free energy of an ion depends on its interaction with the solvent molecules and on the net potential inside the solute cavity. The tetraphenyl arsonium-tetraphenyl borate (TATB) assumption as well as the cluster-continuum quasichemical theory (CC-QCT) approach for Li(+) solvation allows access to a solvation scale excluding the net potential. We have determined this free energy scale investigating the solvation of the lithium ion in water (H2O), acetonitrile (CH3CN) and dimethyl sulfoxide (DMSO) solvents via the CC-QCT approach. Our calculations at the MP2 and MP4 levels with basis sets up to the QZVPP+diff quality, and including solvation of the clusters and solvent molecules by the dielectric continuum SMD method, predict the solvation free energy of Li(+) as -116.1, -120.6 and -123.6 kcal mol(-1) in H2O, CH3CN and DMSO solvents, respectively (1 mol L(-1) standard state). These values are compatible with the solvation free energy of the proton of -253.4, -253.2 and -261.1 kcal mol(-1) in H2O, CH3CN and DMSO solvents, respectively. Deviations from the experimental TATB scale are only 1.3 kcal mol(-1) in H2O and 1.8 kcal mol(-1) in DMSO solvents. However, in the case of CH3CN, the deviation reaches a value of 9.2 kcal mol(-1). The present study suggests that the experimental TATB scale is inconsistent for CH3CN. A total of 125 values of the solvation free energy of ions in these three solvents were obtained. These new data should be useful for the development of theoretical solvation models.

Preparation of cerium halide solvate complexes

DOEpatents

Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

2013-08-06

Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

Difference rule-a new thermodynamic principle: prediction of standard thermodynamic data for inorganic solvates.

PubMed

Jenkins, H Donald Brooke; Glasser, Leslie

2004-12-08

We present a quite general thermodynamic "difference" rule, derived from thermochemical first principles, quantifying the difference between the standard thermodynamic properties, P, of a solid n-solvate (or n-hydrate), n-S, containing n molecules of solvate, S (water or other) and the corresponding solid parent (unsolvated) salt: [P[n-solvate] - P[parent

Bis(2,3,5,6-tetra-2-pyridyl­pyrazine-κ3 N 2,N 1,N 6)nickel(II) dithio­cyanate dihydrate

PubMed Central

De la Pinta, Noelia; Fidalgo, M. Luz; Ezpeleta, José M.; Cortés, Roberto; Madariaga, Gotzon

2011-01-01

In the title compound, [Ni(C24H16N6)2](NCS)2·2H2O, the central NiII ion is octahedrally coordinated by six N atoms of two tridentate 2,3,5,6-tetra-2-pyridyl­pyrazine ligands (tppz). Two thio­cyanate anions act as counter-ions and two water mol­ecules act as solvation agents. O—H⋯N hydrogen bonds are observed in the crystral structure. PMID:21522540

A Comparison of QSAR Based Thermo and Water Solvation Property Prediction Tools and Experimental Data for Selected Traditional Chemical Warfare Agents and Simulants

DTIC Science & Technology

2014-07-01

Labs uses parameterized Hammett -type equations to describe 1500 possible combinations of more than 650 ionizable functional groups. The change in...of the form ⋯ , ⋯ Equation (1) where Ypred is the predicted property, c0 is a constant, c1 to cn are coefficients from the...regression to the training set of measurements, X1 to Xn represent molecular or fragment or field-based descriptors, and the final term in Equation 1

Lithium Ion Solvation and Diffusion in Bulk Organic Electrolytes from First-Principles and Classical Reactive Molecular Dynamics

DOE PAGES

Ong, Mitchell T.; Verners, Osvalds; Draeger, Erik W.; ...

2014-12-19

We report that lithium-ion battery performance is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact both the solvation and diffusivity of Li ions. In this work, we used first-principles molecular dynamics to examine the solvation and diffusion of Li ions in the bulk organic solvents ethylene carbonate (EC), ethyl methyl carbonate (EMC), and a mixture of EC and EMC. We found that Li ions are solvated by either carbonyl or ether oxygen atoms of the solvents and sometimes by the PF more » $$\\bar{6}$$ anion. Li + prefers a tetrahedrally coordinated first solvation shell regardless of which species are involved, with the specific preferred solvation structure dependent on the organic solvent. In addition, we calculated Li diffusion coefficients in each electrolyte, finding slightly larger diffusivities in the linear carbonate EMC compared to the cyclic carbonate EC. The magnitude of the diffusion coefficient correlates with the strength of Li + solvation. Corresponding analysis for the PF $$\\bar{6}$$ anion shows greater diffusivity associated with a weakly bound, poorly defined first solvation shell. In conclusion, these results can be used to aid in the design of new electrolytes to improve Li-ion battery performance.« less

Absolute single-ion solvation free energy scale in methanol determined by the lithium cluster-continuum approach.

PubMed

Pliego, Josefredo R; Miguel, Elizabeth L M

2013-05-02

Absolute solvation free energy of the lithium cation in methanol was calculated by the cluster-continuum quasichemical theory of solvation. Clusters with up to five methanol molecules were investigated using X3LYP, MP2, and MP4 methods with DZVP, 6-311+G(2df,2p), TZVPP+diff, and QZVPP+diff basis sets and including the cluster solvation through the PCM and SMD continuum models. Our calculations have determined a value of -118.1 kcal mol(-1) for the solvation free energy of the lithium, in close agreement with a value of -116.6 kcal mol(-1) consistent with the TATB assumption. Using data of solvation and transfer free energy of a pair of ions, electrode potentials and pKa, we have obtained the solvation free energy of 25 ions in methanol. Our analysis leads to a value of -253.6 kcal mol(-1) for the solvation free energy of the proton, which can be compared with the value of -263.5 kcal mol(-1) obtained by Kelly et al. using the cluster pair approximation. Considering that this difference is due to the methanol surface potential, we have estimated that it corresponds to -0.429 V.

Teaching Ionic Solvation Structure with a Monte Carlo Liquid Simulation Program

NASA Astrophysics Data System (ADS)

Serrano, Agostinho; Santos, Flávia M. T.; Greca, Ileana M.

2004-09-01

It is shown how basic aspects of ionic solvation structure, a fundamental topic for understanding different concepts and levels of representations of chemical structure and transformation, can be taught with the help of a Monte Carlo simulation package for molecular liquids. By performing a pair distribution function analysis of the solvation of Na + , Cl , and Ar in water, it is shown that it is feasible to explain the differences in solvation for these differently charged solutes. Visual representations of the solvated ions can also be employed to help the teaching activity. This may serve as an introduction to the study of solvation structure in chemistry undergraduate courses. The advantages of using tested, up-to-date scientific simulation programs as the fundamental bricks in the construction of virtual laboratories is also discussed.

A fast method for the determination of fractional contributions to solvation in proteins

PubMed Central

Talavera, David; Morreale, Antonio; Meyer, Tim; Hospital, Adam; Ferrer-Costa, Carles; Gelpi, Josep Lluis; de la Cruz, Xavier; Soliva, Robert; Luque, F. Javier; Orozco, Modesto

2006-01-01

A fast method for the calculation of residue contributions to protein solvation is presented. The approach uses the exposed polar and apolar surface of protein residues and has been parametrized from the fractional contributions to solvation determined from linear response theory coupled to molecular dynamics simulations. Application of the method to a large subset of proteins taken from the Protein Data Bank allowed us to compute the expected fractional solvation of residues. This information is used to discuss when a residue or a group of residues presents an uncommon solvation profile. PMID:17001031

Synthesis of chiral chloroquine and its analogues as antimalarial agents.

PubMed

Sinha, Manish; Dola, Vasanth R; Soni, Awakash; Agarwal, Pooja; Srivastava, Kumkum; Haq, Wahajul; Puri, Sunil K; Katti, Seturam B

2014-11-01

In this investigation, we describe a new approach to chiral synthesis of chloroquine and its analogues. All tested compounds displayed potent activity against chloroquine sensitive as well as chloroquine resistant strains of Plasmodium falciparum in vitro and Plasmodium yoelii in vivo. Compounds S-13 b, S-13c, S-13 d and S-13 i displayed excellent in vitro antimalarial activity with an IC50 value of 56.82, 60.41, 21.82 and 7.94 nM, respectively, in the case of resistant strain. Furthermore, compounds S-13a, S-13c and S-13 d showed in vivo suppression of 100% parasitaemia on day 4 in the mouse model against Plasmodium yoelii when administered orally. These results underscore the application of synthetic methodology and need for further lead optimization. Copyright © 2014 Elsevier Ltd. All rights reserved.

The first total synthesis of sporiolide A.

PubMed

Du, Yuguo; Chen, Qi; Linhardt, Robert J

2006-10-27

The first total synthesis of the natural cytotoxic agent sporiolide A has been accomplished from D-glucal in 16 steps with 6.1% overall yield. Carbohydrates were applied as the chiral templates to manipulate the absolute configuration during the synthesis. Pyridinium chlorochromate (PCC)-promoted transformation of the cyclic enol-ether to lactone, followed by Yamaguchi esterification and intramolecular ring closure metathesis, greatly facilitates synthesis of the target compound.

Molecular Innovations Toward Theranostics of Aggressive Prostate Cancer

DTIC Science & Technology

2017-11-01

the positive control. 3. Proposed biodistribution, pharmacokinetics, and potential cytotoxicity evaluation experiments were accomplished. Task 4...Radiochemistry and in vitro assay of the synthesized theranostic agents (Sun/Hsieh) Task 5: In vivo and PET/CT imaging evaluation of the synthesized...were designed, synthesized and evaluated using a well-validated model ligand (integrin αvβ3 ligand). Our work suggests that the chirality of BFC

Nature's Chiral Catalyst and Anti-Malarial Agent: Isolation and Structure Elucidation of Cinchonine and Quinine from "Cinchona calisaya"

ERIC Educational Resources Information Center

Carroll, Anne-Marie; Kavanagh, David J.; McGovern, Fiona P.; Reilly, Joe W.; Walsh, John J.

2012-01-01

Nature is a well-recognized source of compounds of interest, but access is often an issue. One pertinent example is the cinchona alkaloids from the bark of "Cinchona calisaya." In this experiment, students at the third-year undergraduate level undertake the selective isolation and characterization of two of the four main alkaloids present in the…

Enantioselective Decarboxylative Arylation of α-Amino Acids via the Merger of Photoredox and Nickel Catalysis.

PubMed

Zuo, Zhiwei; Cong, Huan; Li, Wei; Choi, Junwon; Fu, Gregory C; MacMillan, David W C

2016-02-17

An asymmetric decarboxylative Csp(3)-Csp(2) cross-coupling has been achieved via the synergistic merger of photoredox and nickel catalysis. This mild, operationally simple protocol transforms a wide variety of naturally abundant α-amino acids and readily available aryl halides into valuable chiral benzylic amines in high enantiomeric excess, thereby producing motifs found in pharmacologically active agents.

Differential geometry based solvation model. III. Quantum formulation

PubMed Central

Chen, Zhan; Wei, Guo-Wei

2011-01-01

Solvation is of fundamental importance to biomolecular systems. Implicit solvent models, particularly those based on the Poisson-Boltzmann equation for electrostatic analysis, are established approaches for solvation analysis. However, ad hoc solvent-solute interfaces are commonly used in the implicit solvent theory. Recently, we have introduced differential geometry based solvation models which allow the solvent-solute interface to be determined by the variation of a total free energy functional. Atomic fixed partial charges (point charges) are used in our earlier models, which depends on existing molecular mechanical force field software packages for partial charge assignments. As most force field models are parameterized for a certain class of molecules or materials, the use of partial charges limits the accuracy and applicability of our earlier models. Moreover, fixed partial charges do not account for the charge rearrangement during the solvation process. The present work proposes a differential geometry based multiscale solvation model which makes use of the electron density computed directly from the quantum mechanical principle. To this end, we construct a new multiscale total energy functional which consists of not only polar and nonpolar solvation contributions, but also the electronic kinetic and potential energies. By using the Euler-Lagrange variation, we derive a system of three coupled governing equations, i.e., the generalized Poisson-Boltzmann equation for the electrostatic potential, the generalized Laplace-Beltrami equation for the solvent-solute boundary, and the Kohn-Sham equations for the electronic structure. We develop an iterative procedure to solve three coupled equations and to minimize the solvation free energy. The present multiscale model is numerically validated for its stability, consistency and accuracy, and is applied to a few sets of molecules, including a case which is difficult for existing solvation models. Comparison is made to many other classic and quantum models. By using experimental data, we show that the present quantum formulation of our differential geometry based multiscale solvation model improves the prediction of our earlier models, and outperforms some explicit solvation model. PMID:22112067

Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li–S Battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

See, Kimberly A.; Wu, Heng -Liang; Lau, Kah Chun

Li-S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed "solvates" that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability; however, hydrofluoroether cosolvents, thought to be inert to the solvate structure itself, can bemore » introduced to reduce viscosity and enhance diffusion. Nazar and co-workers previously reported that addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) to the LiTFSI in acetonitrile solvate, (MeCN) 2-LiTFSI, results in enhanced capacity retention compared to the neat solvate. Here, we evaluate the effect of TTE addition on both the electrochemical behavior of the Li-S cell and the solvation structure of the (MeCN) 2-LiTFSI electrolyte. Contrary to previous suggestions, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that TTE coordinates to Li + at the expense of MeCN coordination, thereby producing a higher content of free MeCN, a good polysulfide solvent, in the electrolyte. Furthermore, the electrolytes containing a higher free MeCN content facilitate faster polysulfide formation kinetics during the electrochemical reduction of S in a Li-S cell likely as a result of the solvation power of the free MeCN.« less

Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li–S Battery

DOE PAGES

See, Kimberly A.; Wu, Heng -Liang; Lau, Kah Chun; ...

2016-11-16

Li-S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed "solvates" that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability; however, hydrofluoroether cosolvents, thought to be inert to the solvate structure itself, can bemore » introduced to reduce viscosity and enhance diffusion. Nazar and co-workers previously reported that addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) to the LiTFSI in acetonitrile solvate, (MeCN) 2-LiTFSI, results in enhanced capacity retention compared to the neat solvate. Here, we evaluate the effect of TTE addition on both the electrochemical behavior of the Li-S cell and the solvation structure of the (MeCN) 2-LiTFSI electrolyte. Contrary to previous suggestions, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that TTE coordinates to Li + at the expense of MeCN coordination, thereby producing a higher content of free MeCN, a good polysulfide solvent, in the electrolyte. Furthermore, the electrolytes containing a higher free MeCN content facilitate faster polysulfide formation kinetics during the electrochemical reduction of S in a Li-S cell likely as a result of the solvation power of the free MeCN.« less

Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li-S Battery.

PubMed

See, Kimberly A; Wu, Heng-Liang; Lau, Kah Chun; Shin, Minjeong; Cheng, Lei; Balasubramanian, Mahalingam; Gallagher, Kevin G; Curtiss, Larry A; Gewirth, Andrew A

2016-12-21

Li-S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed "solvates" that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability; however, hydrofluoroether cosolvents, thought to be inert to the solvate structure itself, can be introduced to reduce viscosity and enhance diffusion. Nazar and co-workers previously reported that addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) to the LiTFSI in acetonitrile solvate, (MeCN) 2 -LiTFSI, results in enhanced capacity retention compared to the neat solvate. Here, we evaluate the effect of TTE addition on both the electrochemical behavior of the Li-S cell and the solvation structure of the (MeCN) 2 -LiTFSI electrolyte. Contrary to previous suggestions, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that TTE coordinates to Li + at the expense of MeCN coordination, thereby producing a higher content of free MeCN, a good polysulfide solvent, in the electrolyte. The electrolytes containing a higher free MeCN content facilitate faster polysulfide formation kinetics during the electrochemical reduction of S in a Li-S cell likely as a result of the solvation power of the free MeCN.

The solvation of ions in acetonitrile and acetone. II. Monte Carlo simulations using polarizable solvent models

NASA Astrophysics Data System (ADS)

Fischer, R.; Richardi, J.; Fries, P. H.; Krienke, H.

2002-11-01

Structural properties and energies of solvation are simulated for alkali and halide ions. The solvation structure is discussed in terms of various site-site distribution functions, of solvation numbers, and of orientational correlation functions of the solvent molecules around the ions. The solvent polarizability has notable effects which cannot be intuitively predicted. In particular, it is necessary to reproduce the experimental solvation numbers of small ions. The changes of solvation properties are investigated along the alkali and halide series. By comparing the solvation of ions in acetone to that in acetonitrile, it is shown that the spatial correlations among the solvent molecules around an ion result in a strong screening of the ion-solvent direct intermolecular potential and are essential to understand the changes in the solvation structures and energies between different solvents. The solvation properties derived from the simulations are compared to earlier predictions of the hypernetted chain (HNC) approximation of the molecular Ornstein-Zernike (MOZ) theory [J. Richardi, P. H. Fries, and H. Krienke, J. Chem. Phys. 108, 4079 (1998)]. The MOZ(HNC) formalism gives an overall qualitatively correct picture of the solvation and its various unexpected findings are corroborated. For the larger ions, its predictions become quantitative. The MOZ approach allows to calculate solvent-solvent and ion-solvent potentials of mean force, which shed light on the 3D labile molecular and ionic architectures in the solution. These potentials of mean force convey a unique information which is necessary to fully interpret the angle-averaged structural functions computed from the simulations. Finally, simulations of solutions at finite concentrations show that the solvent-solvent and ion-solvent spatial correlations at infinite dilution are marginally altered by the introduction of fair amounts of ions.

How to study picosecond solvation dynamics using fluorescent probes with small Stokes shifts

NASA Astrophysics Data System (ADS)

Silori, Yogita; Dey, Shivalee; De, Arijit K.

2018-02-01

Xanthene dyes have wide ranging applications as fluorescent probes in analytical, biochemical and medical contexts. Being cationic/anionic in nature, the solvation dynamics of xanthene dyes confined within a negatively/positively charged interface are very interesting. Unfortunately, the floppy structure and small Stokes shift render any xanthene dye unsuitable for use as a solvation probe. Using di-sodium fluorescein, we present our work on the picosecond solvation dynamics of bulk and confined water (at pH = 9.2). We also propose a new methodology for studying picosecond solvation dynamics using any fluorescent dye with a small Stokes shift. We discuss how scattering contributions can be effectively removed, and propose an alternative way of defining zero time of solvation. Finally, we demonstrate the tuning location of the probe within confinement.

The effect of co-solvent addition on Li-solvation in solvate electrolytes in Li-S batteries

NASA Astrophysics Data System (ADS)

Lau, Kah Chun; See, Kimberly A.; Wu, Heng-Liang; Shin, Minjeong; Curtiss, Larry A.; Gewirth, Andrew A.

Li?S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed `solvates' that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability, however, cosolvents that thought to be inert to the solvate structure itself, can be introduced to reduce viscosity and enhance diffusion. In this work, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations are used to study the unique solvation structure of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether as co-solvent in solvate (MeCN)2?LiTFSI electrolyte that used in Li-S battery. The underlying design rules and implications to Li-S battery performance will be discussed. This work was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

Theory of competitive solvation of polymers by two solvents and entropy-enthalpy compensation in the solvation free energy upon dilution with the second solvent.

PubMed

Dudowicz, Jacek; Freed, Karl F; Douglas, Jack F

2015-06-07

We develop a statistical mechanical lattice theory for polymer solvation by a pair of relatively low molar mass solvents that compete for binding to the polymer backbone. A theory for the equilibrium mixture of solvated polymer clusters {AiBCj} and free unassociated molecules A, B, and C is formulated in the spirit of Flory-Huggins mean-field approximation. This theoretical framework enables us to derive expressions for the boundaries for phase stability (spinodals) and other basic properties of these polymer solutions: the internal energy U, entropy S, specific heat CV, extent of solvation Φsolv, average degree of solvation 〈Nsolv〉, and second osmotic virial coefficient B2 as functions of temperature and the composition of the mixture. Our theory predicts many new phenomena, but the current paper applies the theory to describe the entropy-enthalpy compensation in the free energy of polymer solvation, a phenomenon observed for many years without theoretical explanation and with significant relevance to liquid chromatography and other polymer separation methods.

Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li+ Solvation Structure and Li-S Battery Performance.

PubMed

Shin, Minjeong; Wu, Heng-Liang; Narayanan, Badri; See, Kimberly A; Assary, Rajeev S; Zhu, Lingyang; Haasch, Richard T; Zhang, Shuo; Zhang, Zhengcheng; Curtiss, Larry A; Gewirth, Andrew A

2017-11-15

We evaluate hydrofluoroether (HFE) cosolvents with varying degrees of fluorination in the acetonitrile-based solvate electrolyte to determine the effect of the HFE structure on the electrochemical performance of the Li-S battery. Solvates or sparingly solvating electrolytes are an interesting electrolyte choice for the Li-S battery due to their low polysulfide solubility. The solvate electrolyte with a stoichiometric ratio of LiTFSI salt in acetonitrile, (MeCN) 2 -LiTFSI, exhibits limited polysulfide solubility due to the high concentration of LiTFSI. We demonstrate that the addition of highly fluorinated HFEs to the solvate yields better capacity retention compared to that of less fluorinated HFE cosolvents. Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that HFEs exhibiting a higher degree of fluorination coordinate to Li + at the expense of MeCN coordination, resulting in higher free MeCN content in solution. However, the polysulfide solubility remains low, and no crossover of polysulfides from the S cathode to the Li anode is observed.

Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li+ Solvation Structure and Li-S Battery Performance.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shin, Minjeong; Wu, Heng-Liang; Narayanan, Badri

We evaluate hydrofluoroether (HFE) cosolvents with varying degrees of fluorination in the acetonitrile-based solvate electrolyte to determine the effect of the HFE structure on the electrochemical performance of the Li-S battery. Solvates or sparingly solvating electrolytes are an interesting electrolyte choice for the Li-S battery due to their low polysulfide solubility. The solvate electrolyte with a stoichiometric ratio of LiTFSI salt in acetonitrile, (MeCN)(2)-LiTFSI, exhibits limited polysulfide solubility due to the high concentration of LiTFSI. We demonstrate that the addition of highly fluorinated HFEs to the solvate yields better capacity retention compared to that of less fluorinated HFE cosolvents. Ramanmore » and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that HFEs exhibiting a higher degree of fluorination coordinate to Li+ at the expense of MeCN coordination, resulting in higher free MeCN content in solution. However, the polysulfide solubility remains low, and no crossover of polysulfides from the S cathode to the Li anode is observed.« less

Relative complexation energies for Li(+) ion in solution: molecular level solvation versus polarizable continuum model study.

PubMed

Eilmes, Andrzej; Kubisiak, Piotr

2010-01-21

Relative complexation energies for the lithium cation in acetonitrile and diethyl ether have been studied. Quantum-chemical calculations explicitly describing the solvation of Li(+) have been performed based on structures obtained from molecular dynamics simulations. The effect of an increasing number of solvent molecules beyond the first solvation shell has been found to consist in reduction of the differences in complexation energies for different coordination numbers. Explicit-solvation data have served as a benchmark to the results of polarizable continuum model (PCM) calculations. It has been demonstrated that the PCM approach can yield relative complexation energies comparable to the predictions based on molecular-level solvation, but at significantly lower computational cost. The best agreement between the explicit-solvation and the PCM results has been obtained when the van der Waals surface was adopted to build the molecular cavity.

The First Total Synthesis of Sporiolide A

PubMed Central

Chen, Qi; Linhardt, Robert J.

2014-01-01

The first total synthesis of the natural cytotoxic agent sporiolide A has been accomplished from D-glucal in 16 steps with 6.1% overall yield. Carbohydrates were applied as the chiral templates to manipulate the absolute configuration during the synthesis. Pyridinium chlorochromate (PCC)-promoted transformation of the cyclic enol-ether to lactone, followed by Yamaguchi esterification and intramolecular ring closure metathesis, greatly facilitates synthesis of the target compound. PMID:17064018

Enantioselective Decarboxylative Arylation of α-Amino Acids via the Merger of Photoredox and Nickel Catalysis

PubMed Central

Zuo, Zhiwei; Cong, Huan; Li, Wei; Choi, Junwon; Fu, Gregory C.; MacMillan, David W. C.

2016-01-01

An asymmetric decarboxylative Csp3–Csp2 cross-coupling has been achieved via the synergistic merger of photoredox and nickel catalysis. This mild, operationally simple protocol transforms a wide variety of naturally abundant α-amino acids and readily available aryl halides into valuable chiral benzylic amines in high enantiomeric excess, thereby producing motifs found in pharmacologically active agents. PMID:26849354

Comparative assessment of computational methods for the determination of solvation free energies in alcohol-based molecules.

PubMed

Martins, Silvia A; Sousa, Sergio F

2013-06-05

The determination of differences in solvation free energies between related drug molecules remains an important challenge in computational drug optimization, when fast and accurate calculation of differences in binding free energy are required. In this study, we have evaluated the performance of five commonly used polarized continuum model (PCM) methodologies in the determination of solvation free energies for 53 typical alcohol and alkane small molecules. In addition, the performance of these PCM methods, of a thermodynamic integration (TI) protocol and of the Poisson-Boltzmann (PB) and generalized Born (GB) methods, were tested in the determination of solvation free energies changes for 28 common alkane-alcohol transformations, by the substitution of an hydrogen atom for a hydroxyl substituent. The results show that the solvation model D (SMD) performs better among the PCM-based approaches in estimating solvation free energies for alcohol molecules, and solvation free energy changes for alkane-alcohol transformations, with an average error below 1 kcal/mol for both quantities. However, for the determination of solvation free energy changes on alkane-alcohol transformation, PB and TI yielded better results. TI was particularly accurate in the treatment of hydroxyl groups additions to aromatic rings (0.53 kcal/mol), a common transformation when optimizing drug-binding in computer-aided drug design. Copyright © 2013 Wiley Periodicals, Inc.

MTS-MD of Biomolecules Steered with 3D-RISM-KH Mean Solvation Forces Accelerated with Generalized Solvation Force Extrapolation.

PubMed

Omelyan, Igor; Kovalenko, Andriy

2015-04-14

We developed a generalized solvation force extrapolation (GSFE) approach to speed up multiple time step molecular dynamics (MTS-MD) of biomolecules steered with mean solvation forces obtained from the 3D-RISM-KH molecular theory of solvation (three-dimensional reference interaction site model with the Kovalenko-Hirata closure). GSFE is based on a set of techniques including the non-Eckart-like transformation of coordinate space separately for each solute atom, extension of the force-coordinate pair basis set followed by selection of the best subset, balancing the normal equations by modified least-squares minimization of deviations, and incremental increase of outer time step in motion integration. Mean solvation forces acting on the biomolecule atoms in conformations at successive inner time steps are extrapolated using a relatively small number of best (closest) solute atomic coordinates and corresponding mean solvation forces obtained at previous outer time steps by converging the 3D-RISM-KH integral equations. The MTS-MD evolution steered with GSFE of 3D-RISM-KH mean solvation forces is efficiently stabilized with our optimized isokinetic Nosé-Hoover chain (OIN) thermostat. We validated the hybrid MTS-MD/OIN/GSFE/3D-RISM-KH integrator on solvated organic and biomolecules of different stiffness and complexity: asphaltene dimer in toluene solvent, hydrated alanine dipeptide, miniprotein 1L2Y, and protein G. The GSFE accuracy and the OIN efficiency allowed us to enlarge outer time steps up to huge values of 1-4 ps while accurately reproducing conformational properties. Quasidynamics steered with 3D-RISM-KH mean solvation forces achieves time scale compression of conformational changes coupled with solvent exchange, resulting in further significant acceleration of protein conformational sampling with respect to real time dynamics. Overall, this provided a 50- to 1000-fold effective speedup of conformational sampling for these systems, compared to conventional MD with explicit solvent. We have been able to fold the miniprotein from a fully denatured, extended state in about 60 ns of quasidynamics steered with 3D-RISM-KH mean solvation forces, compared to the average physical folding time of 4-9 μs observed in experiment.

Breaking the polar-nonpolar division in solvation free energy prediction.

PubMed

Wang, Bao; Wang, Chengzhang; Wu, Kedi; Wei, Guo-Wei

2018-02-05

Implicit solvent models divide solvation free energies into polar and nonpolar additive contributions, whereas polar and nonpolar interactions are inseparable and nonadditive. We present a feature functional theory (FFT) framework to break this ad hoc division. The essential ideas of FFT are as follows: (i) representability assumption: there exists a microscopic feature vector that can uniquely characterize and distinguish one molecule from another; (ii) feature-function relationship assumption: the macroscopic features, including solvation free energy, of a molecule is a functional of microscopic feature vectors; and (iii) similarity assumption: molecules with similar microscopic features have similar macroscopic properties, such as solvation free energies. Based on these assumptions, solvation free energy prediction is carried out in the following protocol. First, we construct a molecular microscopic feature vector that is efficient in characterizing the solvation process using quantum mechanics and Poisson-Boltzmann theory. Microscopic feature vectors are combined with macroscopic features, that is, physical observable, to form extended feature vectors. Additionally, we partition a solvation dataset into queries according to molecular compositions. Moreover, for each target molecule, we adopt a machine learning algorithm for its nearest neighbor search, based on the selected microscopic feature vectors. Finally, from the extended feature vectors of obtained nearest neighbors, we construct a functional of solvation free energy, which is employed to predict the solvation free energy of the target molecule. The proposed FFT model has been extensively validated via a large dataset of 668 molecules. The leave-one-out test gives an optimal root-mean-square error (RMSE) of 1.05 kcal/mol. FFT predictions of SAMPL0, SAMPL1, SAMPL2, SAMPL3, and SAMPL4 challenge sets deliver the RMSEs of 0.61, 1.86, 1.64, 0.86, and 1.14 kcal/mol, respectively. Using a test set of 94 molecules and its associated training set, the present approach was carefully compared with a classic solvation model based on weighted solvent accessible surface area. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Effect of chirality on cellular uptake, imaging and photodynamic therapy of photosensitizers derived from chlorophyll-a.

PubMed

Srivatsan, Avinash; Pera, Paula; Joshi, Penny; Wang, Yanfang; Missert, Joseph R; Tracy, Erin C; Tabaczynski, Walter A; Yao, Rutao; Sajjad, Munawwar; Baumann, Heinz; Pandey, Ravindra K

2015-07-01

We have previously shown that the (124)I-analog of methyl 3-(1'-m-iodobenzyloxy) ethyl-3-devinyl-pyropheophorbide-a derived as racemic mixture from chlorophyll-a can be used for PET (positron emission tomography)-imaging in animal tumor models. On the other hand, as a non-radioactive analog, it showed excellent fluorescence and photodynamic therapy (PDT) efficacy. Thus, a single agent in a mixture of radioactive ((124)I-) and non-radioactive ((127)I) material can be used for both dual-imaging and PDT of cancer. Before advancing to Phase I human clinical trials, we evaluated the activity of the individual isomers as well as the impact of a chiral center at position-3(1) in directing in vitro/in vivo cellular uptake, intracellular localization, epithelial tumor cell-specific retention, fluorescence/PET imaging, and photosensitizing ability. The results indicate that both isomers (racemates), either as methyl ester or carboxylic acid, were equally effective. However, the methyl ester analogs, due to subcellular deposition into vesicular structures, were preferentially retained. All derivatives containing carboxylic acid at the position-17(2) were noted to be substrate for the ABCG2 (a member of the ATP binding cassette transporters) protein explaining their low retention in lung tumor cells expressing this transporter. The compounds in which the chirality at position-3 has been substituted by a non-chiral functionality showed reduced cellular uptake, retention and lower PDT efficacy in mice bearing murine Colon26 tumors. Copyright © 2015 Elsevier Ltd. All rights reserved.

Studies of the structural and magnetic properties of an unsymmetrical ligand 1,2,4-benzenetricarboxylic acid based chiral 3-D trinickel coordination polymer as an alkali base-influenced hydrothermal reaction product

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Yi-Ru; Chien, Po-Hsiu; Chung, Huey-Ting

2014-04-01

The reaction of 1,2,4-benzenetricarboxylic acid (H{sub 3}btc), as a ligand, under pH-controlled hydrothermal conditions with nickel salts leads to the formation of a coordination polymer of (CsNi{sub 3}(OH)(H{sub 2}O){sub 3}[C{sub 6}H{sub 3}(CO{sub 2}){sub 3}]{sub 2}·3H{sub 2}O){sub n} (1). The subunit of compound 1 contains a hydroxide- and carboxylate-bridged trinickel clusters that are linked by an unsymmetrical organic carboxylate spacer to form a chiral three-dimensional anionic framework, in which cesium cations and guest water molecules are located in one-dimensional channels. The presence of a hydroxide ion serves both as a deprotonation agent and a cation source during the hydrothermal reaction, thusmore » permitting the extent of deprotonation of the unsymmetrical ligand H{sub 3}btc to be controlled, which is essential for the successful formation of compound 1. The magnetic properties of compound 1 were analyzed. Both dc and ac magnetic susceptibility as well as reduced magnetization measurements confirmed the spin-frustration nature of 1. - Graphical abstract: A chiral three-dimension MOF compound and its magnetic properties are described. - Highlights: • A new chiral three-dimension coordination polymer were made. • An un-symmetric bridging ligand was used. • Alkali metal ion Cs{sup +} was incorporated in the structure. • Magnetic properties were studied.« less

On the solvation of hydronium by carbon dioxide: Structural and infrared spectroscopic study of (H3O+)(CO2)n

NASA Astrophysics Data System (ADS)

Yang, Jianpeng; Kong, Xiangtao; Jiang, Ling

2018-02-01

Hydronium (H3O+) is the smallest member of protonated water. In this work, we use quantum chemical calculations to explore the solvation of H3O+ by adding one CO2 molecule at a time. The effect of stepwise solvation on infrared spectroscopy, structure, and energetics has been systematically studied. It has been found that the first solvation shell of H3O+ is completed at n = 6. Besides the hydrogen-bond interaction, the CCO2-OCO2 intermolecular interaction is also responsible for the stabilization of the larger clusters. The transfer of the proton from H3O+ onto CO2 with the formation of the OCOH+ moiety is not observed in the early stage of solvation process. Calculated IR spectra suggest that vibrational frequencies of H-bonded Osbnd H stretching would afford a sensitive probe for exploring the early stage solvation of hydronium by carbon dioxide. IR spectra for the (H3O+)(CO2)n (n = 1-7) clusters could be measured by the infrared photodissociation spectroscopic technique and thus provide a vivid physical picture about how carbon dioxide solvates the hydronium.

Crystallization of toxic glycol solvates of rifampin from glycerin and propylene glycol contaminated with ethylene glycol or diethylene glycol.

PubMed

de Villiers, Melgardt M; Caira, Mino R; Li, Jinjing; Strydom, Schalk J; Bourne, Susan A; Liebenberg, Wilna

2011-06-06

This study was initiated when it was suspected that syringe blockage experienced upon administration of a compounded rifampin suspension was caused by the recrystallization of toxic glycol solvates of the drug. Single crystal X-ray structure analysis, powder X-ray diffraction, thermal analysis and gas chromatography were used to identify the ethylene glycol in the solvate crystals recovered from the suspension. Controlled crystallization and solubility studies were used to determine the ease with which toxic glycol solvates crystallized from glycerin and propylene glycol contaminated with either ethylene or diethylene glycol. The single crystal structures of two distinct ethylene glycol solvates of rifampin were solved while thermal analysis, GC analysis and solubility studies confirmed that diethylene glycol solvates of the drug also crystallized. Controlled crystallization studies showed that crystallization of the rifampin solvates from glycerin and propylene glycol depended on the level of contamination and changes in the solubility of the drug in the contaminated solvents. Although the exact source of the ethylene glycol found in the compounded rifampin suspension is not known, the results of this study show how important it is to ensure that the drug and excipients comply with pharmacopeial or FDA standards.

Synergistic behavior of glycine betaine-urea mixture: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Kumar, Narendra; Kishore, Nand

2013-09-01

Glycine betaine (GB) is one of the most important osmolyte which is known to stabilize proteins as well as counteract the denaturing effect of urea. There have been many studies indicating protein stabilization and counteraction of the effect of urea by GB. However, the exact mechanism of counteraction is still debated and is of important research interest. In this study, distribution functions, hydrogen bonds, and energetics were analysed to understand different interactions between GB and urea, and their solvation properties in presence of each other. The results show that in the GB-urea mixture, GB acted as a stronger osmolyte and urea became a weaker denaturing agent than its individual counterparts. The increase in the solvation of urea and GB in GB-urea mixture and their mutual interactions through hydrogen bonding and coulombic energy resulted in more involvement of GB and urea with solvent as well as with themselves. This might result in the increase of the exclusion of GB from protein surface and decrease in the protein-urea interactions in the mixture. This synergistic behavior might be the prime reason for the counteraction of denaturing effect of urea by GB.

Rationalization of the solvation effects on the AtO+ ground-state change.

PubMed

Ayed, Tahra; Réal, Florent; Montavon, Gilles; Galland, Nicolas

2013-09-12

(211)At radionuclide is of considerable interest as a radiotherapeutic agent for targeted alpha therapy in nuclear medicine, but major obstacles remain because the basic chemistry of astatine (At) is not well understood. The AtO(+) cationic form might be currently used for (211)At-labeling protocols in aqueous solution and has proved to readily react with inorganic/organic ligands. But AtO(+) reactivity must be hindered at first glance by spin restriction quantum rules: the ground state of the free cation has a dominant triplet character. Investigating AtO(+) clustered with an increasing number of water molecules and using various flavors of relativistic quantum methods, we found that AtO(+) adopts in solution a Kramers restricted closed-shell configuration resembling a scalar-relativistic singlet. The ground-state change was traced back to strong interactions, namely, attractive electrostatic interactions and charge transfer, with water molecules of the first solvation shell that lift up the degeneracy of the frontier π* molecular orbitals (MOs). This peculiarity brings an alternative explanation to the highly variable reproducibility reported for some astatine reactions: depending on the production protocols (with distillation in gas-phase or "wet chemistry" extraction), (211)At may or may not readily react.

Hydrophobic Solvation: Aqueous Methane Solutions

ERIC Educational Resources Information Center

Konrod, Oliver; Lankau, Timm

2007-01-01

A basic introduction to concept of a solvation shell around an apolar solute as well as its detection is presented. The hydrophobic solvation of toluene is found to be a good teaching example which connects macroscopic, phenomenological thermodynamic results with an atomistic point of view.

Role of Dispersive Fluorous Interaction in the Solvation Dynamics of the Perfluoro Group Containing Molecules.

PubMed

Mondal, Saptarsi; Chaterjee, Soumit; Halder, Ritaban; Jana, Biman; Singh, Prashant Chandra

2017-08-17

Perfluoro group containing molecules possess an important self-aggregation property through the fluorous (F···F) interaction which makes them useful for diverse applications such as medicinal chemistry, separation techniques, polymer technology, and biology. In this article, we have investigated the solvation dynamics of coumarin-153 (C153) and coumarin-6H (C6H) in ethanol (ETH), 2-fluoroethanol (MFE), and 2,2,2-trifluoroethanol (TFE) using the femtosecond upconversion technique and molecular dynamics (MD) simulation to understand the role of fluorous interaction between the solute and solvent molecules in the solvation dynamics of perfluoro group containing molecules. The femtosecond upconversion data show that the time scales of solvation dynamics of C6H in ETH, MFE, and TFE are approximately the same whereas the solvation dynamics of C153 in TFE is slow as compared to that of ETH and MFE. It has also been observed that the time scale of solvation dynamics of C6H in ETH and MFE is higher than that of C153 in the same solvents. MD simulation results show a qualitative agreement with the experimental data in terms of the time scale of the slow components of the solvation for all the systems. The experimental and simulation studies combined lead to the conclusion that the solvation dynamics of C6H in all solvents as well as C153 in ETH and MFE is mostly governed by the charge distribution of ester moieties (C═O and O) of dye molecules whereas the solvation of C153 in TFE is predominantly due to the dispersive fluorous interaction (F···F) between the perfluoro groups of the C153 and solvent molecules.

Biomolecular electrostatics and solvation: a computational perspective

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ren, Pengyu; Chun, Jaehun; Thomas, Dennis G.

2012-11-01

An understanding of molecular interactions is essential for insight into biological systems at the molecular scale. Among the various components of molecular interactions, electrostatics are of special importance because of their long-range nature and their influence on polar or charged molecules, including water, aqueous ions, proteins, nucleic acids, carbohydrates, and membrane lipids. In particular, robust models of electrostatic interactions are essential for understanding the solvation properties of biomolecules and the effects of solvation upon biomolecular folding, binding, enzyme catalysis and dynamics. Electrostatics, therefore, are of central importance to understanding biomolecular structure and modeling interactions within and among biological molecules. Thismore » review discusses the solvation of biomolecules with a computational biophysics view towards describing the phenomenon. While our main focus lies on the computational aspect of the models, we summarize the common characteristics of biomolecular solvation (e.g., solvent structure, polarization, ion binding, and nonpolar behavior) in order to provide reasonable backgrounds to understand the solvation models.« less

Biomolecular electrostatics and solvation: a computational perspective

PubMed Central

Ren, Pengyu; Chun, Jaehun; Thomas, Dennis G.; Schnieders, Michael J.; Marucho, Marcelo; Zhang, Jiajing; Baker, Nathan A.

2012-01-01

An understanding of molecular interactions is essential for insight into biological systems at the molecular scale. Among the various components of molecular interactions, electrostatics are of special importance because of their long-range nature and their influence on polar or charged molecules, including water, aqueous ions, proteins, nucleic acids, carbohydrates, and membrane lipids. In particular, robust models of electrostatic interactions are essential for understanding the solvation properties of biomolecules and the effects of solvation upon biomolecular folding, binding, enzyme catalysis, and dynamics. Electrostatics, therefore, are of central importance to understanding biomolecular structure and modeling interactions within and among biological molecules. This review discusses the solvation of biomolecules with a computational biophysics view towards describing the phenomenon. While our main focus lies on the computational aspect of the models, we provide an overview of the basic elements of biomolecular solvation (e.g., solvent structure, polarization, ion binding, and nonpolar behavior) in order to provide a background to understand the different types of solvation models. PMID:23217364

Biomolecular electrostatics and solvation: a computational perspective.

PubMed

Ren, Pengyu; Chun, Jaehun; Thomas, Dennis G; Schnieders, Michael J; Marucho, Marcelo; Zhang, Jiajing; Baker, Nathan A

2012-11-01

An understanding of molecular interactions is essential for insight into biological systems at the molecular scale. Among the various components of molecular interactions, electrostatics are of special importance because of their long-range nature and their influence on polar or charged molecules, including water, aqueous ions, proteins, nucleic acids, carbohydrates, and membrane lipids. In particular, robust models of electrostatic interactions are essential for understanding the solvation properties of biomolecules and the effects of solvation upon biomolecular folding, binding, enzyme catalysis, and dynamics. Electrostatics, therefore, are of central importance to understanding biomolecular structure and modeling interactions within and among biological molecules. This review discusses the solvation of biomolecules with a computational biophysics view toward describing the phenomenon. While our main focus lies on the computational aspect of the models, we provide an overview of the basic elements of biomolecular solvation (e.g. solvent structure, polarization, ion binding, and non-polar behavior) in order to provide a background to understand the different types of solvation models.

Readily Made Solvated Electrons

ERIC Educational Resources Information Center

Ibanez, Jorge G.; Guerra-Millan, Francisco J.; Hugerat, Muhamad; Vazquez-Olavarrieta, Jorge L.; Basheer, Ahmad; Abu-Much, Riam

2011-01-01

The existence of solvated electrons has been known for a long time. Key methods for their production (i.e., photoionization of reducing ions, water radiolysis, and the reaction between H[middle dot] and OH[superscript -]) are unsuitable for most school laboratories. We describe a simple experiment to produce liquid ammonia and solvated electrons…

Solvated Electrons in Organic Chemistry Laboratory

ERIC Educational Resources Information Center

Ilich, Predrag-Peter; McCormick, Kathleen R.; Atkins, Adam D.; Mell, Geoffrey J.; Flaherty, Timothy J.; Bruck, Martin J.; Goodrich, Heather A.; Hefel, Aaron L.; Juranic, Nenad; Seleem, Suzanne

2010-01-01

A novel experiment is described in which solvated electrons in liquid ammonia reduce a benzyl alcohol carbon without affecting the aromatic ring. The reductive activity of solvated electrons can be partially or completely quenched through the addition of electron scavengers to the reaction mixture. The effectiveness of these scavengers was found…

How High Pressure Unifies Solvation Processes in Liquid Chromatography.

PubMed

Bocian, Szymon; Škrinjar, Tea; Bolanca, Tomislav; Buszewski, Bogusław

2017-11-01

A series of core-shell-based stationary phases of varying surface chemistry were subjected to solvent adsorption investigation under ultra-HPLC conditions. Acetonitrile and water excess isotherms were measured using a minor disturbance method. It was observed that adsorption of organic solvent is unified under high pressure. Preferential solvation due to specific interactions between the stationary phases and solvent molecules was limited. The obtained results showed that the solvation process is almost independent of surface chemistry, in contrast to HPLC conditions in which specific interactions differentiate solvation processes.

Atomic decomposition of the protein solvation free energy and its application to amyloid-beta protein in water

NASA Astrophysics Data System (ADS)

Chong, Song-Ho; Ham, Sihyun

2011-07-01

We report the development of an atomic decomposition method of the protein solvation free energy in water, which ascribes global change in the solvation free energy to local changes in protein conformation as well as in hydration structure. So far, empirical decomposition analyses based on simple continuum solvation models have prevailed in the study of protein-protein interactions, protein-ligand interactions, as well as in developing scoring functions for computer-aided drug design. However, the use of continuum solvation model suffers serious drawbacks since it yields the protein free energy landscape which is quite different from that of the explicit solvent model and since it does not properly account for the non-polar hydrophobic effects which play a crucial role in biological processes in water. Herein, we develop an exact and general decomposition method of the solvation free energy that overcomes these hindrances. We then apply this method to elucidate the molecular origin for the solvation free energy change upon the conformational transitions of 42-residue amyloid-beta protein (Aβ42) in water, whose aggregation has been implicated as a primary cause of Alzheimer's disease. We address why Aβ42 protein exhibits a great propensity to aggregate when transferred from organic phase to aqueous phase.

Anisotropic solvent model of the lipid bilayer. 1. Parameterization of long-range electrostatics and first solvation shell effects.

PubMed

Lomize, Andrei L; Pogozheva, Irina D; Mosberg, Henry I

2011-04-25

A new implicit solvation model was developed for calculating free energies of transfer of molecules from water to any solvent with defined bulk properties. The transfer energy was calculated as a sum of the first solvation shell energy and the long-range electrostatic contribution. The first term was proportional to solvent accessible surface area and solvation parameters (σ(i)) for different atom types. The electrostatic term was computed as a product of group dipole moments and dipolar solvation parameter (η) for neutral molecules or using a modified Born equation for ions. The regression coefficients in linear dependencies of solvation parameters σ(i) and η on dielectric constant, solvatochromic polarizability parameter π*, and hydrogen-bonding donor and acceptor capacities of solvents were optimized using 1269 experimental transfer energies from 19 organic solvents to water. The root-mean-square errors for neutral compounds and ions were 0.82 and 1.61 kcal/mol, respectively. Quantification of energy components demonstrates the dominant roles of hydrophobic effect for nonpolar atoms and of hydrogen-bonding for polar atoms. The estimated first solvation shell energy outweighs the long-range electrostatics for most compounds including ions. The simplicity and computational efficiency of the model allows its application for modeling of macromolecules in anisotropic environments, such as biological membranes.

Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sundararaman, Ravishankar; Gunceler, Deniz; Arias, T. A.

2014-10-07

Continuum solvation models enable efficient first principles calculations of chemical reactions in solution, but require extensive parametrization and fitting for each solvent and class of solute systems. Here, we examine the assumptions of continuum solvation models in detail and replace empirical terms with physical models in order to construct a minimally-empirical solvation model. Specifically, we derive solvent radii from the nonlocal dielectric response of the solvent from ab initio calculations, construct a closed-form and parameter-free weighted-density approximation for the free energy of the cavity formation, and employ a pair-potential approximation for the dispersion energy. We show that the resulting modelmore » with a single solvent-independent parameter: the electron density threshold (n c), and a single solvent-dependent parameter: the dispersion scale factor (s 6), reproduces solvation energies of organic molecules in water, chloroform, and carbon tetrachloride with RMS errors of 1.1, 0.6 and 0.5 kcal/mol, respectively. We additionally show that fitting the solvent-dependent s 6 parameter to the solvation energy of a single non-polar molecule does not substantially increase these errors. Parametrization of this model for other solvents, therefore, requires minimal effort and is possible without extensive databases of experimental solvation free energies.« less

Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sundararaman, Ravishankar; Gunceler, Deniz; Arias, T. A.

2014-10-07

Continuum solvation models enable efficient first principles calculations of chemical reactions in solution, but require extensive parametrization and fitting for each solvent and class of solute systems. Here, we examine the assumptions of continuum solvation models in detail and replace empirical terms with physical models in order to construct a minimally-empirical solvation model. Specifically, we derive solvent radii from the nonlocal dielectric response of the solvent from ab initio calculations, construct a closed-form and parameter-free weighted-density approximation for the free energy of the cavity formation, and employ a pair-potential approximation for the dispersion energy. We show that the resulting modelmore » with a single solvent-independent parameter: the electron density threshold (n{sub c}), and a single solvent-dependent parameter: the dispersion scale factor (s{sub 6}), reproduces solvation energies of organic molecules in water, chloroform, and carbon tetrachloride with RMS errors of 1.1, 0.6 and 0.5 kcal/mol, respectively. We additionally show that fitting the solvent-dependent s{sub 6} parameter to the solvation energy of a single non-polar molecule does not substantially increase these errors. Parametrization of this model for other solvents, therefore, requires minimal effort and is possible without extensive databases of experimental solvation free energies.« less

Solvation thermodynamics of amino acid side chains on a short peptide backbone

NASA Astrophysics Data System (ADS)

Hajari, Timir; van der Vegt, Nico F. A.

2015-04-01

The hydration process of side chain analogue molecules differs from that of the actual amino acid side chains in peptides and proteins owing to the effects of the peptide backbone on the aqueous solvent environment. A recent molecular simulation study has provided evidence that all nonpolar side chains, attached to a short peptide backbone, are considerably less hydrophobic than the free side chain analogue molecules. In contrast to this, the hydrophilicity of the polar side chains is hardly affected by the backbone. To analyze the origin of these observations, we here present a molecular simulation study on temperature dependent solvation free energies of nonpolar and polar side chains attached to a short peptide backbone. The estimated solvation entropies and enthalpies of the various amino acid side chains are compared with existing side chain analogue data. The solvation entropies and enthalpies of the polar side chains are negative, but in absolute magnitude smaller compared with the corresponding analogue data. The observed differences are large; however, owing to a nearly perfect enthalpy-entropy compensation, the solvation free energies of polar side chains remain largely unaffected by the peptide backbone. We find that a similar compensation does not apply to the nonpolar side chains; while the backbone greatly reduces the unfavorable solvation entropies, the solvation enthalpies are either more favorable or only marginally affected. This results in a very small unfavorable free energy cost, or even free energy gain, of solvating the nonpolar side chains in strong contrast to solvation of small hydrophobic or nonpolar molecules in bulk water. The solvation free energies of nonpolar side chains have been furthermore decomposed into a repulsive cavity formation contribution and an attractive dispersion free energy contribution. We find that cavity formation next to the peptide backbone is entropically favored over formation of similar sized nonpolar side chain cavities in bulk water, in agreement with earlier work in the literature on analysis of cavity fluctuations at nonpolar molecular surfaces. The cavity and dispersion interaction contributions correlate quite well with the solvent accessible surface area of the nonpolar side chains attached to the backbone. This correlation however is weak for the overall solvation free energies owing to the fact that the cavity and dispersion free energy contributions are almost exactly cancelling each other.

Anti-cancer agents based on N-acyl-2, 3-dihydro-1H-pyrrolo[2,3-b] quinoline derivatives and a method of making

DOEpatents

Gakh, Andrei; Krasavin, Mikhail; Karapetian, Ruben; Rufanov, Konstantin A; Konstantinov, Igor; Godovykh, Elena; Soldatkina, Olga; Sosnov, Andrey V

2013-04-16

The present disclosure relates to novel compounds that can be used as anti-cancer agents in the prostate cancer therapy. In particular, the invention relates to N-acyl derivatives of 2,3-dihydro-1H-pyrrolo[2,3-b]quinolines having the structural Formula (I), ##STR00001## stereoisomers, tautomers, racemics, prodrugs, metabolites thereof, or pharmaceutically acceptable salt and/or solvate thereof. The meaning of R1 is independently selected from H; C1-C6 Alkyl, cyclo-Alkyl or iso-Alkyl substituents; R2 is selected from C1-C6 Alkyl, cyclo-Alkyl or iso-Alkyl; substituted or non-substituted, fused or non-fused to substituted or non-substituted aromatic ring, aryl or heteroaryl groups. The invention also relates to methods for preparing said compounds, and to pharmaceutical compositions comprising said compounds.

The impact of surface area, volume, curvature, and Lennard-Jones potential to solvation modeling.

PubMed

Nguyen, Duc D; Wei, Guo-Wei

2017-01-05

This article explores the impact of surface area, volume, curvature, and Lennard-Jones (LJ) potential on solvation free energy predictions. Rigidity surfaces are utilized to generate robust analytical expressions for maximum, minimum, mean, and Gaussian curvatures of solvent-solute interfaces, and define a generalized Poisson-Boltzmann (GPB) equation with a smooth dielectric profile. Extensive correlation analysis is performed to examine the linear dependence of surface area, surface enclosed volume, maximum curvature, minimum curvature, mean curvature, and Gaussian curvature for solvation modeling. It is found that surface area and surfaces enclosed volumes are highly correlated to each other's, and poorly correlated to various curvatures for six test sets of molecules. Different curvatures are weakly correlated to each other for six test sets of molecules, but are strongly correlated to each other within each test set of molecules. Based on correlation analysis, we construct twenty six nontrivial nonpolar solvation models. Our numerical results reveal that the LJ potential plays a vital role in nonpolar solvation modeling, especially for molecules involving strong van der Waals interactions. It is found that curvatures are at least as important as surface area or surface enclosed volume in nonpolar solvation modeling. In conjugation with the GPB model, various curvature-based nonpolar solvation models are shown to offer some of the best solvation free energy predictions for a wide range of test sets. For example, root mean square errors from a model constituting surface area, volume, mean curvature, and LJ potential are less than 0.42 kcal/mol for all test sets. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Structure of solvates of o-hydroxybenzoic acid in supercritical CO2-cosolvent media, according to molecular dynamics data

NASA Astrophysics Data System (ADS)

Petrenko, V. E.; Antipova, M. L.; Gurina, D. L.

2015-03-01

Three-component supercritical carbon dioxide-cosolvent (methanol, ethanol, water)- o-hydroxybenzoic acid ( o-HBA) mixtures at a density of 0.7 g/cm3 and temperatures of 318 and 348 K are simulated by means of molecular dynamics. The solvate structures are investigated. It is shown that the solvation mechanism of o-HBA (particularly the o-HBA molecule forming a stable solvate complex with one molecule of a cosolvent via a hydrogen bond through the carboxyl group) does not depend on the temperature or the cosolvent. It is noted that the form of the cosolvent in a supercritical fluid varies: alcohols are distributed in the bulk in the form of monomers and hydrogen-bonded dimers, and water molecules tend to form microclusters along with chained and spatially branched structures by means of hydrogen bonds. It is established that the local molar fraction of cosolvent around the solvate complexes grows. It is concluded that the solvation of o-HBA is determined by the behavior of cosolvent in media of supercritical CO2.

Long-ranged contributions to solvation free energies from theory and short-ranged models

PubMed Central

Remsing, Richard C.; Liu, Shule; Weeks, John D.

2016-01-01

Long-standing problems associated with long-ranged electrostatic interactions have plagued theory and simulation alike. Traditional lattice sum (Ewald-like) treatments of Coulomb interactions add significant overhead to computer simulations and can produce artifacts from spurious interactions between simulation cell images. These subtle issues become particularly apparent when estimating thermodynamic quantities, such as free energies of solvation in charged and polar systems, to which long-ranged Coulomb interactions typically make a large contribution. In this paper, we develop a framework for determining very accurate solvation free energies of systems with long-ranged interactions from models that interact with purely short-ranged potentials. Our approach is generally applicable and can be combined with existing computational and theoretical techniques for estimating solvation thermodynamics. We demonstrate the utility of our approach by examining the hydration thermodynamics of hydrophobic and ionic solutes and the solvation of a large, highly charged colloid that exhibits overcharging, a complex nonlinear electrostatic phenomenon whereby counterions from the solvent effectively overscreen and locally invert the integrated charge of the solvated object. PMID:26929375

Anion Solvation in Carbonate-Based Electrolytes

DOE PAGES

von Wald Cresce, Arthur; Gobet, Mallory; Borodin, Oleg; ...

2015-11-16

The correlation between Li + solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation–solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. Now, most studies are dedicated to the solvation of Li +, and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. Moreover, as a mirror effort to prior Li + solvation studies, this work focuses on the interactions between carbonate-based solvents andmore » two anions (hexafluorophosphate, PF 6–, and tetrafluoroborate, BF 4–) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.« less

A comparison of the solvation structure and dynamics of the lithium ion in linear organic carbonates with different alkyl chain lengths.

PubMed

Fulfer, K D; Kuroda, D G

2017-09-20

The structure and dynamics of electrolytes composed of lithium hexafluorophosphate (LiPF 6 ) in dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate were investigated using a combination of linear and two-dimensional infrared spectroscopies. The solutions studied here have a LiPF 6 concentration of X(LiPF 6 ) = 0.09, which is typically found in commercial lithium ion batteries. This study focuses on comparing the differences in the solvation shell structure and dynamics produced by linear organic carbonates of different alkyl chain lengths. The IR experiments show that either linear carbonate forms a tetrahedral solvation shell (coordination number of 4) around the lithium ion irrespective of whether the solvation shell has anions in close proximity to the carbonates. Moreover, analysis of the absorption cross sections via FTIR and DFT computations reveals a distortion in the angle formed by Li + -O[double bond, length as m-dash]C which decreases from the expected 180° when the alkyl chains of the carbonate are lengthened. In addition, our findings also reveal that, likely due to its asymmetric structure, ethyl methyl carbonate has a significantly more distorted tetrahedral lithium ion solvation shell than either of the other two investigated carbonates. IR photon echo studies further demonstrate that the motions of the solvation shell have a time scale of a few picoseconds for all three linear carbonates. Interestingly, a slowdown of the in place-motions of the first solvation shell is observed when the carbonate has a longer alkyl chain length irrespective of the symmetry. In addition, vibrational energy transfer with a time scale of tens of picoseconds is observed between strongly coupled modes arising from the solvation shell structure of the Li + which corroborates the modeling of these solvation shells in terms of highly coupled vibrational states. Results of this study provide new insights into the molecular structure and dynamics of the lithium ion electrolyte components as a function of solvent structure.

Competitive chiral induction in a 2D molecular assembly: Intrinsic chirality versus coadsorber-induced chirality.

PubMed

Chen, Ting; Li, Shu-Ying; Wang, Dong; Wan, Li-Jun

2017-11-01

Noncovalently introducing stereogenic information is a promising approach to embed chirality in achiral molecular systems. However, the interplay of the noncovalently introduced chirality with the intrinsic chirality of molecules or molecular aggregations has rarely been addressed. We report a competitive chiral expression of the noncovalent interaction-mediated chirality induction and the intrinsic stereogenic center-controlled chirality induction in a two-dimensional (2D) molecular assembly at the liquid/solid interface. Two enantiomorphous honeycomb networks are formed by the coassembly of an achiral 5-(benzyloxy)isophthalic acid (BIC) derivative and 1-octanol at the liquid/solid interface. The preferential formation of the globally homochiral assembly can be achieved either by using the chiral analog of 1-octanol, ( S )-6-methyl-1-octanol, as a chiral coadsorber to induce chirality to the BIC assembly via noncovalent hydrogen bonding or by covalently linking a chiral center in the side chain of BIC. Both the chiral coadsorber and the intrinsically chiral BIC derivative can act as a chiral seeds to induce a preferred handedness in the assembly of the achiral BIC derivatives. Furthermore, the noncovalent interaction-mediated chirality induction can restrain or even overrule the manifestation of the intrinsic chirality of the BIC molecule and dominate the handedness of the 2D molecular coassembly. This study provides insight into the interplay of intrinsically chiral centers and external chiral coadsorbers in the chiral induction, transfer, and amplification processes of 2D molecular assembly.

Competitive chiral induction in a 2D molecular assembly: Intrinsic chirality versus coadsorber-induced chirality

PubMed Central

Chen, Ting; Li, Shu-Ying; Wang, Dong; Wan, Li-Jun

2017-01-01

Noncovalently introducing stereogenic information is a promising approach to embed chirality in achiral molecular systems. However, the interplay of the noncovalently introduced chirality with the intrinsic chirality of molecules or molecular aggregations has rarely been addressed. We report a competitive chiral expression of the noncovalent interaction–mediated chirality induction and the intrinsic stereogenic center–controlled chirality induction in a two-dimensional (2D) molecular assembly at the liquid/solid interface. Two enantiomorphous honeycomb networks are formed by the coassembly of an achiral 5-(benzyloxy)isophthalic acid (BIC) derivative and 1-octanol at the liquid/solid interface. The preferential formation of the globally homochiral assembly can be achieved either by using the chiral analog of 1-octanol, (S)-6-methyl-1-octanol, as a chiral coadsorber to induce chirality to the BIC assembly via noncovalent hydrogen bonding or by covalently linking a chiral center in the side chain of BIC. Both the chiral coadsorber and the intrinsically chiral BIC derivative can act as a chiral seeds to induce a preferred handedness in the assembly of the achiral BIC derivatives. Furthermore, the noncovalent interaction–mediated chirality induction can restrain or even overrule the manifestation of the intrinsic chirality of the BIC molecule and dominate the handedness of the 2D molecular coassembly. This study provides insight into the interplay of intrinsically chiral centers and external chiral coadsorbers in the chiral induction, transfer, and amplification processes of 2D molecular assembly. PMID:29119137

Application of antibody-mediated extraction for the stereoselective determination of the active metabolite of loxoprofen in human and rat plasma.

PubMed

Takasaki, W; Tanaka, Y

1992-01-01

Antibody-mediated extraction followed by chiral high-performance liquid chromatography (HPLC) was applied to stereoselective determination in human and rat plasma of the active metabolite [(2S,1'R,2'S)-trans-alcohol] with three chiral centers of Loxoprofen, a 2-arylpropionic acid antiinflammatory agent after oral administration. Antiserum against the (1'R,2'S)-cyclopentanol moiety was obtained from a rabbit immunized with bovine serum albumin conjugate linked to the propionic acid moiety, in which another chiral center is located. Then, the immunoglobulin G purified by a protein A column was coupled to BrCN-activated Sepharose 4B. Plasma samples were applied to the immobilized antibody column. After washing the column to remove unrequired stereoisomers, a mixture of two diastereomers whose configurations were 1'R,2'S in the cyclopentanol moiety was extracted with 95% methanol. The solvent was evaporated and the residue was derivatized with (+)-(R)-1-(1-naphthyl)ethylamine as a chiral reagent to separate the diastereomers by HPLC. This combined analytical method showed the stereoselective metabolism of Loxoprofen in human, that is, 64% of the total amount of four trans-alcohol stereoisomers was in the 2S,1'R,2'S form, which is the active metabolite. This phenomenon was also observed in rats given Loxoprofen and its (2S)- and (2R)-isomers, and is explained by stereoselective ketone reduction of Loxoprofen to the (1'R,2'S)-trans-alcohol and inversion from 2R to 2S in the propionic acid moiety. Antibody-mediated extraction should be a selective and simple clean-up method for determining haptens with complicated structures, combined with an appropriate analytical method.

Chiral Platinum(II) Complexes Featuring Phosphine and Chloroquine Ligands as Cytotoxic and Monofunctional DNA-Binding Agents.

PubMed

Villarreal, Wilmer; Colina-Vegas, Legna; Rodrigues de Oliveira, Clayton; Tenorio, Juan C; Ellena, Javier; Gozzo, Fábio C; Cominetti, Marcia Regina; Ferreira, Antonio G; Ferreira, Marco Antonio Barbosa; Navarro, Maribel; Batista, Alzir A

2015-12-21

Chiral molecules in nature are involved in many biological events; their selectivity and specificity make them of great interest for understanding the behavior of bioactive molecules, by providing information about the chiral discrimination. Inspired by these conformational properties, we present the design and synthesis of novel chiral platinum(II) complexes featuring phosphine and chloroquine ligands with the general formula [PtCl(P)2(CQ)]PF6 (where (P)2 = triphenylphosphine (PPh3) (5), 1,3-bis(diphenylphosphine)propane (dppp) (6), 1,4-bis(diphenylphosphine)butane (dppb) (7), 1,1'-bis(diphenylphosphine)ferrocene (dppf) (8), and CQ = chloroquine] and their precursors of the type [PtCl2(P)2] are described. The complexes were characterized by elemental analysis, absorption spectroscopy in the infrared and ultraviolet-visible (UV-vis) regions, multinuclear ((1)H, (13)C, (31)P, (15)N, and (195)Pt) NMR spectroscopy, cyclic voltammetry, and mass spectrometry (in the case of chloroquine complexes). The interactions of the new platinum-chloroquine complexes with both albumin (BSA), using fluorescence spectroscopy, and DNA, by four widely reported methods were also evaluated. These experiments showed that these Pt-CQ complexes interact strongly with DNA and have high affinities for BSA, in contrast to CQ and CQDP (chloroquine diphosphate), which interact weakly with these biomolecules. Additional assays were performed in order to investigate the cytotoxicity of the platinum complexes against two healthy cell lines (mouse fibroblasts (L929) and the Chinese hamster lung (V79-4)) and four tumor cell lines (human breast (MDA-MB-231 and MCF-7), human lung (A549), and human prostate (DU-145)). The results suggest that the Pt-CQ complexes are generally more cytotoxic than the free CQ, showing that they are promising as anticancer drugs.

Modeling ultrafast solvated electronic dynamics using time-dependent density functional theory and polarizable continuum model.

PubMed

Liang, Wenkel; Chapman, Craig T; Ding, Feizhi; Li, Xiaosong

2012-03-01

A first-principles solvated electronic dynamics method is introduced. Solvent electronic degrees of freedom are coupled to the time-dependent electronic density of a solute molecule by means of the implicit reaction field method, and the entire electronic system is propagated in time. This real-time time-dependent approach, incorporating the polarizable continuum solvation model, is shown to be very effective in describing the dynamical solvation effect in the charge transfer process and yields a consistent absorption spectrum in comparison to the conventional linear response results in solution. © 2012 American Chemical Society

Differential geometry based solvation model II: Lagrangian formulation.

PubMed

Chen, Zhan; Baker, Nathan A; Wei, G W

2011-12-01

Solvation is an elementary process in nature and is of paramount importance to more sophisticated chemical, biological and biomolecular processes. The understanding of solvation is an essential prerequisite for the quantitative description and analysis of biomolecular systems. This work presents a Lagrangian formulation of our differential geometry based solvation models. The Lagrangian representation of biomolecular surfaces has a few utilities/advantages. First, it provides an essential basis for biomolecular visualization, surface electrostatic potential map and visual perception of biomolecules. Additionally, it is consistent with the conventional setting of implicit solvent theories and thus, many existing theoretical algorithms and computational software packages can be directly employed. Finally, the Lagrangian representation does not need to resort to artificially enlarged van der Waals radii as often required by the Eulerian representation in solvation analysis. The main goal of the present work is to analyze the connection, similarity and difference between the Eulerian and Lagrangian formalisms of the solvation model. Such analysis is important to the understanding of the differential geometry based solvation model. The present model extends the scaled particle theory of nonpolar solvation model with a solvent-solute interaction potential. The nonpolar solvation model is completed with a Poisson-Boltzmann (PB) theory based polar solvation model. The differential geometry theory of surfaces is employed to provide a natural description of solvent-solute interfaces. The optimization of the total free energy functional, which encompasses the polar and nonpolar contributions, leads to coupled potential driven geometric flow and PB equations. Due to the development of singularities and nonsmooth manifolds in the Lagrangian representation, the resulting potential-driven geometric flow equation is embedded into the Eulerian representation for the purpose of computation, thanks to the equivalence of the Laplace-Beltrami operator in the two representations. The coupled partial differential equations (PDEs) are solved with an iterative procedure to reach a steady state, which delivers desired solvent-solute interface and electrostatic potential for problems of interest. These quantities are utilized to evaluate the solvation free energies and protein-protein binding affinities. A number of computational methods and algorithms are described for the interconversion of Lagrangian and Eulerian representations, and for the solution of the coupled PDE system. The proposed approaches have been extensively validated. We also verify that the mean curvature flow indeed gives rise to the minimal molecular surface and the proposed variational procedure indeed offers minimal total free energy. Solvation analysis and applications are considered for a set of 17 small compounds and a set of 23 proteins. The salt effect on protein-protein binding affinity is investigated with two protein complexes by using the present model. Numerical results are compared to the experimental measurements and to those obtained by using other theoretical methods in the literature. © Springer-Verlag 2011

Differential geometry based solvation model II: Lagrangian formulation

PubMed Central

Chen, Zhan; Baker, Nathan A.; Wei, G. W.

2010-01-01

Solvation is an elementary process in nature and is of paramount importance to more sophisticated chemical, biological and biomolecular processes. The understanding of solvation is an essential prerequisite for the quantitative description and analysis of biomolecular systems. This work presents a Lagrangian formulation of our differential geometry based solvation model. The Lagrangian representation of biomolecular surfaces has a few utilities/advantages. First, it provides an essential basis for biomolecular visualization, surface electrostatic potential map and visual perception of biomolecules. Additionally, it is consistent with the conventional setting of implicit solvent theories and thus, many existing theoretical algorithms and computational software packages can be directly employed. Finally, the Lagrangian representation does not need to resort to artificially enlarged van der Waals radii as often required by the Eulerian representation in solvation analysis. The main goal of the present work is to analyze the connection, similarity and difference between the Eulerian and Lagrangian formalisms of the solvation model. Such analysis is important to the understanding of the differential geometry based solvation model. The present model extends the scaled particle theory (SPT) of nonpolar solvation model with a solvent-solute interaction potential. The nonpolar solvation model is completed with a Poisson-Boltzmann (PB) theory based polar solvation model. The differential geometry theory of surfaces is employed to provide a natural description of solvent-solute interfaces. The minimization of the total free energy functional, which encompasses the polar and nonpolar contributions, leads to coupled potential driven geometric flow and Poisson-Boltzmann equations. Due to the development of singularities and nonsmooth manifolds in the Lagrangian representation, the resulting potential-driven geometric flow equation is embedded into the Eulerian representation for the purpose of computation, thanks to the equivalence of the Laplace-Beltrami operator in the two representations. The coupled partial differential equations (PDEs) are solved with an iterative procedure to reach a steady state, which delivers desired solvent-solute interface and electrostatic potential for problems of interest. These quantities are utilized to evaluate the solvation free energies and protein-protein binding affinities. A number of computational methods and algorithms are described for the interconversion of Lagrangian and Eulerian representations, and for the solution of the coupled PDE system. The proposed approaches have been extensively validated. We also verify that the mean curvature flow indeed gives rise to the minimal molecular surface (MMS) and the proposed variational procedure indeed offers minimal total free energy. Solvation analysis and applications are considered for a set of 17 small compounds and a set of 23 proteins. The salt effect on protein-protein binding affinity is investigated with two protein complexes by using the present model. Numerical results are compared to the experimental measurements and to those obtained by using other theoretical methods in the literature. PMID:21279359

Effect of unsaturation on the absorption of ethane and ethylene in imidazolium-based ionic liquids.

PubMed

Moura, Leila; Mishra, Manas; Bernales, Varinia; Fuentealba, Patricio; Padua, Agilio A H; Santini, Catherine C; Costa Gomes, Margarida F

2013-06-20

The influence of the presence of imidazolium side chain unsaturation on the solubility of ethane and ethylene was studied in three ionic liquids: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide-saturated alkyl side-chain in the cation; 1-methyl-3-(buten-3-yl)imidazolium bis(trifluorosulfonyl)imide-double bond in the side-chain of the cation; and 1-methyl-3-benzylimidazolium bis(trifluorosulfonyl)imide-benzyl group in the side-chain of the cation. The solubility of both gases decreases when the side-chain of the cations is functionalized with an unsaturated group. This can be explained by a less favorable enthalpy of solvation. The difference of solubility between ethane and ethylene can be explained from a balance of enthalpic and entropic factors: for the ionic liquid with the saturated alkyl side-chain and the benzyl-substituted side-chain, it is the favorable entropy of solvation that explains the larger ethylene solubility, whereas in the case of the saturated side-chain, it is the more favorable enthalpy of solvation. Molecular simulation allowed the identification of the mechanisms of solvation and the preferential solvation sites for each gas in the different ionic liquids. Simulations have shown that the entropy of solvation is more favorable when the presence of the gas weakens the cation-anion interactions or when the gas can be solvated near different sites of the ionic liquid.

Niclosamide methanol solvate and niclosamide hydrate: structure, solvent inclusion mode and implications for properties.

PubMed

Harriss, Bethany I; Wilson, Claire; Radosavljevic Evans, Ivana

2014-08-01

Structural studies have been carried out of two solid forms of niclosamide [5-chloro-N-(2-chloro-4-nitrophenyl)-2-hydroxybenzamide, NCL], a widely used anthelmintic drug, namely niclosamide methanol monosolvate, C13H8Cl2N2O4·CH3OH or NCL·MeOH, and niclosamide monohydrate, denoted HA. The structure of the methanol solvate obtained from single-crystal X-ray diffraction is reported for the first time, elucidating the key host-guest hydrogen-bonding interactions which lead to solvate formation. The essentially planar NCL host molecules interact via π-stacking and pack in a herringbone-type arrangement, giving rise to channels along the crystallographic a axis in which the methanol guest molecules are located. The methanol and NCL molecules interact via short O-H...O hydrogen bonds. Laboratory powder X-ray diffraction (PXRD) measurements reveal that the initially phase-pure NCL·MeOH solvate readily transforms into NCL monohydrate within hours under ambient conditions. PXRD further suggests that the NCL monohydrate, HA, is isostructural with the NCL·MeOH solvate. This is consistent with the facile transformation of the methanol solvate into the hydrate when stored in air. The crystal packing and the topology of guest-molecule inclusion are compared with those of other NCL solvates for which the crystal structures are known, giving a consistent picture which correlates well with known experimentally observed desolvation properties.

Olefin Metathesis in Peptidomimetics, Dynamic Combinatorial Chemistry, and Molecular Imprinting

DTIC Science & Technology

2006-08-01

aryl iodide to the Grignard reagent . Treatment of the magnesium compound with allyl bromide and CuCN·2LiCl afforded benzoate 4-11, which was then...cyclization of a linear peptide by conventional coupling agents to form a new amide bond (Scheme 1-12)36,44 Some common reagents are...dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide (DIC), and expensive reagents such as HATU or PyBroP, which are more efficient.44 Racemization of the chiral

Chiral Separation of G-type Chemical Warfare Nerve Agents via Analytical Seupercritical Fluid Chromatography

DTIC Science & Technology

2014-01-01

UNCLASSIFIED b . ABSTRACT UNCLASSIFIED c. THIS PAGE UNCLASSIFIED UNLIMITED 8 19b. TELEPHONE NUMBER (include area code) 410-436-4412 Standard Form 298...plates (N), retention fac- tor ( k ), separation factor (α), and resolution (RS). 16 Parameters were used to verify both the enantioselectivity and the...time, tR, was determined by averaging the time to peak max- ima from subsequent injections. Calculation of k was carried out using the following

Gelation induced supramolecular chirality: chirality transfer, amplification and application.

PubMed

Duan, Pengfei; Cao, Hai; Zhang, Li; Liu, Minghua

2014-08-14

Supramolecular chirality defines chirality at the supramolecular level, and is generated from the spatial arrangement of component molecules assembling through non-covalent interactions such as hydrogen bonding, van der Waals interactions, π-π stacking, hydrophobic interactions and so on. During the formation of low molecular weight gels (LMWGs), one kind of fascinating soft material, one frequently encounters the phenomenon of chirality as well as chiral nanostructures, either from chiral gelators or even achiral gelators. A view of gelation-induced supramolecular chirality will be very helpful to understand the self-assembly process of the gelator molecules as well as the chiral structures, the regulation of the chirality in the gels and the development of the "smart" chiral materials such as chiroptical devices, catalysts and chiral sensors. It necessitates fundamental understanding of chirality transfer and amplification in these supramolecular systems. In this review, recent progress in gelation-induced supramolecular chirality is discussed.

Electric line source illumination of a chiral cylinder placed in another chiral background medium

NASA Astrophysics Data System (ADS)

Aslam, M.; Saleem, A.; Awan, Z. A.

2018-05-01

An electric line source illumination of a chiral cylinder embedded in a chiral background medium is considered. The field expressions inside and outside of a chiral cylinder have been derived using the wave field decomposition approach. The effects of various chiral cylinders, chiral background media and source locations upon the scattering gain pattern have been investigated. It is observed that the chiral background reduces the backward scattering gain as compared to the free space background for a dielectric cylinder. It is also studied that by moving a line source away from a cylinder reduces the backward scattering gain for a chiral cylinder placed in a chiral background under some specific conditions. A unique phenomenon of reduced scattering gain has been observed at a specific observation angle for a chiral cylinder placed in a chiral background having an electric line source location of unity free space wavelength. An isotropic scattering gain pattern is observed for a chiral nihility background provided that if cylinder is chiral or chiral nihility type. It is also observed that this isotropic behaviour is independent of background and cylinder chirality.

Tuned range separated hybrid functionals for solvated low bandgap oligomers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Queiroz, Thiago B. de, E-mail: thiago.branquinho-de-queiroz@uni-bayreuth.de; Kümmel, Stephan

2015-07-21

The description of charge transfer excitations has long been a challenge to time dependent density functional theory. The recently developed concept of “optimally tuned range separated hybrid (OT-RSH) functionals” has proven to describe charge transfer excitations accurately in many cases. However, describing solvated or embedded systems is yet a challenge. This challenge is not only computational but also conceptual, because the tuning requires identifying a specific orbital, typically the highest occupied one of the molecule under study. For solvated molecules, this orbital may be delocalized over the solvent. We here demonstrate that one way of overcoming this problem is tomore » use a locally projected self-consistent field diagonalization on an absolutely localized molecular orbital expansion. We employ this approach to determine ionization energies and the optical gap of solvated oligothiophenes, i.e., paradigm low gap systems that are of relevance in organic electronics. Dioxane solvent molecules are explicitly represented in our calculations, and the ambiguities of straightforward parameter tuning in solution are elucidated. We show that a consistent estimate of the optimal range separated parameter (ω) at the limit of bulk solvation can be obtained by gradually extending the solvated system. In particular, ω is influenced by the solvent beyond the first coordination sphere. For determining ionization energies, a considerable number of solvent molecules on the first solvation shell must be taken into account. We demonstrate that accurately calculating optical gaps of solvated systems using OT-RSH can be done in three steps: (i) including the chemical environment when determining the range-separation parameter, (ii) taking into account the screening due to the solvent, and (iii) using realistic molecular geometries.« less

Zero-point energy effects in anion solvation shells.

PubMed

Habershon, Scott

2014-05-21

By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways

NASA Astrophysics Data System (ADS)

Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Arias, T. A.; Hennig, Richard G.

2014-02-01

Solid-liquid interfaces are at the heart of many modern-day technologies and provide a challenge to many materials simulation methods. A realistic first-principles computational study of such systems entails the inclusion of solvent effects. In this work, we implement an implicit solvation model that has a firm theoretical foundation into the widely used density-functional code Vienna ab initio Software Package. The implicit solvation model follows the framework of joint density functional theory. We describe the framework, our algorithm and implementation, and benchmarks for small molecular systems. We apply the solvation model to study the surface energies of different facets of semiconducting and metallic nanocrystals and the SN2 reaction pathway. We find that solvation reduces the surface energies of the nanocrystals, especially for the semiconducting ones and increases the energy barrier of the SN2 reaction.

Enhancing and reducing chirality by opposite circularly-polarized light irradiation on crystalline chiral domains consisting of nonchiral photoresponsive W-shaped liquid crystal molecules.

PubMed

Choi, Suk-Won; Takezoe, Hideo

2016-09-28

We found possible chirality enhancement and reduction in chiral domains formed by photoresponsive W-shaped molecules by irradiation with circularly polarized light (CPL). The W-shaped molecules exhibit a unique smectic phase with spontaneously segregated chiral domains, although the molecules are nonchiral. The chirality control was generated in the crystalline phase, which shows chiral segregation as in the upper smectic phase, and the result appeared to be as follows: for a certain chiral domain, right-CPL stimuli enhanced the chirality, while left-CPL stimuli reduced the chirality, and vice versa for another chiral domain. Interestingly, no domain-size change could be observed after CPL irradiation, suggesting some changes in the causes of chirality. In this way, the present system can recognize the handedness of the applied chiral stimuli. In other words, the present material can be used as a sensitive chiral-stimuli-recognizing material and should find invaluable applications, including in chiroptical switches, sensors, and memories as well as in chiral recognition.

Optimized multi-step NMR-crystallography approach for structural characterization of a stable quercetin solvate.

PubMed

Filip, Xenia; Miclaus, Maria; Martin, Flavia; Filip, Claudiu; Grosu, Ioana Georgeta

2017-05-10

Herein we report the preparation and solid state structural investigation of the 1,4-dioxane-quercetin solvate. NMR crystallography methods were employed for crystal structure determination of the solvate from microcrystalline powder. The stability of the compound relative to other reported quercetin solvates is discussed and found to be in perfect agreement with the hydrogen bonding networks/supra-molecular architectures formed in each case. It is also clearly shown that NMR crystallography represents an ideal analytical tool in such cases when hydrogen-bonding networks are required to be constrained at a high accuracy level. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydration property of globular proteins: An analysis of solvation free energy by energy representation method

NASA Astrophysics Data System (ADS)

Saito, Hiroaki; Matubayasi, Nobuyuki; Nishikawa, Kiyoshi; Nagao, Hidemi

2010-09-01

Molecular dynamics simulations and solvation free energy calculations of five globular proteins (BPTI, RNase A, Lysozyme, β-lactoglobulin A, and α-chymotrypsinogen A) have been carried out to elucidate the hydration properties. Solvation free energies of the proteins with explicit solvent were estimated by energy representation (ER) method. The calculated solvation free energies were correlated with the solvent accessible surface area of hydrophilic portion, being consistent with the hydrophilic property of the proteins. These results showed that the ER method should be a powerful tool for estimating the hydration property of proteins, showing a progress of the free energy calculation with explicit solvent.

Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

NASA Astrophysics Data System (ADS)

Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A.

2018-04-01

Reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the potential of zero charge and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristics of a solvation model suitable for first-principles electrochemistry of metal surfaces in non-adsorbing, aqueous electrolytes: dielectric and ionic nonlinearity, and a dielectric-only region at the interface. The dielectric nonlinearity, caused by the saturation of dipole rotational response in water, creates the capacitance hump, while ionic nonlinearity, caused by the compactness of the diffuse layer, generates the capacitance dip seen at low ionic strength. We show that none of the previously developed solvation models simultaneously meet all these criteria. We design the nonlinear electrochemical soft-sphere solvation model which both captures the capacitance features observed experimentally and serves as a general-purpose continuum solvation model.

"Martinizing" the Variational Implicit Solvent Method (VISM): Solvation Free Energy for Coarse-Grained Proteins.

PubMed

Ricci, Clarisse G; Li, Bo; Cheng, Li-Tien; Dzubiella, Joachim; McCammon, J Andrew

2017-07-13

Solvation is a fundamental driving force in many biological processes including biomolecular recognition and self-assembly, not to mention protein folding, dynamics, and function. The variational implicit solvent method (VISM) is a theoretical tool currently developed and optimized to estimate solvation free energies for systems of very complex topology, such as biomolecules. VISM's theoretical framework makes it unique because it couples hydrophobic, van der Waals, and electrostatic interactions as a functional of the solvation interface. By minimizing this functional, VISM produces the solvation interface as an output of the theory. In this work, we push VISM to larger scale applications by combining it with coarse-grained solute Hamiltonians adapted from the MARTINI framework, a well-established mesoscale force field for modeling large-scale biomolecule assemblies. We show how MARTINI-VISM ( M VISM) compares with atomistic VISM ( A VISM) for a small set of proteins differing in size, shape, and charge distribution. We also demonstrate M VISM's suitability to study the solvation properties of an interesting encounter complex, barnase-barstar. The promising results suggest that coarse-graining the protein with the MARTINI force field is indeed a valuable step to broaden VISM's and MARTINI's applications in the near future.

Performance of the SMD and SM8 models for predicting solvation free energy of neutral solutes in methanol, dimethyl sulfoxide and acetonitrile.

PubMed

Zanith, Caroline C; Pliego, Josefredo R

2015-03-01

The continuum solvation models SMD and SM8 were developed using 2,346 solvation free energy values for 318 neutral molecules in 91 solvents as reference. However, no solvation data of neutral solutes in methanol was used in the parametrization, while only few solvation free energy values of solutes in dimethyl sulfoxide and acetonitrile were used. In this report, we have tested the performance of the models for these important solvents. Taking data from literature, we have generated solvation free energy, enthalpy and entropy values for 37 solutes in methanol, 21 solutes in dimethyl sulfoxide and 19 solutes in acetonitrile. Both SMD and SM8 models have presented a good performance in methanol and acetonitrile, with mean unsigned error equal or less than 0.66 and 0.55 kcal mol(-1) in methanol and acetonitrile, respectively. However, the correlation is worse in dimethyl sulfoxide, where the SMD and SM8 methods present mean unsigned error of 1.02 and 0.95 kcal mol(-1), respectively. Our results point out the SMx family of models need be improved for dimethyl sulfoxide solvent.

Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions

DOE PAGES

Duignan, Timothy T.; Baer, Marcel D.; Schenter, Gregory K.; ...

2017-07-26

Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into simple and intuitive contributions will have important implications for models of electrolyte solution. In this paper, we provide definitions of the various types of single ion solvation free energies based on different simulation protocols. We calculate solvation free energies of charged hard spheres using density functional theory interaction potentials with molecular dynamics simulation and isolate the effects of charge and cavitation, comparing tomore » the Born (linear response) model. We show that using uncorrected Ewald summation leads to unphysical values for the single ion solvation free energy and that charging free energies for cations are approximately linear as a function of charge but that there is a small non-linearity for small anions. The charge hydration asymmetry for hard spheres, determined with quantum mechanics, is much larger than for the analogous real ions. Finally, this suggests that real ions, particularly anions, are significantly more complex than simple charged hard spheres, a commonly employed representation.« less

Standard electrode potential, Tafel equation, and the solvation thermodynamics.

PubMed

Matyushov, Dmitry V

2009-06-21

Equilibrium in the electronic subsystem across the solution-metal interface is considered to connect the standard electrode potential to the statistics of localized electronic states in solution. We argue that a correct derivation of the Nernst equation for the electrode potential requires a careful separation of the relevant time scales. An equation for the standard metal potential is derived linking it to the thermodynamics of solvation. The Anderson-Newns model for electronic delocalization between the solution and the electrode is combined with a bilinear model of solute-solvent coupling introducing nonlinear solvation into the theory of heterogeneous electron transfer. We therefore are capable of addressing the question of how nonlinear solvation affects electrochemical observables. The transfer coefficient of electrode kinetics is shown to be equal to the derivative of the free energy, or generalized force, required to shift the unoccupied electronic level in the bulk. The transfer coefficient thus directly quantifies the extent of nonlinear solvation of the redox couple. The current model allows the transfer coefficient to deviate from the value of 0.5 of the linear solvation models at zero electrode overpotential. The electrode current curves become asymmetric in respect to the change in the sign of the electrode overpotential.

A salient effect of density on the dynamics of nonaqueous electrolytes.

PubMed

Han, Sungho

2017-04-24

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duignan, Timothy T.; Baer, Marcel D.; Schenter, Gregory K.

Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into simple and intuitive contributions will have important implications for models of electrolyte solution. In this paper, we provide definitions of the various types of single ion solvation free energies based on different simulation protocols. We calculate solvation free energies of charged hard spheres using density functional theory interaction potentials with molecular dynamics simulation and isolate the effects of charge and cavitation, comparing tomore » the Born (linear response) model. We show that using uncorrected Ewald summation leads to unphysical values for the single ion solvation free energy and that charging free energies for cations are approximately linear as a function of charge but that there is a small non-linearity for small anions. The charge hydration asymmetry for hard spheres, determined with quantum mechanics, is much larger than for the analogous real ions. Finally, this suggests that real ions, particularly anions, are significantly more complex than simple charged hard spheres, a commonly employed representation.« less

Solvated dissipative electro-elastic network model of hydrated proteins

NASA Astrophysics Data System (ADS)

Martin, Daniel

2013-03-01

Elastic network models coarse grain proteins into a network of residue beads connected by springs. We add dissipative dynamics to this mechanical system by applying overdamped Langevin equations of motion to normal-mode vibrations of the network. In addition, the network is made heterogeneous and softened at the protein surface by accounting for hydration of the ionized residues. Solvation changes the network Hessian in two ways. Diagonal solvation terms soften the spring constants and off-diagonal dipole-dipole terms correlate displacements of the ionized residues. The model is used to formulate the response functions of the electrostatic potential and electric field appearing in theories of redox reactions and spectroscopy. We also formulate the dielectric response of the protein and find that solvation of the surface ionized residues leads to a slow relaxation peak in the dielectric loss spectrum, about two orders of magnitude slower than the main peak of protein relaxation. Finally, the solvated network is used to formulate the allosteric response of the protein to ion binding. The global thermodynamics of ion binding is not strongly affected by the network solvation, but it dramatically enhances conformational changes in response to placing a charge at the a the active site.

Solvated dissipative electro-elastic network model of hydrated proteins

NASA Astrophysics Data System (ADS)

Martin, Daniel R.; Matyushov, Dmitry V.

2012-10-01

Elastic network models coarse grain proteins into a network of residue beads connected by springs. We add dissipative dynamics to this mechanical system by applying overdamped Langevin equations of motion to normal-mode vibrations of the network. In addition, the network is made heterogeneous and softened at the protein surface by accounting for hydration of the ionized residues. Solvation changes the network Hessian in two ways. Diagonal solvation terms soften the spring constants and off-diagonal dipole-dipole terms correlate displacements of the ionized residues. The model is used to formulate the response functions of the electrostatic potential and electric field appearing in theories of redox reactions and spectroscopy. We also formulate the dielectric response of the protein and find that solvation of the surface ionized residues leads to a slow relaxation peak in the dielectric loss spectrum, about two orders of magnitude slower than the main peak of protein relaxation. Finally, the solvated network is used to formulate the allosteric response of the protein to ion binding. The global thermodynamics of ion binding is not strongly affected by the network solvation, but it dramatically enhances conformational changes in response to placing a charge at the active site of the protein.

Hydrophilic Solvation Dominates the Terahertz Fingerprint of Amino Acids in Water.

PubMed

Esser, Alexander; Forbert, Harald; Sebastiani, Federico; Schwaab, Gerhard; Havenith, Martina; Marx, Dominik

2018-02-01

Spectroscopy in the terahertz frequency regime is a sensitive tool to probe solvation-induced effects in aqueous solutions. Yet, a systematic understanding of spectral lineshapes as a result of distinct solvation contributions remains terra incognita. We demonstrate that modularization of amino acids in terms of functional groups allows us to compute their distinct contributions to the total terahertz response. Introducing the molecular cross-correlation analysis method provides unique access to these site-specific contributions. Equivalent groups in different amino acids lead to look-alike spectral contributions, whereas side chains cause characteristic but additive complexities. Specifically, hydrophilic solvation of the zwitterionic groups in valine and glycine leads to similar terahertz responses which are fully decoupled from the side chain. The terahertz response due to H-bonding within the large hydrophobic solvation shell of valine turns out to be nearly indistinguishable from that in bulk water in direct comparison to the changes imposed by the charged functional groups that form strong H-bonds with their hydration shells. Thus, the hydrophilic groups and their solvation shells dominate the terahertz absorption difference, while on the same intensity scale, the influence of hydrophobic water can be neglected.

A salient effect of density on the dynamics of nonaqueous electrolytes

NASA Astrophysics Data System (ADS)

Han, Sungho

2017-04-01

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

Protons in non-ionic aqueous reverse micelles.

PubMed

Rodriguez, Javier; Martí, Jordi; Guàrdia, Elvira; Laria, Daniel

2007-05-03

Using molecular dynamics techniques, we investigate the solvation of an excess proton within an aqueous reverse micelle in vacuo, with the neutral surfactant diethylene glycol monodecyl ether [CH3(CH2)11(OC2H4)2OH]. The simulation experiments were performed using a multistate empirical valence bond Hamiltonian model. Our results show that the stable solvation environments for the excess proton are located in the water-surfactant interface and that its first solvation shell is composed exclusively by water molecules. The relative prevalence of Eigen- versus Zundel-like solvation structures is investigated; compared to bulk results, Zundel-like structures in micelles become somewhat more stable. Characteristic times for the proton translocation jumps have been computed using population relaxation time correlation functions. The micellar rate for proton transfer is approximately 40x smaller than that found in bulk water at ambient conditions. Differences in the computed rates are examined in terms of the hydrogen-bond connectivity involving the first solvation shell of the excess charge with the rest of the micellar environment. Simulation results would indicate that proton transfers are correlated with rare episodes during which the HB connectivity between the first and second solvation shells suffers profound modifications.

Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions

NASA Astrophysics Data System (ADS)

Duignan, Timothy T.; Baer, Marcel D.; Schenter, Gregory K.; Mundy, Chistopher J.

2017-10-01

Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into simple and intuitive contributions will have important implications for models of electrolyte solution. Here, we provide definitions of the various types of single ion solvation free energies based on different simulation protocols. We calculate solvation free energies of charged hard spheres using density functional theory interaction potentials with molecular dynamics simulation and isolate the effects of charge and cavitation, comparing to the Born (linear response) model. We show that using uncorrected Ewald summation leads to unphysical values for the single ion solvation free energy and that charging free energies for cations are approximately linear as a function of charge but that there is a small non-linearity for small anions. The charge hydration asymmetry for hard spheres, determined with quantum mechanics, is much larger than for the analogous real ions. This suggests that real ions, particularly anions, are significantly more complex than simple charged hard spheres, a commonly employed representation.

Performance of the SMD and SM8 models for predicting solvation free energy of neutral solutes in methanol, dimethyl sulfoxide and acetonitrile

NASA Astrophysics Data System (ADS)

Zanith, Caroline C.; Pliego, Josefredo R.

2015-03-01

The continuum solvation models SMD and SM8 were developed using 2,346 solvation free energy values for 318 neutral molecules in 91 solvents as reference. However, no solvation data of neutral solutes in methanol was used in the parametrization, while only few solvation free energy values of solutes in dimethyl sulfoxide and acetonitrile were used. In this report, we have tested the performance of the models for these important solvents. Taking data from literature, we have generated solvation free energy, enthalpy and entropy values for 37 solutes in methanol, 21 solutes in dimethyl sulfoxide and 19 solutes in acetonitrile. Both SMD and SM8 models have presented a good performance in methanol and acetonitrile, with mean unsigned error equal or less than 0.66 and 0.55 kcal mol-1 in methanol and acetonitrile, respectively. However, the correlation is worse in dimethyl sulfoxide, where the SMD and SM8 methods present mean unsigned error of 1.02 and 0.95 kcal mol-1, respectively. Our results point out the SMx family of models need be improved for dimethyl sulfoxide solvent.

Solvent effects on the crystal growth structure and morphology of the pharmaceutical dirithromycin

NASA Astrophysics Data System (ADS)

Wang, Yuan; Liang, Zuozhong

2017-12-01

Solvent effects on the crystal structure and morphology of pharmaceutical dirithromycin molecules were systematically investigated using both experimental crystallization and theoretical simulation. Dirithromycin is one of the new generation of macrolide antibiotics with two polymorphic forms (Form I and Form II) and many solvate forms. Herein, six solvates of the dirithromycin, including acetonitrile, acetonitrile/water, acetone, 1-propanol, N,N-dimethylformamide (DMF) and cyclohexane, were studied. Experimentally, we crystallized the dirithromycin molecules in different solvents by the solvent evaporating method and measured the crystal structures with the X-ray diffraction (XRD). We compared these crystal structures of dirithromycin solvates and analyzed the solvent property-determined structure evolution. The solvents have a strong interaction with the dirithromycin molecule due to the formation of inter-molecular interactions (such as the hydrogen bonding and close contacts (sum of vdW radii)). Theoretically, we calculated the ideal crystal habit based on the solvated structures with the attachment growth (AE) model. The predicted morphologies and aspect ratios of dirithromycin solvates agree well with the experimental results. This work could be helpful to better understand the structure and morphology evolution of solvates controlled by solvents and guide the crystallization of active pharmaceutical ingredients in the pharmaceutical industry.

Solvation thermodynamics of amino acid side chains on a short peptide backbone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hajari, Timir; Vegt, Nico F. A. van der, E-mail: vandervegt@csi.tu-darmstadt.de

The hydration process of side chain analogue molecules differs from that of the actual amino acid side chains in peptides and proteins owing to the effects of the peptide backbone on the aqueous solvent environment. A recent molecular simulation study has provided evidence that all nonpolar side chains, attached to a short peptide backbone, are considerably less hydrophobic than the free side chain analogue molecules. In contrast to this, the hydrophilicity of the polar side chains is hardly affected by the backbone. To analyze the origin of these observations, we here present a molecular simulation study on temperature dependent solvationmore » free energies of nonpolar and polar side chains attached to a short peptide backbone. The estimated solvation entropies and enthalpies of the various amino acid side chains are compared with existing side chain analogue data. The solvation entropies and enthalpies of the polar side chains are negative, but in absolute magnitude smaller compared with the corresponding analogue data. The observed differences are large; however, owing to a nearly perfect enthalpy-entropy compensation, the solvation free energies of polar side chains remain largely unaffected by the peptide backbone. We find that a similar compensation does not apply to the nonpolar side chains; while the backbone greatly reduces the unfavorable solvation entropies, the solvation enthalpies are either more favorable or only marginally affected. This results in a very small unfavorable free energy cost, or even free energy gain, of solvating the nonpolar side chains in strong contrast to solvation of small hydrophobic or nonpolar molecules in bulk water. The solvation free energies of nonpolar side chains have been furthermore decomposed into a repulsive cavity formation contribution and an attractive dispersion free energy contribution. We find that cavity formation next to the peptide backbone is entropically favored over formation of similar sized nonpolar side chain cavities in bulk water, in agreement with earlier work in the literature on analysis of cavity fluctuations at nonpolar molecular surfaces. The cavity and dispersion interaction contributions correlate quite well with the solvent accessible surface area of the nonpolar side chains attached to the backbone. This correlation however is weak for the overall solvation free energies owing to the fact that the cavity and dispersion free energy contributions are almost exactly cancelling each other.« less

Association Thermodynamics and Conformational Stability of β-Sheet Amyloid β(17-42) Oligomers: Effects of E22Q (Dutch) Mutation and Charge Neutralization

PubMed Central

Blinov, Nikolay; Dorosh, Lyudmyla; Wishart, David; Kovalenko, Andriy

2010-01-01

Amyloid fibrils are associated with many neurodegenerative diseases. It was found that amyloidogenic oligomers, not mature fibrils, are neurotoxic agents related to these diseases. Molecular mechanisms of infectivity, pathways of aggregation, and molecular structure of these oligomers remain elusive. Here, we use all-atom molecular dynamics, molecular mechanics combined with solvation analysis by statistical-mechanical, three-dimensional molecular theory of solvation (also known as 3D-RISM-KH) in a new MM-3D-RISM-KH method to study conformational stability, and association thermodynamics of small wild-type Aβ17–42 oligomers with different protonation states of Glu22, as well the E22Q (Dutch) mutants. The association free energy of small β-sheet oligomers shows near-linear trend with the dimers being thermodynamically more stable relative to the larger constructs. The linear (within statistical uncertainty) dependence of the association free energy on complex size is a consequence of the unilateral stacking of monomers in the β-sheet oligomers. The charge reduction of the wild-type Aβ17–42 oligomers upon protonation of the solvent-exposed Glu22 at acidic conditions results in lowering the association free energy compared to the wild-type oligomers at neutral pH and the E22Q mutants. The neutralization of the peptides because of the E22Q mutation only marginally affects the association free energy, with the reduction of the direct electrostatic interactions mostly compensated by the unfavorable electrostatic solvation effects. For the wild-type oligomers at acidic conditions such compensation is not complete, and the electrostatic interactions, along with the gas-phase nonpolar energetic and the overall entropic effects, contribute to the lowering of the association free energy. The differences in the association thermodynamics between the wild-type Aβ17–42 oligomers at neutral pH and the Dutch mutants, on the one hand, and the Aβ17–42 oligomers with protonated Glu22, on the other, may be explained by destabilization of the inter- and intrapeptide salt bridges between Asp23 and Lys28. Peculiarities in the conformational stability and the association thermodynamics for the different models of the Aβ17–42 oligomers are rationalized based on the analysis of the local physical interactions and the microscopic solvation structure. PMID:20338850

Aptamer-Encoded Nanopore for Ultrasensitive Detection of Bioterrorist Agent Ricin at Single-Molecule Resolution

PubMed Central

Gu, Li-Qun; Ding, Shu; Gao, Changlu

2011-01-01

The molecular-scale pore structure, called nanopore, can be formed from protein ion channels by genetic engineering or fabricated on solid substrates using fashion nanotechnology. Target molecules in interaction with the functionalized lumen of nanopore, can produce characteristic changes in the pore conductance, which act as fingerprints, allowing us to identify single molecules and simultaneously quantify each target species in the mixture. Nanopore sensors have been created for tremendous biomedical detections, with targets ranging from metal ions, drug compounds and cellular second messengers, to proteins and DNAs. Here we will review our recent discoveries with a lab-in-hand glass nanopore: single-molecule discrimination of chiral enantiomers with a trapped cyclodextrin, and sensing of bioterrorist agent ricin. PMID:19964179

Asymmetric intramolecular α-cyclopropanation of aldehydes using a donor/acceptor carbene mimetic

PubMed Central

Luo, Chaosheng; Wang, Zhen; Huang, Yong

2015-01-01

Enantioselective α-alkylation of carbonyl is considered as one of the most important processes for asymmetric synthesis. Common alkylation agents, that is, alkyl halides, are notorious substrates for both Lewis acids and organocatalysts. Recently, olefins emerged as a benign alkylating species via photo/radical mechanisms. However, examples of enantioselective alkylation of aldehydes/ketones are scarce and direct asymmetric dialkylation remains elusive. Here we report an intramolecular α-cyclopropanation reaction of olefinic aldehydes to form chiral cyclopropane aldehydes. We demonstrate that an α-iodo aldehyde can function as a donor/acceptor carbene equivalent, which engages in a formal [2+1] annulation with a tethered double bond. Privileged bicyclo[3.1.0]hexane-type scaffolds are prepared in good optical purity using a chiral amine. The synthetic utility of the products is demonstrated by versatile transformations of the bridgehead formyl functionality. We expect the concept of using α-iodo iminium as a donor/acceptor carbene surrogate will find wide applications in chemical reaction development. PMID:26644194

In vitro DNA binding, pBR322 plasmid cleavage and molecular modeling study of chiral benzothiazole Schiff-base-valine Cu(II) and Zn(II) complexes to evaluate their enantiomeric biological disposition for molecular target DNA

NASA Astrophysics Data System (ADS)

Alizadeh, Rahman; Afzal, Mohd; Arjmand, Farukh

2014-10-01

Bicyclic heterocyclic compounds viz. benzothiazoles are key components of deoxyribonucleic acid (DNA) molecules and participate directly in the encoding of genetic information. Benzothiazoles, therefore, represent a potent and selective class of antitumor compounds. The design and synthesis of chiral antitumor chemotherapeutic agents of Cu(II) and Zn(II), L- and -D benzothiazole Schiff base-valine complexes 1a &b and 2a &b, respectively were carried out and thoroughly characterized by spectroscopic and analytical techniques. Interaction of 1a and b and 2a and b with CT DNA by employing UV-vis, florescence, circular dichroic methods and cleavage studies of 1a with pBR322 plasmid, molecular docking were done in order to demonstrate their enantiomeric disposition toward the molecular drug target DNA. Interestingly, these studies unambiguously demonstrated the greater potency of L-enantiomer in comparison to D-enantiomer.

Reactivity between biphenyl and precursor of solvated electrons in tetrahydrofuran measured by picosecond pulse radiolysis in near-ultraviolet, visible, and infrared.

PubMed

Saeki, Akinori; Kozawa, Takahiro; Ohnishi, Yuko; Tagawa, Seiichi

2007-02-22

The initial decrease of solvated electrons in tetrahydrofuran (THF) upon addition of biphenyl was investigated by picosecond pulse radiolysis. Transient absorption spectra derived from the biphenyl radical anion (centered at 408 and 655 nm) and solvated electrons of THF (infrared) were successfully measured in the wavelength region from 400 to 900 nm by the extension of a femtosecond continuum probe light to near-ultraviolet using a second harmonic generation of Ti:sapphire laser and a CaF2 plate. From the analysis of kinetic traces at 1300 nm considering the overlap of primary solvated electrons and partial biphenyl radical anion, C37, which is defined by the solute concentration to reduce the initial yield of solvated electrons to 1/e, was found to be 87 +/- 3 mM. The rate constant of solvated electrons with biphenyl was determined as 5.8 +/- 0.3 x 10(10) M(-1) s(-1). We demonstrate that the kinetic traces at both 408 nm mainly due to biphenyl radical anion and 1300 nm mainly due to solvated electrons are reproduced with high accuracy and consistency by a simple kinetic analysis. Much higher concentrations of biphenyl (up to 2 M) were examined, showing further increase of the initial yield of biphenyl radical anion accompanying a fast decay component. This observation is discussed in terms of geminate ion recombination, scavenging, delayed geminate ion recombination, and direct ionization of biphenyl at high concentration.

Investigation of rubidium(I) ion solvation in liquid ammonia using QMCF-MD simulation and NBO analysis of first solvation shell structure.

PubMed

Hidayat, Yuniawan; Armunanto, Ria; Pranowo, Harno Dwi

2018-04-27

Rb(I) ion solvation in liquid ammonia has been studied by an ab initio quantum mechanical charge field molecular dynamics simulation, and the first solvation shell structure has been analyzed using natural bond orbital. The simulation was performed for an ion and 593 ammonia molecules in a box with a length of 29.03 Å corresponding to a liquid ammonia density of 0.69 g/mL at 235.16 K. The quantum mechanical calculation was carried out for atomic interactions in the radius of 6.4 Å from the ion using LANL2DZ ECP and DZP (Dunning) basis sets for Rb(I) ion and ammonia respectively. The trajectories of the simulation were analyzed in terms of radial, angular, and coordination number distribution functions, vibration, and mean residence time (MRT). Two solvation shell regions are observed for the Rb(I)-N as well as the Rb(I)-H. The maximum distance of Rb(I)-N in the first solvation shell is in accordance with experimental data where a coordination number of 8 is favorable. A non-single coordination number of the first and second shell indicates dynamic solvation structure. It is confirmed by frequent exchange ligand processes observed within a simulation time of 15 ps. The low stabilization energy of donor acceptor ion-ligand interaction with a small Wiberg bond index affirms that the Rb(I)-NH 3 interaction is weak electrostatically.

Chiral Gold Nanoclusters: Atomic Level Origins of Chirality.

PubMed

Zeng, Chenjie; Jin, Rongchao

2017-08-04

Chiral nanomaterials have received wide interest in many areas, but the exact origin of chirality at the atomic level remains elusive in many cases. With recent significant progress in atomically precise gold nanoclusters (e.g., thiolate-protected Au n (SR) m ), several origins of chirality have been unveiled based upon atomic structures determined by using single-crystal X-ray crystallography. The reported chiral Au n (SR) m structures explicitly reveal a predominant origin of chirality that arises from the Au-S chiral patterns at the metal-ligand interface, as opposed to the chiral arrangement of metal atoms in the inner core (i.e. kernel). In addition, chirality can also be introduced by a chiral ligand, manifested in the circular dichroism response from metal-based electronic transitions other than the ligand's own transition(s). Lastly, the chiral arrangement of carbon tails of the ligands has also been discovered in a very recent work on chiral Au 133 (SR) 52 and Au 246 (SR) 80 nanoclusters. Overall, the origins of chirality discovered in Au n (SR) m nanoclusters may provide models for the understanding of chirality origins in other types of nanomaterials and also constitute the basis for the development of various applications of chiral nanoparticles. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral signs of TPPS co-assemblies with chiral gelators: role of molecular and supramolecular chirality.

PubMed

Wang, Qiuling; Zhang, Li; Yang, Dong; Li, Tiesheng; Liu, Minghua

2016-10-13

A dianionic tetrakis(4-sulfonatophenyl)porphyrin (TPPS) self-assembled into J-aggregates when it co-assembled with a chiral cationic amphiphile via supramolecular gelation. The chiral signs of TPPS J aggregates followed the supramolecular chirality of amphiphilic assemblies rather than the molecular chirality of the amphiphile.

Formation of Enhanced Uniform Chiral Fields in Symmetric Dimer Nanostructures

PubMed Central

Tian, Xiaorui; Fang, Yurui; Sun, Mengtao

2015-01-01

Chiral fields with large optical chirality are very important in chiral molecules analysis, sensing and other measurements. Plasmonic nanostructures have been proposed to realize such super chiral fields for enhancing weak chiral signals. However, most of them cannot provide uniform chiral near-fields close to the structures, which makes these nanostructures not so efficient for applications. Plasmonic helical nanostructures and blocked squares have been proved to provide uniform chiral near-fields, but structure fabrication is a challenge. In this paper, we show that very simple plasmonic dimer structures can provide uniform chiral fields in the gaps with large enhancement of both near electric fields and chiral fields under linearly polarized light illumination with polarization off the dimer axis at dipole resonance. An analytical dipole model is utilized to explain this behavior theoretically. 30 times of volume averaged chiral field enhancement is gotten in the whole gap. Chiral fields with opposite handedness can be obtained simply by changing the polarization to the other side of the dimer axis. It is especially useful in Raman optical activity measurement and chiral sensing of small quantity of chiral molecule. PMID:26621558

Chiral Separations

NASA Astrophysics Data System (ADS)

Stalcup, A. M.

2010-07-01

The main goal of this review is to provide a brief overview of chiral separations to researchers who are versed in the area of analytical separations but unfamiliar with chiral separations. To researchers who are not familiar with this area, there is currently a bewildering array of commercially available chiral columns, chiral derivatizing reagents, and chiral selectors for approaches that span the range of analytical separation platforms (e.g., high-performance liquid chromatography, gas chromatography, supercritical-fluid chromatography, and capillary electrophoresis). This review begins with a brief discussion of chirality before examining the general strategies and commonalities among all of the chiral separation techniques. Rather than exhaustively listing all the chiral selectors and applications, this review highlights significant issues and differences between chiral and achiral separations, providing salient examples from specific classes of chiral selectors where appropriate.

Spectrum of Slow and Super-Slow (Picosecond to Nanosecond) Water Dynamics around Organic and Biological Solutes.

PubMed

Ramakrishnan, Gopakumar; González-Jiménez, Mario; Lapthorn, Adrian J; Wynne, Klaas

2017-07-06

Water dynamics in the solvation shell of solutes plays a very important role in the interaction of biomolecules and in chemical reaction dynamics. However, a selective spectroscopic study of the solvation shell is difficult because of the interference of the solute dynamics. Here we report on the observation of heavily slowed down water dynamics in the solvation shell of different solutes by measuring the low-frequency spectrum of solvation water, free from the contribution of the solute. A slowdown factor of ∼50 is observed even for relatively low concentrations of the solute. We go on to show that the effect can be generalized to different solutes including proteins.

Kamlet-Taft solvent parameters, NMR spectroscopic analysis and thermoelectrochemistry of lithium-glyme solvate ionic liquids and their dilute solutions.

PubMed

Black, Jeffrey J; Dolan, Andrew; Harper, Jason B; Aldous, Leigh

2018-06-06

Solvate ionic liquids are a relatively new class of liquids produced by combining a coordinating solvent with a salt. They have a variety of uses and their suitability for such depends upon the ratio of salt to coordinating solvent. This work investigates the Kamlet-Taft solvent parameters of, NMR chemical shifts of nuclei in, and thermoelectrochemistry of a selected set of solvate ionic liquids produced from glymes (methyl terminated oligomers of ethylene glycol) and lithium bis(trifluoromethylsulfonyl)imide at two different compositions. The aim is to improve the understanding of the interactions occurring in these ionic liquids to help select suitable solvate ionic liquids for future applications.

Evidence for Reduced Hydrogen-Bond Cooperativity in Ionic Solvation Shells from Isotope-Dependent Dielectric Relaxation

NASA Astrophysics Data System (ADS)

Cota, Roberto; Ottosson, Niklas; Bakker, Huib J.; Woutersen, Sander

2018-05-01

We find that the reduction in dielectric response (depolarization) of water caused by solvated ions is different for H2O and D2O . This isotope dependence allows us to reliably determine the kinetic contribution to the depolarization, which is found to be significantly smaller than predicted by existing theory. The discrepancy can be explained from a reduced hydrogen-bond cooperativity in the solvation shell: we obtain quantitative agreement between theory and experiment by reducing the Kirkwood correlation factor of the solvating water from 2.7 (the bulk value) to ˜1.6 for NaCl and ˜1 (corresponding to completely uncorrelated motion of water molecules) for CsCl.

Chirality-Controlled Synthesis and Applications of Single-Wall Carbon Nanotubes.

PubMed

Liu, Bilu; Wu, Fanqi; Gui, Hui; Zheng, Ming; Zhou, Chongwu

2017-01-24

Preparation of chirality-defined single-wall carbon nanotubes (SWCNTs) is the top challenge in the nanotube field. In recent years, great progress has been made toward preparing single-chirality SWCNTs through both direct controlled synthesis and postsynthesis separation approaches. Accordingly, the uses of single-chirality-dominated SWCNTs for various applications have emerged as a new front in nanotube research. In this Review, we review recent progress made in the chirality-controlled synthesis of SWCNTs, including metal-catalyst-free SWCNT cloning by vapor-phase epitaxy elongation of purified single-chirality nanotube seeds, chirality-specific growth of SWCNTs on bimetallic solid alloy catalysts, chirality-controlled synthesis of SWCNTs using bottom-up synthetic strategy from carbonaceous molecular end-cap precursors, etc. Recent major progresses in postsynthesis separation of single-chirality SWCNT species, as well as methods for chirality characterization of SWCNTs, are also highlighted. Moreover, we discuss some examples where single-chirality SWCNTs have shown clear advantages over SWCNTs with broad chirality distributions. We hope this review could inspire more research on the chirality-controlled preparation of SWCNTs and equally important inspire the use of single-chirality SWCNT samples for more fundamental studies and practical applications.

Computational analysis of the solvation of coffee ingredients in aqueous ionic liquid mixtures.

PubMed

Zeindlhofer, Veronika; Khlan, Diana; Bica, Katharina; Schröder, Christian

2017-01-13

In this paper, we investigate the solvation of coffee ingredients including caffeine, gallic acid as representative for phenolic compounds and quercetin as representative for flavonoids in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate [C 2 mim][OAc] at various concentrations. Due to the anisotropy of the solutes we show that classical Kirkwood-Buff theory is not appropriate to study solvation effects with increasing ionic liquid content. However, excess coordination numbers as well as the mean residence time of solvent molecules at the surface of the solutes can be determined by Voronoi tessellation. Since the volume of the hydration shells is also available by this method, solvation free energies will be discussed as a function of the ionic liquid concentration to yield a physical meaningful picture of solvation for the anisotropic solutes. Hydrogen bonding capabilities of the solutes and their relevance for experimental extraction yields from spent coffee grounds are also discussed.

Elucidating Solvation Structures for Rational Design of Multivalent Electrolytes-A Review.

PubMed

Rajput, Nav Nidhi; Seguin, Trevor J; Wood, Brandon M; Qu, Xiaohui; Persson, Kristin A

2018-04-26

Fundamental molecular-level understanding of functional properties of liquid solutions provides an important basis for designing optimized electrolytes for numerous applications. In particular, exhaustive knowledge of solvation structure, stability, and transport properties is critical for developing stable electrolytes for fast-charging and high-energy-density next-generation energy storage systems. Accordingly, there is growing interest in the rational design of electrolytes for beyond lithium-ion systems by tuning the molecular-level interactions of solvate species present in the electrolytes. Here we present a review of the solvation structure of multivalent electrolytes and its impact on the electrochemical performance of these batteries. A direct correlation between solvate species present in the solution and macroscopic properties of electrolytes is sparse for multivalent electrolytes and contradictory results have been reported in the literature. This review aims to illustrate the current understanding, compare results, and highlight future needs and directions to enable the deep understanding needed for the rational design of improved multivalent electrolytes.

Stabilization of Quinapril by Incorporating Hydrogen Bonding Interactions

PubMed Central

Roy, B. N.; Singh, G. P.; Godbole, H. M.; Nehate, S. P.

2009-01-01

In the present study stability of various known solvates of quinapril hydrochloride has been compared with nitromethane solvate. Nitromethane solvate was found to be more stable compared to other known solvates. Single crystal X-ray diffraction analysis of quinapril nitromethane solvate shows intermolecular hydrogen bonding between quinapril molecule and nitromethane. Stabilization of quinapril by forming strong hydrogen bonding network as in case of co-crystals was further studied by forming co-crystal with tris(hydroxymethyl)amino methane. Quinapril free base forms a stable salt with tris(hydroxymethyl)amino methane not reported earlier. Quinapril tris(hydroxymethyl)amino methane salt found to be stable even at 80° for 72 h i.e. hardly any formation of diketopiperazine and diacid impurity. As expected single crystal X-ray diffraction analysis reveals tris(hydroxymethyl)amino methane salt of quinapril shows complex hydrogen bonding network between the two entities along with ionic bond. The properties of this stable salt - stable in solid as well as solution phase, might lead to an alternate highly stable formulation. PMID:20502545

Extrapolating Single Organic Ion Solvation Thermochemistry from Simulated Water Nanodroplets.

PubMed

Coles, Jonathan P; Houriez, Céline; Meot-Ner Mautner, Michael; Masella, Michel

2016-09-08

We compute the ion/water interaction energies of methylated ammonium cations and alkylated carboxylate anions solvated in large nanodroplets of 10 000 water molecules using 10 ns molecular dynamics simulations and an all-atom polarizable force-field approach. Together with our earlier results concerning the solvation of these organic ions in nanodroplets whose molecular sizes range from 50 to 1000, these new data allow us to discuss the reliability of extrapolating absolute single-ion bulk solvation energies from small ion/water droplets using common power-law functions of cluster size. We show that reliable estimates of these energies can be extrapolated from a small data set comprising the results of three droplets whose sizes are between 100 and 1000 using a basic power-law function of droplet size. This agrees with an earlier conclusion drawn from a model built within the mean spherical framework and paves the road toward a theoretical protocol to systematically compute the solvation energies of complex organic ions.

Communication: Free-energy analysis of hydration effect on protein with explicit solvent: Equilibrium fluctuation of cytochrome c

NASA Astrophysics Data System (ADS)

Karino, Yasuhito; Matubayasi, Nobuyuki

2011-01-01

The relationship between the protein conformation and the hydration effect is investigated for the equilibrium fluctuation of cytochrome c. To elucidate the hydration effect with explicit solvent, the solvation free energy of the protein immersed in water was calculated using the molecular dynamics simulation coupled with the method of energy representation. The variations of the protein intramolecular energy and the solvation free energy are found to compensate each other in the course of equilibrium structural fluctuation. The roles of the attractive and repulsive components in the protein-water interaction are further examined for the solvation free energy. The attractive component represented as the average sum of protein-water interaction energy is dominated by the electrostatic effect and is correlated to the solvation free energy through the linear-response-type relationship. No correlation with the (total) solvation free energy is seen, on the other hand, for the repulsive component expressed as the excluded-volume effect.

Ultrafast Decay of the Solvated Electron in a Neat Polar Solvent: The Unusual Case of Propylene Carbonate.

PubMed

Le Caër, Sophie; Ortiz, Daniel; Marignier, Jean-Louis; Schmidhammer, Uli; Belloni, Jacqueline; Mostafavi, Mehran

2016-01-07

The behavior of carbonates is critical for a detailed understanding of aging phenomena in Li-ion batteries. Here we study the first reaction stages of propylene carbonate (PC), a cyclical carbonate, by picosecond pulse radiolysis. An absorption band with a maximum around 1360 nm is observed at 20 ps after the electron pulse and is shifted to 1310 nm after 50 ps. This band presents the features of a solvated electron absorption band, the solvation lasting up to 50 ps. Surprisingly, in this polar solvent, the solvated electron follows an ultrafast decay and disappears with a half time of 360 ps. This is attributed to the formation of a radical anion PC(-•). The yield of the solvated electron is low, suggesting that the radical anions are mainly directly produced from presolvated electrons. These results demonstrate that the initial electron transfers mechanisms are strongly different in linear compared with cyclical carbonates.

Electron solvation and localization at interfaces

NASA Astrophysics Data System (ADS)

Harris, Charles B.; Szymanski, Paul; Garrett-Roe, Sean; Miller, Andre D.; Gaffney, Kelly J.; Liu, Simon H.; Bezel, Ilya

2003-12-01

Two-photon photoemission of thiolate/Ag(111), nitrile/Ag(111), and alcohol/Ag(111) interfaces elucidates electron solvation and localization in two dimensions. For low coverages of thiolates on Ag(111), the occupied (HOMO) and unoccupied (LUMO) electronic states of the sulfer-silver bond are localized due to the lattice gas structure of the adsorbate. As the coverage saturates and the adsorbate-adsorbate nearest neighbor distance decreases, the HOMO and LUMO delocalize across many adsorbate molecules. Alcohol- and nitrile-covered Ag(111) surfaces solvate excess image potential state (IPS) electrons. In the case of alcohol-covered surfaces, this solvation is due to a shift in the local workfunction of the surface. For two-monolayer coverages of nitriles/Ag(111), localization accompanies solvation of the IPS. The size of the localized electron can be estimated by Fourier transformation of the wavefunction from momentum- to position-space. The IPS electron localizes to 15 +/- 4 angstroms full-width at half maximum in the plane of the surface, i.e., to a single lattice site.

Solvation and Dynamics of Sodium and Potassium in Ethylene Carbonate from ab Initio Molecular Dynamics Simulations

DOE PAGES

Pham, Tuan Anh; Kweon, Kyoung E.; Samanta, Amit; ...

2017-09-18

The development of sodium and potassium batteries offers a promising way to meet the scaling and cost challenges of energy storage. However, compared to Li +, several intrinsic properties of Na + and K +, including their solvation and dynamics in typical organic electrolytes utilized in battery applications, are less well-understood. Here in this paper, we report a systematic investigation of Na + and K + in ethylene carbonate (EC) using first-principles molecular dynamics simulations. Our simulations reveal significant differences in the solvation structure and dynamical properties of Na + and K + compared to Li +. We find that,more » in contrast to Li + which exhibits a well-defined first solvation shell, the larger Na+ and K+ ions show more disordered and flexible solvation structures. These differences in solvation were found to significantly influence the ion dynamics, leading to larger diffusion coefficients of Na + and K + compared to Li +. Our simulations also reveal a clear and interesting analog in the behavior of the ions in EC and aqueous environments, particularly in the specific ion effects on the solvent dynamics. Lastly, this work provides fundamental understanding of the intrinsic properties of Na + and K + in organic electrolytes, which may ultimately influence the intercalation mechanism at the electrode–electrolyte interface and therefore battery performance, lifetime, and safety.« less

Solvatochromism and preferential solvation of 1,4-dihydroxy-2,3-dimethyl-9,10-anthraquinone by UV-vis absorption and laser-induced fluorescence measurements

NASA Astrophysics Data System (ADS)

Sasirekha, V.; Vanelle, P.; Terme, T.; Ramakrishnan, V.

2008-12-01

Solvation characteristics of 1,4-dihydroxy-2,3-dimethyl-9,10-anthraquinone ( 1) in pure and binary solvent mixtures have been studied by UV-vis absorption spectroscopy and laser-induced fluorescence techniques. The binary solvent mixtures used as CCl 4 (tetrachloromethane)-DMF ( N, N-dimethylformamide), AN (acetonitrile)-DMSO (dimethylsulfoxide), CHCl 3 (chloroform)-DMSO, CHCl 3-MeOH (methanol), and MeOH-DMSO. The longest wavelength band of 1 has been studied in pure solvents as well as in binary solvent mixtures as a function of the bulk mole fraction. The Vis absorption band maxima show an unusual blue shift with increasing solvent polarity. The emission maxima of 1 show changes with varying the pure solvents and the composition in the case of binary solvent mixtures. Non-ideal solvation characteristics are observed in all binary solvent mixtures. It has been observed that the quantity [ ν-(Xν+Xν)] serves as a measure of the extent of preferential solvation, where ν˜ and X are the position of band maximum in wavenumbers (cm -1) and the bulk mole fraction values, respectively. The preferential solvation parameters local mole fraction ( X2L), solvation index ( δs2), and exchange constant ( k12) are evaluated.

Preferential solvation and solvation shell composition of free base and protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents

NASA Astrophysics Data System (ADS)

Farajtabar, Ali; Jaberi, Fatemeh; Gharib, Farrokh

2011-12-01

The solvatochromic properties of the free base and the protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) were studied in pure water, methanol, ethanol (protic solvents), dimethylsulfoxide, DMSO, (non-protic solvent), and their corresponding aqueous-organic binary mixed solvents. The correlation of the empirical solvent polarity scale ( ET) values of TPPS with composition of the solvents was analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition and the synergistic effects in preferential solvation of the solute dyes were investigated in terms of both solvent-solvent and solute-solvent interactions and also, the local mole fraction of each solvent composition was calculated in cybotactic region of the probe. The effective mole fraction variation may provide significant physico-chemical insights in the microscopic and molecular level of interactions between TPPS species and the solvent components and therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TPPS. The obtained results from the preferential solvation and solvent-solvent interactions have been successfully applied to explain the variation of equilibrium behavior of protonation of TPPS occurring in aqueous organic mixed solvents of methanol, ethanol and DMSO.

“Martinizing” the Variational Implicit Solvent Method (VISM): Solvation Free Energy for Coarse-Grained Proteins

PubMed Central

2017-01-01

Solvation is a fundamental driving force in many biological processes including biomolecular recognition and self-assembly, not to mention protein folding, dynamics, and function. The variational implicit solvent method (VISM) is a theoretical tool currently developed and optimized to estimate solvation free energies for systems of very complex topology, such as biomolecules. VISM’s theoretical framework makes it unique because it couples hydrophobic, van der Waals, and electrostatic interactions as a functional of the solvation interface. By minimizing this functional, VISM produces the solvation interface as an output of the theory. In this work, we push VISM to larger scale applications by combining it with coarse-grained solute Hamiltonians adapted from the MARTINI framework, a well-established mesoscale force field for modeling large-scale biomolecule assemblies. We show how MARTINI-VISM (MVISM) compares with atomistic VISM (AVISM) for a small set of proteins differing in size, shape, and charge distribution. We also demonstrate MVISM’s suitability to study the solvation properties of an interesting encounter complex, barnase–barstar. The promising results suggest that coarse-graining the protein with the MARTINI force field is indeed a valuable step to broaden VISM’s and MARTINI’s applications in the near future. PMID:28613904

Solvent-Induced Shift of Spectral Lines in Polar–Polarizable Solvents

DOE PAGES

Matyushov, Dmitry V.; Newton, Marshall D.

2017-03-09

Solvent-induced shift of optical transition lines is traditionally described by the Lippert- McRae equation given in terms of the Onsager theory for dipole solvation. It splits the overall shift into the equilibrium solvation by induced dipoles and the reaction field by the permanent dipoles in equilibrium with the chromophore in the ground state. Here we have reconsidered this classical problem from the perspective of microscopic solvation theories. A microscopic solvation functional is derived and continuum solvation is consistently introduced by taking the limit of zero wavevector in the reciprocal-space solvation susceptibility functions. We show that the phenomenological expression for themore » reaction field of permanent dipoles in the Lippert-McRae equation is not consistent with the microscopic theory. The main deficiency of the Lippert- McRae equation equation is the use of additivity of the response by permanent and induced dipoles of the liquid. An alternative closed-form equation for the spectral shift is derived. Its continuum limit allows a new, non-additive functionality for the solvent-induced shift in terms of the high-frequency and static dielectric constants. Finally, the main qualitative outcome of the theory is a significantly weaker dependence of the spectral shift on the polarizability of the solvent than predicted by the Lippert-McRae formula.« less

Combined Quantum Chemical/Raman Spectroscopic Analyses of Li+ Cation Solvation: Cyclic Carbonate Solvents - Ethylene Carbonate and Propylene Earbonate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allen, Joshua L.; Borodin, Oleg; Seo, D. M.

2014-12-01

Combined computational/Raman spectroscopic analyses of ethylene carbonate (EC) and propylene carbonate (PC) solvation interactions with lithium salts are reported. It is proposed that previously reported Raman analyses of (EC)n-LiX mixtures have utilized faulty assumptions. In the present studies, density functional theory (DFT) calculations have provided corrections in terms of both the scaling factors for the solvent's Raman band intensity variations and information about band overlap. By accounting for these factors, the solvation numbers obtained from two different EC solvent bands are in excellent agreement with one another. The same analysis for PC, however, was found to be quite challenging. Commerciallymore » available PC is a racemic mixture of (S)- and (R)-PC isomers. Based upon the quantum chemistry calculations, each of these solvent isomers may exist as multiple conformers due to a low energy barrier for ring inversion, making deconvolution of the Raman bands daunting and inherently prone to significant error. Thus, Raman spectroscopy is able to accurately determine the extent of the EC...Li+ cation solvation interactions using the provided methodology, but a similar analysis of PC...Li+ cation solvation results in a significant underestimation of the actual solvation numbers.« less

Solvent-Induced Shift of Spectral Lines in Polar-Polarizable Solvents.

PubMed

Matyushov, Dmitry V; Newton, Marshall D

2017-03-23

Solvent-induced shift of optical transition lines is traditionally described by the Lippert-McRae equation given in terms of the Onsager theory for dipole solvation. It splits the overall shift into the equilibrium solvation by induced dipoles and the reaction field by the permanent dipoles in equilibrium with the chromophore in the ground state. We have reconsidered this classical problem from the perspective of microscopic solvation theories. A microscopic solvation functional is derived, and continuum solvation is consistently introduced by taking the limit of zero wavevector in the reciprocal-space solvation susceptibility functions. We show that the phenomenological expression for the reaction field of permanent dipoles in the Lippert-McRae equation is not consistent with the microscopic theory. The main deficiency of the Lippert-McRae equation is the use of additivity of the response by permanent and induced dipoles of the liquid. An alternative closed-form equation for the spectral shift is derived. Its continuum limit allows a new, nonadditive functionality for the solvent-induced shift in terms of the high-frequency and static dielectric constants. The main qualitative outcome of the theory is a significantly weaker dependence of the spectral shift on the polarizability of the solvent than predicted by the Lippert-McRae formula.

Chiral supramolecular organization from a sheet-like achiral gel: a study of chiral photoinduction.

PubMed

Royes, Jorge; Polo, Víctor; Uriel, Santiago; Oriol, Luis; Piñol, Milagros; Tejedor, Rosa M

2017-05-31

Chiral photoinduction in a photoresponsive gel based on an achiral 2D architecture with high geometric anisotropy and low roughness has been investigated. Circularly polarized light (CPL) was used as a chiral source and an azobenzene chromophore was employed as a chiral trigger. The chiral photoinduction was studied by evaluating the preferential excitation of enantiomeric conformers of the azobenzene units. Crystallographic data and density functional theory (DFT) calculations show how chirality is transferred to the achiral azomaterials as a result of the combination of chiral photochemistry and supramolecular interactions. This procedure could be applied to predict and estimate chirality transfer from a chiral physical source to a supramolecular organization using different light-responsive units.

Understanding the influence of capillary waves on solvation at the liquid-vapor interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rane, Kaustubh, E-mail: rane@csi.tu-darmstadt.de; Vegt, Nico F. A. van der

2016-03-21

This work investigates the question if surface capillary waves (CWs) affect interfacial solvation thermodynamic properties that determine the propensity of small molecules toward the liquid-vapor interface. We focus on (1) the evaluation of these properties from molecular simulations in a practical manner and (2) understanding them from the perspective of theories in solvation thermodynamics, especially solvent reorganization effects. Concerning the former objective, we propose a computational method that exploits the relationship between an external field acting on the liquid-vapor interface and the magnitude of CWs. The system considered contains the solvent, an externally applied field (f) and the solute moleculemore » fixed at a particular location. The magnitude of f is selected to induce changes in CWs. The difference between the solvation free energies computed in the presence and in the absence of f is then shown to quantify the contribution of CWs to interfacial solvation. We describe the implementation of this method in the canonical ensemble by using a Lennard-Jones solvent and a non-ionic solute. Results are shown for three types of solutes that differ in the nature of short-ranged repulsive (hard-core) interactions. Overall, we observe that CWs have a negligible or very small effect on the interfacial solvation free energy of a solute molecule fixed near the liquid-vapor interface for the above systems. We also explain how the effects of pinning or dampening of CWs caused by a fixed solute are effectively compensated and do not contribute to the solvation free energy.« less

Phenolic Polymer Solvation in Water and Ethylene Glycol, I: Molecular Dynamics Simulations

NASA Technical Reports Server (NTRS)

Bucholz, Eric W.; Haskins, Justin B.; Monk, Joshua D.; Bauschlicher, Charles W.; Lawson, John W.

2017-01-01

Interactions between pre-cured phenolic polymer chains and a solvent have a significant impact on the structure and properties of the final post-cured phenolic resin. Developing an understanding of the nature of these interactions is important and will aid in the selection of the proper solvent that will lead to the desired final product. Here, we investigate the role of phenolic chain structure and solvent type on the overall solvation performance of the system through molecular dynamics simulations. Two types of solvents are considered, ethylene glycol (EGL) and H2O. In addition, three phenolic chain structures were considered including two novolac-type chains with either an ortho-ortho (OON) or ortho-para (OPN) backbone network and a resole-type (RES) chain with an ortho-ortho network. Each system is characterized through structural analysis of the solvation shell and hydrogen bonding environment as well as through quantification of the solvation free energy along with partitioned interaction energies between specific molecular species. The combination of the simulations and analyses indicate that EGL provides a larger solvation free energy than H2O due to more energetically favorable hydrophilic interactions as well as favorable hydrophobic interactions between CH element groups. In addition, phenolic chain structure significantly impacts solvation performance with OON having limited intermolecular hydrogen bond formations while OPN and RES interact more favorably with the solvent molecules. The results suggest that a resole-type phenolic chain with an ortho-para network should have the best solvation performance in EGL, H2O, and other similar solvents.

Phenolic Polymer Solvation in Water and Ethylene Glycol, I: Molecular Dynamics Simulations.

PubMed

Bucholz, Eric W; Haskins, Justin B; Monk, Joshua D; Bauschlicher, Charles W; Lawson, John W

2017-04-06

Interactions between pre-cured phenolic polymer chains and a solvent have a significant impact on the structure and properties of the final postcured phenolic resin. Developing an understanding of the nature of these interactions is important and will aid in the selection of the proper solvent that will lead to the desired final product. Here, we investigate the role of the phenolic chain structure and the solvent type on the overall solvation performance of the system through molecular dynamics simulations. Two types of solvents are considered: ethylene glycol (EGL) and H 2 O. In addition, three phenolic chain structures are considered, including two novolac-type chains with either an ortho-ortho (OON) or an ortho-para (OPN) backbone network and a resole-type (RES) chain with an ortho-ortho network. Each system is characterized through a structural analysis of the solvation shell and the hydrogen-bonding environment as well as through a quantification of the solvation free energy along with partitioned interaction energies between specific molecular species. The combination of simulations and the analyses indicate that EGL provides a higher solvation free energy than H 2 O due to more energetically favorable hydrophilic interactions as well as favorable hydrophobic interactions between CH element groups. In addition, the phenolic chain structure significantly affects the solvation performance, with OON having limited intermolecular hydrogen-bond formations, while OPN and RES interact more favorably with the solvent molecules. The results suggest that a resole-type phenolic chain with an ortho-para network should have the best solvation performance in EGL, H 2 O, and other similar solvents.

Development of a methodology to compute solvation free energies on the basis of the theory of energy representation for solutions represented with a polarizable force field.

PubMed

Suzuoka, Daiki; Takahashi, Hideaki; Ishiyama, Tatsuya; Morita, Akihiro

2012-12-07

We have developed a method of molecular simulations utilizing a polarizable force field in combination with the theory of energy representation (ER) for the purpose of establishing an efficient and accurate methodology to compute solvation free energies. The standard version of the ER method is, however, based on the assumption that the solute-solvent interaction is pairwise additive for its construction. A crucial step in the present method is to introduce an intermediate state in the solvation process to treat separately the many-body interaction associated with the polarizable model. The intermediate state is chosen so that the solute-solvent interaction can be formally written in the pairwise form, though the solvent molecules are interacting with each other with polarizable charges dependent on the solvent configuration. It is, then, possible to extract the free energy contribution δμ due to the many-body interaction between solute and solvent from the total solvation free energy Δμ. It is shown that the free energy δμ can be computed by an extension of the recent development implemented in quantum mechanical∕molecular mechanical simulations. To assess the numerical robustness of the approach, we computed the solvation free energies of a water and a methanol molecule in water solvent, where two paths for the solvation processes were examined by introducing different intermediate states. The solvation free energies of a water molecule associated with the two paths were obtained as -5.3 and -5.8 kcal∕mol. Those of a methanol molecule were determined as -3.5 and -3.7 kcal∕mol. These results of the ER simulations were also compared with those computed by a numerically exact approach. It was demonstrated that the present approach produces the solvation free energies in comparable accuracies to simulations of thermodynamic integration (TI) method within a tenth of computational time used for the TI simulations.

Molecular basis for competitive solvation of the Burkholderia cepacia lipase by sorbitol and urea.

PubMed

Oliveira, Ivan P; Martínez, Leandro

2016-08-21

Increasing the stability of proteins is important for their application in industrial processes. In the intracellular environment many small molecules, called osmolytes, contribute to protein stabilization under physical or chemical stress. Understanding the nature of the interactions of these osmolytes with proteins can help the design of solvents and mutations to increase protein stability in extracellular media. One of the most common stabilizing osmolyes is sorbitol and one of the most common chemical denaturants is urea. In this work, we use molecular dynamics simulations to obtain a detailed picture of the solvation of the Burkholderia cepacia lipase (BCL) in the presence of the protecting osmolyte sorbitol and of the urea denaturant. We show that both sorbitol and urea compete with water for interactions with the protein surface. Overall, sorbitol promotes the organization of water in the first solvation shell and displaces water from the second solvation shell, while urea causes opposite effects. These effects are, however, highly heterogeneous among residue types. For instance, the depletion of water from the first protein solvation shell by urea can be traced down essentially to the side chain of negatively charged residues. The organization of water in the first solvation shell promoted by sorbitol occurs at polar (but not charged) residues, where the urea effect is minor. By contrast, sorbitol depletes water from the second solvation shell of polar residues, while urea promotes water organization at the same distances. The interactions of urea with negatively charged residues are insensitive to the presence of sorbitol. This osmolyte removes water and urea particularly from the second solvation shell of polar and non-polar residues. In summary, we provide a comprehensive description of the diversity of protein-solvent interactions, which can guide further investigations on the stability of proteins in non-conventional media, and assist solvent and protein design.

Hierarchical chirality transfer in the growth of Towel Gourd tendrils

PubMed Central

Wang, Jian-Shan; Wang, Gang; Feng, Xi-Qiao; Kitamura, Takayuki; Kang, Yi-Lan; Yu, Shou-Wen; Qin, Qing-Hua

2013-01-01

Chirality plays a significant role in the physical properties and biological functions of many biological materials, e.g., climbing tendrils and twisted leaves, which exhibit chiral growth. However, the mechanisms underlying the chiral growth of biological materials remain unclear. In this paper, we investigate how the Towel Gourd tendrils achieve their chiral growth. Our experiments reveal that the tendrils have a hierarchy of chirality, which transfers from the lower levels to the higher. The change in the helical angle of cellulose fibrils at the subcellular level induces an intrinsic torsion of tendrils, leading to the formation of the helical morphology of tendril filaments. A chirality transfer model is presented to elucidate the chiral growth of tendrils. This present study may help understand various chiral phenomena observed in biological materials. It also suggests that chirality transfer can be utilized in the development of hierarchically chiral materials having unique properties. PMID:24173107

Direct Detection of Hardly Detectable Hidden Chirality of Hydrocarbons and Deuterated Isotopomers by a Helical Polyacetylene through Chiral Amplification and Memory.

PubMed

Maeda, Katsuhiro; Hirose, Daisuke; Okoshi, Natsuki; Shimomura, Kouhei; Wada, Yuya; Ikai, Tomoyuki; Kanoh, Shigeyoshi; Yashima, Eiji

2018-03-07

We report the first direct chirality sensing of a series of chiral hydrocarbons and isotopically chiral compounds (deuterated isotopomers), which are almost impossible to detect by conventional optical spectroscopic methods, by a stereoregular polyacetylene bearing 2,2'-biphenol-derived pendants. The polyacetylene showed a circular dichroism due to a preferred-handed helix formation in response to the hardly detectable hidden chirality of saturated tertiary or chiroptical quaternary hydrocarbons, and deuterated isotopomers. In sharp contrast to the previously reported sensory systems, the chirality detection by the polyacetylene relies on an excess one-handed helix formation induced by the chiral hydrocarbons and deuterated isotopomers via significant amplification of the chirality followed by its static memory, through which chiral information on the minute and hidden chirality can be stored as an excess of a single-handed helix memory for a long time.

Chiral Recognition and Separation by Chirality-Enriched Metal-Organic Frameworks.

PubMed

Das, Saikat; Xu, Shixian; Ben, Teng; Qiu, Shilun

2018-05-16

Endowed with chiral channels and pores, chiral metal-organic frameworks (MOFs) are highly useful; however, their synthesis remains a challenge given that most chiral building blocks are expensive. Although MOFs with induced chirality have been reported to avoid this shortcoming, no study providing evidence for the ee value of such MOFs has yet been reported. We herein describe the first study on the efficiency of chiral induction in MOFs using inexpensive achiral building blocks and fully recoverable chiral dopants to control the handedness of racemic MOFs. This method yielded chirality-enriched MOFs with accessible pores. The ability of the materials to form host-guest complexes was probed with enantiomers of varying size and coordination and in solvents with varying polarity. Furthermore, mixed-matrix membranes (MMMs) composed of chirality-enriched MOF particles dispersed in a polymer matrix demonstrated a new route for chiral separation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent progress of chiral stationary phases for separation of enantiomers in gas chromatography.

PubMed

Xie, Sheng-Ming; Yuan, Li-Ming

2017-01-01

Chromatography techniques based on chiral stationary phases are widely used for the separation of enantiomers. In particular, gas chromatography has developed rapidly in recent years due to its merits such as fast analysis speed, lower consumption of stationary phases and analytes, higher column efficiency, making it a better choice for chiral separation in diverse industries. This article summarizes recent progress of novel chiral stationary phases based on cyclofructan derivatives and chiral porous materials including chiral metal-organic frameworks, chiral porous organic frameworks, chiral inorganic mesoporous materials, and chiral porous organic cages in gas chromatography, covering original research papers published since 2010. The chiral recognition properties and mechanisms of separation toward enantiomers are also introduced. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thin Metallic Films From Solvated Metal Atoms

NASA Astrophysics Data System (ADS)

Trivino, Galo C.; Klabunde, Kenneth J.; Dale, Brock

1988-02-01

Metals were evaporated under vacuum and the metal atoms solvated by excess organic solvents at low temperature. Upon warming stable colloidal metal particles were formed by controlled metal atom clustering. The particles were stabilized toward flocculation by solvation and electrostatic effects. Upon solvent removal the colloidal particles grew to form thin films that were metallic in appearance, but showed higher resistivities than pure metallic films. Gold, palladium, platinium, and especially indium are discussed.

Analysis of biomolecular solvation sites by 3D-RISM theory.

PubMed

Sindhikara, Daniel J; Hirata, Fumio

2013-06-06

We derive, implement, and apply equilibrium solvation site analysis for biomolecules. Our method utilizes 3D-RISM calculations to quickly obtain equilibrium solvent distributions without either necessity of simulation or limits of solvent sampling. Our analysis of these distributions extracts highest likelihood poses of solvent as well as localized entropies, enthalpies, and solvation free energies. We demonstrate our method on a structure of HIV-1 protease where excellent structural and thermodynamic data are available for comparison. Our results, obtained within minutes, show systematic agreement with available experimental data. Further, our results are in good agreement with established simulation-based solvent analysis methods. This method can be used not only for visual analysis of active site solvation but also for virtual screening methods and experimental refinement.

Revisiting structure and dynamics of preferential solvation of K(I) ion in aqueous ammonia using QMCF-MD simulation

NASA Astrophysics Data System (ADS)

Hidayat, Yuniawan; Pranowo, Harno Dwi; Armunanto, Ria

2018-05-01

Structure and dynamics of preferential solvation of K(I) ion in aqueous ammonia have been reinvestigated using ab initio quantum mechanical charge field (QMCF) molecular dynamics (MD) simulation. The average coordination number of the first solvation consists of 2 ammonia and 4 waters. The mean residence time is less than 2 ps confirming the rapid mobility of ligands. The distance evolution data shows the frequent of ligand exchanges. The second solvation shell shows a more labile structure. The NBO analysis of the first shell structure emphasizes that interaction of K(I)-H2O is stronger than K(I)-NH3. The Wiberg bond confirms a weak electrostatic of ion-ligand interaction.

Decomposition of total solvation energy into core, side-chains and water contributions: Role of cross correlations and protein conformational fluctuations in dynamics of hydration layer

NASA Astrophysics Data System (ADS)

Mondal, Sayantan; Mukherjee, Saumyak; Bagchi, Biman

2017-09-01

Dynamical coupling between water and amino acid side-chain residues in solvation dynamics is investigated by selecting residues often used as natural probes, namely tryptophan, tyrosine and histidine, located at different positions on protein surface. Such differently placed residues are found to exhibit different timescales of relaxation. The total solvation response measured by the probe is decomposed in terms of its interactions with (i) protein core, (ii) side-chain and (iii) water. Significant anti cross-correlation among these contributions are observed. When the motion of the protein side-chains is quenched, solvation either becomes faster or slower depending on the location of the probe.

The Generalized Born solvation model: What is it?

NASA Astrophysics Data System (ADS)

Onufriev, Alexey

2004-03-01

Implicit solvation models provide, for many applications, an effective way of describing the electrostatic effects of aqueous solvation. Here we outline the main approximations behind the popular Generalized Born solvation model. We show how its accuracy, relative to the Poisson-Boltzmann treatment, can be significantly improved in a computationally inexpensive manner to make the model useful in the studies of large-scale conformational transitions at the atomic level. The improved model is tested in a molecular dynamics simulation of folding of a 46-residue (three helix bundle) protein. Starting from an extended structure at 450K, the protein folds to the lowest energy conformation within 6 ns of simulation time, and the predicted structure differs from the native one by 2.4 A (backbone RMSD).

Chiral Magnetic Effect in Condensed Matters

NASA Astrophysics Data System (ADS)

Li, Qiang

The chiral magnetic effect is the generation of electrical current induced by chirality imbalance in the presence of magnetic field. It is a macroscopic manifestation of the quantum chiral anomaly in systems possessing charged chiral fermions. In quark-gluon plasma containing nearly massless quarks, the chirality imbalance is sourced by the topological transitions. In condensed matter systems, the chiral quasiparticles emerge in the 3D Dirac and Weyl semimetals having a linear dispersion relation. Recently, the chiral magnetic effect was discovered in a 3D Dirac semimetal - zirconium pentatelluride, ZrTe5, in which a large negative magnetoresistance is observed when magnetic field is parallel with the current. It is now reported in more than a dozen Dirac and Weyl semimetals. Broadly speaking, the chiral magnetic effect can exist in a variety of condensed matters. In some cases, a material may be transformed into a Weyl semimetal by magnetic field, exhibiting the chiral magnetic effect. In other cases, the chiral magnetic current may be generated in magnetic Dirac semimetals without external magnetic field, or in asymmetric Weyl semimetals without electric field where only a magnetic field and the source of chiral quasipartiles would be necessary. In the limit of conserved quasiparticle chirality, charge transport by the chiral magnetic current is non-dissipative. The powerful notion of chirality, originally discovered in high-energy and nuclear physics, holds promise in new ways of transmitting and processing information and energy. At the same time, chiral materials have opened a fascinating possibility to study the quantum dynamics of relativistic field theory in condensed matter experiments.

Fluoro-alcohol phase modifiers and process for cesium solvent extraction

DOEpatents

Bonnesen, Peter V.; Moyer, Bruce A.; Sachleben, Richard A.

2003-05-20

The invention relates to a class of phenoxy fluoro-alcohols, their preparation, and their use as phase modifiers and solvating agents in a solvent composition for the extraction of cesium from alkaline solutions. These phenoxy fluoro-alcohols comply with the formula: ##STR1## in which n=2 to 4; X represents a hydrogen or a fluorine atom, and R.sup.2 -R.sup.6 are hydrogen or alkyl substituents. These phenoxy fluoro-alcohol phase modifiers are a necessary component to a robust solvent composition and process useful for the removal of radioactive cesium from alkaline nuclear waste streams. The fluoro-alcohols can also be used in solvents designed to extract other cesium from acidic or neutral solutions.

Can a Non-Chiral Object Be Made of Two Identical Chiral Moieties?

ERIC Educational Resources Information Center

LeMarechal, Jean Francois

2008-01-01

Several pedagogical objects can be used to discuss chirality. Here, we use the cut of an apple to show that the association of identical chiral moieties can form a non-chiral object. Octahedral chirality is used to find situations equivalent to the cut of the apple. (Contains 5 figures.)

Meta-Chirality: Fundamentals, Construction and Applications

PubMed Central

Ma, Xiaoliang; Pu, Mingbo; Li, Xiong; Guo, Yinghui; Gao, Ping; Luo, Xiangang

2017-01-01

Chiral metamaterials represent a special type of artificial structures that cannot be superposed to their mirror images. Due to the lack of mirror symmetry, cross-coupling between electric and magnetic fields exist in chiral mediums and present unique electromagnetic characters of circular dichroism and optical activity, which provide a new opportunity to tune polarization and realize negative refractive index. Chiral metamaterials have attracted great attentions in recent years and have given rise to a series of applications in polarization manipulation, imaging, chemical and biological detection, and nonlinear optics. Here we review the fundamental theory of chiral media and analyze the construction principles of some typical chiral metamaterials. Then, the progress in extrinsic chiral metamaterials, absorbing chiral metamaterials, and reconfigurable chiral metamaterials are summarized. In the last section, future trends in chiral metamaterials and application in nonlinear optics are introduced. PMID:28513560

Chiral acidic amino acids induce chiral hierarchical structure in calcium carbonate

PubMed Central

Jiang, Wenge; Pacella, Michael S.; Athanasiadou, Dimitra; Nelea, Valentin; Vali, Hojatollah; Hazen, Robert M.; Gray, Jeffrey J.; McKee, Marc D.

2017-01-01

Chirality is ubiquitous in biology, including in biomineralization, where it is found in many hardened structures of invertebrate marine and terrestrial organisms (for example, spiralling gastropod shells). Here we show that chiral, hierarchically organized architectures for calcium carbonate (vaterite) can be controlled simply by adding chiral acidic amino acids (Asp and Glu). Chiral, vaterite toroidal suprastructure having a ‘right-handed' (counterclockwise) spiralling morphology is induced by L-enantiomers of Asp and Glu, whereas ‘left-handed' (clockwise) morphology is induced by D-enantiomers, and sequentially switching between amino-acid enantiomers causes a switch in chirality. Nanoparticle tilting after binding of chiral amino acids is proposed as a chiral growth mechanism, where a ‘mother' subunit nanoparticle spawns a slightly tilted, consequential ‘daughter' nanoparticle, which by amplification over various length scales creates oriented mineral platelets and chiral vaterite suprastructures. These findings suggest a molecular mechanism for how biomineralization-related enantiomers might exert hierarchical control to form extended chiral suprastructures. PMID:28406143

Chirality Differentiation by Diffusion in Chiral Nematic Liquid Crystals

NASA Astrophysics Data System (ADS)

Jiang, Jinghua; Yang, Deng-Ke

2017-01-01

Chirality is of great importance in the living world. It helps differentiate biochemical reactions such as those that take place during digestion. It may also help differentiate physical processes such as diffusion. Aiming to study the latter effect, we investigate the diffusion of guest chiral molecules in chiral nematic (cholesteric) liquid-crystal hosts. We discover that the diffusion dramatically depends on the handedness of the guest and host molecules and the chiral differentiation is greatly enhanced by the proper alignment of the liquid-crystal host. The diffusion of a guest chiral molecule in a chiral host with the same handedness is much faster than in a chiral host with opposite handedness. We also observe that the differentiation of chirality depends on the diffusion direction with respect to the twisting direction (helical axis). These results might be important in understanding effects of chirality on physical processes that take place in biological organisms. In addition, this effect could be utilized for enantiomer separation.

Photoexcitation circular dichroism in chiral molecules

NASA Astrophysics Data System (ADS)

Beaulieu, S.; Comby, A.; Descamps, D.; Fabre, B.; Garcia, G. A.; Géneaux, R.; Harvey, A. G.; Légaré, F.; Mašín, Z.; Nahon, L.; Ordonez, A. F.; Petit, S.; Pons, B.; Mairesse, Y.; Smirnova, O.; Blanchet, V.

2018-05-01

Chiral effects appear in a wide variety of natural phenomena and are of fundamental importance in science, from particle physics to metamaterials. The standard technique of chiral discrimination—photoabsorption circular dichroism—relies on the magnetic properties of a chiral medium and yields an extremely weak chiral response. Here, we propose and demonstrate an orders of magnitude more sensitive type of circular dichroism in neutral molecules: photoexcitation circular dichroism. This technique does not rely on weak magnetic effects, but takes advantage of the coherent helical motion of bound electrons excited by ultrashort circularly polarized light. It results in an ultrafast chiral response and the efficient excitation of a macroscopic chiral density in an initially isotropic ensemble of randomly oriented chiral molecules. We probe this excitation using linearly polarized laser pulses, without the aid of further chiral interactions. Our time-resolved study of vibronic chiral dynamics opens a way to the efficient initiation, control and monitoring of chiral chemical change in neutral molecules at the level of electrons.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Maoyuan; Besford, Quinn Alexander; Mulvaney, Thomas

The entropy of hydrophobic solvation has been explained as the result of ordered solvation structures, of hydrogen bonds, of the small size of the water molecule, of dispersion forces, and of solvent density fluctuations. We report a new approach to the calculation of the entropy of hydrophobic solvation, along with tests of and comparisons to several other methods. The methods are assessed in the light of the available thermodynamic and spectroscopic information on the effects of temperature on hydrophobic solvation. Five model hydrophobes in SPC/E water give benchmark solvation entropies via Widom’s test-particle insertion method, and other methods and modelsmore » are tested against these particle-insertion results. Entropies associated with distributions of tetrahedral order, of electric field, and of solvent dipole orientations are examined. We find these contributions are small compared to the benchmark particle-insertion entropy. Competitive with or better than other theories in accuracy, but with no free parameters, is the new estimate of the entropy contributed by correlations between dipole moments. Dipole correlations account for most of the hydrophobic solvation entropy for all models studied and capture the distinctive temperature dependence seen in thermodynamic and spectroscopic experiments. Entropies based on pair and many-body correlations in number density approach the correct magnitudes but fail to describe temperature and size dependences, respectively. Hydrogen-bond definitions and free energies that best reproduce entropies from simulations are reported, but it is difficult to choose one hydrogen bond model that fits a variety of experiments. The use of information theory, scaled-particle theory, and related methods is discussed briefly. Our results provide a test of the Frank-Evans hypothesis that the negative solvation entropy is due to structured water near the solute, complement the spectroscopic detection of that solvation structure by identifying the structural feature responsible for the entropy change, and point to a possible explanation for the observed dependence on length scale. Our key results are that the hydrophobic effect, i.e. the signature, temperature-dependent, solvation entropy of nonpolar molecules in water, is largely due to a dispersion force arising from correlations between rotating permanent dipole moments, that the strength of this force depends on the Kirkwood g-factor, and that the strength of this force may be obtained exactly without simulation.« less

Ionic size effects to molecular solvation energy and to ion current across a channel resulted from the nonuniform size-modified PNP equations.

PubMed

Qiao, Yu; Tu, Bin; Lu, Benzhuo

2014-05-07

Ionic finite size can impose considerable effects to both the equilibrium and non-equilibrium properties of a solvated molecular system, such as the solvation energy, ionic concentration, and transport in a channel. As discussed in our former work [B. Lu and Y. C. Zhou, Biophys. J. 100, 2475 (2011)], a class of size-modified Poisson-Boltzmann (PB)/Poisson-Nernst-Planck (PNP) models can be uniformly studied through the general nonuniform size-modified PNP (SMPNP) equations deduced from the extended free energy functional of Borukhov et al. [I. Borukhov, D. Andelman, and H. Orland, Phys. Rev. Lett. 79, 435 (1997)] This work focuses on the nonuniform size effects to molecular solvation energy and to ion current across a channel for real biomolecular systems. The main contributions are: (1) we prove that for solvation energy calculation with nonuniform size effects (through equilibrium SMPNP simulation), there exists a simplified approximation formulation which is the same as the widely used one in PB community. This approximate form avoids integration over the whole domain and makes energy calculations convenient. (2) Numerical calculations show that ionic size effects tend to negate the solvation effects, which indicates that a higher molecular solvation energy (lower absolute value) is to be predicted when ionic size effects are considered. For both calculations on a protein and a DNA fragment systems in a 0.5M 1:1 ionic solution, a difference about 10 kcal/mol in solvation energies is found between the PB and the SMPNP predictions. Moreover, it is observed that the solvation energy decreases as ionic strength increases, which behavior is similar as those predicted by the traditional PB equation (without size effect) and by the uniform size-modified Poisson-Boltzmann equation. (3) Nonequilibrium SMPNP simulations of ion permeation through a gramicidin A channel show that the ionic size effects lead to reduced ion current inside the channel compared with the results without considering size effects. As a component of the current, the drift term is the main contribution to the total current. The ionic size effects to the total current almost come through the drift term, and have little influence on the diffusion terms in SMPNP.

Cell Chirality Drives Left-Right Asymmetric Morphogenesis.

PubMed

Inaki, Mikiko; Sasamura, Takeshi; Matsuno, Kenji

2018-01-01

Most macromolecules found in cells are chiral, meaning that they cannot be superimposed onto their mirror image. However, cells themselves can also be chiral, a subject that has received little attention until very recently. In our studies on the mechanisms of left-right (LR) asymmetric development in Drosophila , we discovered that cells can have an intrinsic chirality to their structure, and that this "cell chirality" is generally responsible for the LR asymmetric development of certain organs in this species. The actin cytoskeleton plays important roles in the formation of cell chirality. In addition, Myosin31DF ( Myo31DF ), which encodes Drosophila Myosin ID, was identified as a molecular switch for cell chirality. In other invertebrate species, including snails and Caenorhabditis elegans , chirality of the blastomeres, another type of cell chirality, determines the LR asymmetry of structures in the body. Thus, chirality at the cellular level may broadly contribute to LR asymmetric development in various invertebrate species. Recently, cell chirality was also reported for various vertebrate cultured cells, and studies suggested that cell chirality is evolutionarily conserved, including the essential role of the actin cytoskeleton. Although the biological roles of cell chirality in vertebrates remain unknown, it may control LR asymmetric development or other morphogenetic events. The investigation of cell chirality has just begun, and this new field should provide valuable new insights in biology and medicine.

Cell chirality: its origin and roles in left–right asymmetric development

PubMed Central

Inaki, Mikiko; Liu, Jingyang

2016-01-01

An item is chiral if it cannot be superimposed on its mirror image. Most biological molecules are chiral. The homochirality of amino acids ensures that proteins are chiral, which is essential for their functions. Chirality also occurs at the whole-cell level, which was first studied mostly in ciliates, single-celled protozoans. Ciliates show chirality in their cortical structures, which is not determined by genetics, but by ‘cortical inheritance’. These studies suggested that molecular chirality directs whole-cell chirality. Intriguingly, chirality in cellular structures and functions is also found in metazoans. In Drosophila, intrinsic cell chirality is observed in various left–right (LR) asymmetric tissues, and appears to be responsible for their LR asymmetric morphogenesis. In other invertebrates, such as snails and Caenorhabditis elegans, blastomere chirality is responsible for subsequent LR asymmetric development. Various cultured cells of vertebrates also show intrinsic chirality in their cellular behaviours and intracellular structural dynamics. Thus, cell chirality may be a general property of eukaryotic cells. In Drosophila, cell chirality drives the LR asymmetric development of individual organs, without establishing the LR axis of the whole embryo. Considering that organ-intrinsic LR asymmetry is also reported in vertebrates, this mechanism may contribute to LR asymmetric development across phyla. This article is part of the themed issue ‘Provocative questions in left–right asymmetry’. PMID:27821533

Cell chirality: its origin and roles in left-right asymmetric development.

PubMed

Inaki, Mikiko; Liu, Jingyang; Matsuno, Kenji

2016-12-19

An item is chiral if it cannot be superimposed on its mirror image. Most biological molecules are chiral. The homochirality of amino acids ensures that proteins are chiral, which is essential for their functions. Chirality also occurs at the whole-cell level, which was first studied mostly in ciliates, single-celled protozoans. Ciliates show chirality in their cortical structures, which is not determined by genetics, but by 'cortical inheritance'. These studies suggested that molecular chirality directs whole-cell chirality. Intriguingly, chirality in cellular structures and functions is also found in metazoans. In Drosophila, intrinsic cell chirality is observed in various left-right (LR) asymmetric tissues, and appears to be responsible for their LR asymmetric morphogenesis. In other invertebrates, such as snails and Caenorhabditis elegans, blastomere chirality is responsible for subsequent LR asymmetric development. Various cultured cells of vertebrates also show intrinsic chirality in their cellular behaviours and intracellular structural dynamics. Thus, cell chirality may be a general property of eukaryotic cells. In Drosophila, cell chirality drives the LR asymmetric development of individual organs, without establishing the LR axis of the whole embryo. Considering that organ-intrinsic LR asymmetry is also reported in vertebrates, this mechanism may contribute to LR asymmetric development across phyla.This article is part of the themed issue 'Provocative questions in left-right asymmetry'. © 2016 The Authors.

Selectively transporting small chiral particles with circularly polarized Airy beams.

PubMed

Lu, Wanli; Chen, Huajin; Guo, Sandong; Liu, Shiyang; Lin, Zhifang

2018-05-01

Based on the full wave simulation, we demonstrate that a circularly polarized vector Airy beam can selectively transport small chiral particles along a curved trajectory via the chirality-tailored optical forces. The transverse optical forces can draw the chiral particles with different particle chirality towards or away from the intensity maxima of the beam, leading to the selective trapping in the transverse plane. The transversely trapped chiral particles are then accelerated along a curved trajectory of the Airy beam by the chirality-tailored longitudinal scattering force, rendering an alternative way to sort and/or transport chiral particles with specified helicity. Finally, the underlying physics of the chirality induced transverse trap and de-trap phenomena are examined by the analytical theory within the dipole approximation.

Silver Films with Hierarchical Chirality.

PubMed

Ma, Liguo; Cao, Yuanyuan; Duan, Yingying; Han, Lu; Che, Shunai

2017-07-17

Physical fabrication of chiral metallic films usually results in singular or large-sized chirality, restricting the optical asymmetric responses to long electromagnetic wavelengths. The chiral molecule-induced formation of silver films prepared chemically on a copper substrate through a redox reaction is presented. Three levels of chirality were identified: primary twisted nanoflakes with atomic crystal lattices, secondary helical stacking of these nanoflakes to form nanoplates, and tertiary micrometer-sized circinates consisting of chiral arranged nanoplates. The chiral Ag films exhibited multiple plasmonic absorption- and scattering-based optical activities at UV/Vis wavelengths based on their hierarchical chirality. The Ag films showed chiral selectivity for amino acids in catalytic electrochemical reactions, which originated from their primary atomic crystal lattices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

SISGR: Linking Ion Solvation and Lithium Battery Electrolyte Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trulove, Paul C.; Foley, Matthew P.

2012-09-30

The solvation and phase behavior of the model battery electrolyte salt lithium trifluoromethanesulfonate (LiCF 3SO 3) in commonly used organic solvents; ethylene carbonate (EC), gamma-butyrolactone (GBL), and propylene carbonate (PC) was explored. Data from differential scanning calorimetry (DSC), Raman spectroscopy, and X-ray diffraction were correlated to provide insight into the solvation states present within a sample mixture. Data from DSC analyses allowed the construction of phase diagrams for each solvent system. Raman spectroscopy enabled the determination of specific solvation states present within a solvent-salt mixture, and X-ray diffraction data provided exact information concerning the structure of a solvates that couldmore » be isolated Thermal analysis of the various solvent-salt mixtures revealed the phase behavior of the model electrolytes was strongly dependent on solvent symmetry. The point groups of the solvents were (in order from high to low symmetry): C2V for EC, CS for GBL, and C1 for PC(R). The low symmetry solvents exhibited a crystallinity gap that increased as solvent symmetry decreased; no gap was observed for EC-LiTf, while a crystallinity gap was observed spanning 0.15 to 0.3 mole fraction for GBL-LiTf, and 0.1 to 0.33 mole fraction for PC(R)-LiTf mixtures. Raman analysis demonstrated the dominance of aggregated species in almost all solvent compositions. The AGG and CIP solvates represent the majority of the species in solutions for the more concentrated mixtures, and only in very dilute compositions does the SSIP solvate exist in significant amounts. Thus, the poor charge transport characteristics of CIP and AGG account for the low conductivity and transport properties of LiTf and explain why is a poor choice as a source of Li + ions in a Li-ion battery.« less

The road not taken: Applications of fluorescence spectroscopy and electronic structure theory to systems of materials and biological relevance

NASA Astrophysics Data System (ADS)

Carlson, Philip Joseph

Applications of Fluorescence Spectroscopy and Electronic Structure Theory to Systems of Materials and Biological Relevance. The photophysics of curcumin was studied in micelles and the solvation dynamics were probed. The high-energy ionic liquid HEATN was also studied using the fragment molecular orbital method. The solvation dynamics of the HEATN system were determined. This marks the first study of the solvation dynamics in a triazolium ionic liquid system.

Phase-Equilibria and Nanostructure Formation in Charged Rigid-Rod Polymers and Carbon Nanotubes

DTIC Science & Technology

2002-11-10

or liquid crystalline) and the crystalline polymer state. The form-I crystal solvate, identi- fied as a cocrystal of the protonated polymer and the...dissolution temperature, below 100 °C.12,13 The form-II crystal solvate, considered a polymer-solvent cocrystal in which the polymer is deprotonated,11,12...solvate that is a cocrystal of protonated PBZT and PPA anions. As previously mentioned, the fact that these two extreme cases result in similar

Calculating pKa values for substituted phenols and hydration energies for other compounds with the first-order Fuzzy-Border continuum solvation model

PubMed Central

Sharma, Ity; Kaminski, George A.

2012-01-01

We have computed pKa values for eleven substituted phenol compounds using the continuum Fuzzy-Border (FB) solvation model. Hydration energies for 40 other compounds, including alkanes, alkenes, alkynes, ketones, amines, alcohols, ethers, aromatics, amides, heterocycles, thiols, sulfides and acids have been calculated. The overall average unsigned error in the calculated acidity constant values was equal to 0.41 pH units and the average error in the solvation energies was 0.076 kcal/mol. We have also reproduced pKa values of propanoic and butanoic acids within ca. 0.1 pH units from the experimental values by fitting the solvation parameters for carboxylate ion carbon and oxygen atoms. The FB model combines two distinguishing features. First, it limits the amount of noise which is common in numerical treatment of continuum solvation models by using fixed-position grid points. Second, it employs either second- or first-order approximation for the solvent polarization, depending on a particular implementation. These approximations are similar to those used for solute and explicit solvent fast polarization treatment which we developed previously. This article describes results of employing the first-order technique. This approximation places the presented methodology between the Generalized Born and Poisson-Boltzmann continuum solvation models with respect to their accuracy of reproducing the many-body effects in modeling a continuum solvent. PMID:22815192

Understanding Lithium Solvation and Diffusion through Topological Analysis of First-Principles Molecular Dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhatia, Harsh; Gyulassy, Attila; Ong, Mitchell

2016-09-27

The performance of lithium-ion batteries is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact, both, the solvation and diffusivity of Li ions. In this work, we present our application of the topological techniques to extract and predict such behavior in the data generated by the first-principles molecular dynamics simulation of Li ions in an important organic solvent -ethylene carbonate. More specifically, we use the scalar topology of the electron charge density field tomore » analyze the evolution of the solvation structures. This allows us to derive a parameter-free bond definition for lithium-oxygen bonds, to provide a quantitative measure for bond strength, and to understand the regions of influence of each atom in the simulation. This has provided new insights into how and under what conditions certain bonds may form and break. As a result, we can identify and, more importantly, predict, unstable configurations in solvation structures. This can be very useful in understanding when small changes to the atoms' movements can cause significantly different bond structures to evolve. Ultimately, this promises to allow scientists to explore lithium ion solvation and diffusion more systematically, with the aim of new insights and potentially accelerating the calculations themselves.« less

Maltodextrins as chiral selectors in CE: molecular structure effect of basic chiral compounds on the enantioseparation.

PubMed

Tabani, Hadi; Fakhari, Ali Reza; Nojavan, Saeed

2014-10-01

Prediction of chiral separation for a compound using a chiral selector is an interesting and debatable work. For this purpose, in this study 23 chiral basic drugs with different chemical structures were selected as model solutes and the influence of their chemical structures on the enantioseparation in the presence of maltodextrin (MD) as chiral selector was investigated. For chiral separation, a 100-mM phosphate buffer solution (pH 3.0) containing 10% (w/v) MD with dextrose equivalent (DE) of 4-7 as chiral selector at the temperature of 25°C and voltage of 20 kV was used. Under this condition, baseline separation was achieved for nine chiral compounds and partial separation was obtained for another six chiral compounds while no enantioseparation was obtained for the remaining eight compounds. The results showed that the existence of at least two aromatic rings or cycloalkanes and an oxygen or nitrogen atom or -CN group directly bonded to the chiral center are necessary for baseline separation. With the obtained results in this study, chiral separation of a chiral compound can be estimated with MD-modified capillary electrophoresis before analysis. This prediction will minimize the number of preliminary experiments required to resolve enantiomers and will save time and cost. © 2014 Wiley Periodicals, Inc.

Switching chiral solitons for algebraic operation of topological quaternary digits

NASA Astrophysics Data System (ADS)

Kim, Tae-Hwan; Cheon, Sangmo; Yeom, Han Woong

2017-02-01

Chiral objects can be found throughout nature; in condensed matter chiral objects are often excited states protected by a system's topology. The use of chiral topological excitations to carry information has been demonstrated, where the information is robust against external perturbations. For instance, reading, writing, and transfer of binary information have been demonstrated with chiral topological excitations in magnetic systems, skyrmions, for spintronic devices. The next step is logic or algebraic operations of such topological bits. Here, we show experimentally the switching between chiral topological excitations or chiral solitons of different chirality in a one-dimensional electronic system with Z4 topological symmetry. We found that a fast-moving achiral soliton merges with chiral solitons to switch their handedness. This can lead to the realization of algebraic operation of Z4 topological charges. Chiral solitons could be a platform for storage and operation of robust topological multi-digit information.

Chirality-controlled crystallization via screw dislocations.

PubMed

Sung, Baeckkyoung; de la Cotte, Alexis; Grelet, Eric

2018-04-11

Chirality plays an important role in science from enantiomeric separation in chemistry to chiral plasmonics in nanotechnology. However, the understanding of chirality amplification from chiral building blocks to ordered helical superstructures remains a challenge. Here, we demonstrate that topological defects, such as screw dislocations, can drive the chirality transfer from particle to supramolecular structure level during the crystallization process. By using a model system of chiral particles, which enables direct imaging of single particle incorporation into growing crystals, we show that the crystallization kinetic pathway is the key parameter for monitoring, via the defects, the chirality amplification of the crystalline structures from racemic to predominantly homohelical. We provide an explanation based on the interplay between geometrical frustration, racemization induced by thermal fluctuations, and particle chirality. Our results demonstrate that screw dislocations not only promote the growth, but also control the chiral morphology and therefore the functionality of crystalline states.

Influence of Chirality in Ordered Block Copolymer Phases

NASA Astrophysics Data System (ADS)

Prasad, Ishan; Grason, Gregory

2015-03-01

Block copolymers are known to assemble into rich spectrum of ordered phases, with many complex phases driven by asymmetry in copolymer architecture. Despite decades of study, the influence of intrinsic chirality on equilibrium mesophase assembly of block copolymers is not well understood and largely unexplored. Self-consistent field theory has played a major role in prediction of physical properties of polymeric systems. Only recently, a polar orientational self-consistent field (oSCF) approach was adopted to model chiral BCP having a thermodynamic preference for cholesteric ordering in chiral segments. We implement oSCF theory for chiral nematic copolymers, where segment orientations are characterized by quadrupolar chiral interactions, and focus our study on the thermodynamic stability of bi-continuous network morphologies, and the transfer of molecular chirality to mesoscale chirality of networks. Unique photonic properties observed in butterfly wings have been attributed to presence of chiral single-gyroid networks, this has made it an attractive target for chiral metamaterial design.

Enzymatic synthesis of chiral amino‐alcohols by coupling transketolase and transaminase‐catalyzed reactions in a cascading continuous‐flow microreactor system

PubMed Central

Gruber, Pia; Carvalho, Filipe; Marques, Marco P. C.; O'Sullivan, Brian; Subrizi, Fabiana; Dobrijevic, Dragana; Ward, John; Hailes, Helen C.; Fernandes, Pedro; Wohlgemuth, Roland; Baganz, Frank

2017-01-01

Abstract Rapid biocatalytic process development and intensification continues to be challenging with currently available methods. Chiral amino‐alcohols are of particular interest as they represent key industrial synthons for the production of complex molecules and optically pure pharmaceuticals. (2S,3R)‐2‐amino‐1,3,4‐butanetriol (ABT), a building block for the synthesis of protease inhibitors and detoxifying agents, can be synthesized from simple, non‐chiral starting materials, by coupling a transketolase‐ and a transaminase‐catalyzed reaction. However, until today, full conversion has not been shown and, typically, long reaction times are reported, making process modifications and improvement challenging. In this contribution, we present a novel microreactor‐based approach based on free enzymes, and we report for the first time full conversion of ABT in a coupled enzyme cascade for both batch and continuous‐flow systems. Using the compartmentalization of the reactions afforded by the microreactor cascade, we overcame inhibitory effects, increased the activity per unit volume, and optimized individual reaction conditions. The transketolase‐catalyzed reaction was completed in under 10 min with a volumetric activity of 3.25 U ml−1. Following optimization of the transaminase‐catalyzed reaction, a volumetric activity of 10.8 U ml−1 was attained which led to full conversion of the coupled reaction in 2 hr. The presented approach illustrates how continuous‐flow microreactors can be applied for the design and optimization of biocatalytic processes. PMID:28986983

Generating carbyne equivalents with photoredox catalysis

NASA Astrophysics Data System (ADS)

Wang, Zhaofeng; Herraiz, Ana G.; Del Hoyo, Ana M.; Suero, Marcos G.

2018-02-01

Carbon has the unique ability to bind four atoms and form stable tetravalent structures that are prevalent in nature. The lack of one or two valences leads to a set of species—carbocations, carbanions, radicals and carbenes—that is fundamental to our understanding of chemical reactivity. In contrast, the carbyne—a monovalent carbon with three non-bonded electrons—is a relatively unexplored reactive intermediate; the design of reactions involving a carbyne is limited by challenges associated with controlling its extreme reactivity and the lack of efficient sources. Given the innate ability of carbynes to form three new covalent bonds sequentially, we anticipated that a catalytic method of generating carbynes or related stabilized species would allow what we term an ‘assembly point’ disconnection approach for the construction of chiral centres. Here we describe a catalytic strategy that generates diazomethyl radicals as direct equivalents of carbyne species using visible-light photoredox catalysis. The ability of these carbyne equivalents to induce site-selective carbon-hydrogen bond cleavage in aromatic rings enables a useful diazomethylation reaction, which underpins sequencing control for the late-stage assembly-point functionalization of medically relevant agents. Our strategy provides an efficient route to libraries of potentially bioactive molecules through the installation of tailored chiral centres at carbon-hydrogen bonds, while complementing current translational late-stage functionalization processes. Furthermore, we exploit the dual radical and carbene character of the generated carbyne equivalent in the direct transformation of abundant chemical feedstocks into valuable chiral molecules.

Chiral alkylated-aniline as a noninvasive fluorescence sensor: Spectroscopic and molecular modeling studies

NASA Astrophysics Data System (ADS)

Sengupta, Bidisha; Mukherjee, Chirantan Sen; Chakraborty, Sandipan; Muhammad, Maria Jones; Gladney, William; Armstrong, George

2017-12-01

Aniline, heterocyclic aromatic amines, and arylamines are known carcinogens. Recently aniline mustard has come into prominence as a novel anticancer agent. In this project, microwave irradiation has been used to synthesize an optically active alkylated aniline namely 2,6-dimethyl-4-(1-(p-tolyl)ethyl)aniline (abbreviated DMPA). The presence of quartet and doublet peaks in NMR and a single chromatogram in HPLC verified that the final product DMPA, prepared from the synthesis reactions, had no major impurities. By using a Lux chiral column in HPLC, two peaks have been detected in the chromatogram, which correspond to two enantiomers of the chiral aniline derivative. Fluorescence spectroscopic measurements on DMPA indicated conspicuous dependence of its emission behavior on the polarity (in terms of the empirical polarity parameter ET(30)) of the homogeneous solvents used, a property important for an optical sensor. The nature of the emission profiles, along with the relevant parameter namely wavelength at emission maximum (λemmax) is used to infer the distribution, binding and microenvironment of the DMPA molecules in human serum albumin protein (HSA). DMPA is weakly fluorescent in aqueous buffer medium, with a dramatic enhancement in the fluorescence emission in the presence of HSA. Molecular modeling studies have been carried out on the two enantiomers (R and S) of DMPA with HSA. The implications of these findings are examined in relation to the potentialities of DMPA as a novel fluorescence sensor for biological systems.

Chiral alkylated-aniline as a noninvasive fluorescence sensor: Spectroscopic and molecular modeling studies.

PubMed

Sengupta, Bidisha; Mukherjee, Chirantan Sen; Chakraborty, Sandipan; Muhammad, Maria Jones; Gladney, William; Armstrong, George

2017-12-05

Aniline, heterocyclic aromatic amines, and arylamines are known carcinogens. Recently aniline mustard has come into prominence as a novel anticancer agent. In this project, microwave irradiation has been used to synthesize an optically active alkylated aniline namely 2,6-dimethyl-4-(1-(p-tolyl)ethyl)aniline (abbreviated DMPA). The presence of quartet and doublet peaks in NMR and a single chromatogram in HPLC verified that the final product DMPA, prepared from the synthesis reactions, had no major impurities. By using a Lux chiral column in HPLC, two peaks have been detected in the chromatogram, which correspond to two enantiomers of the chiral aniline derivative. Fluorescence spectroscopic measurements on DMPA indicated conspicuous dependence of its emission behavior on the polarity (in terms of the empirical polarity parameter E T (30)) of the homogeneous solvents used, a property important for an optical sensor. The nature of the emission profiles, along with the relevant parameter namely wavelength at emission maximum (λ em max ) is used to infer the distribution, binding and microenvironment of the DMPA molecules in human serum albumin protein (HSA). DMPA is weakly fluorescent in aqueous buffer medium, with a dramatic enhancement in the fluorescence emission in the presence of HSA. Molecular modeling studies have been carried out on the two enantiomers (R and S) of DMPA with HSA. The implications of these findings are examined in relation to the potentialities of DMPA as a novel fluorescence sensor for biological systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Preparative enantiomer separation of dichlorprop with a cinchona-derived chiral selector employing centrifugal partition chromatography and high-performance liquid chromatography: a comparative study.

PubMed

Gavioli, Elena; Maier, Norbert M; Minguillón, Cristina; Lindner, Wolfgang

2004-10-01

A countercurrent chromatography protocol for support-free preparative enantiomer separation of the herbicidal agent 2-(2,4-dichlorphenoxy)propionic acid (dichlorprop) was developed utilizing a purposefully designed, highly enantioselective chiral stationary-phase additive (CSPA) derived from bis-1,4-(dihydroquinidinyl)phthalazine. Guided by liquid-liquid extraction experiments, a solvent system consisting of 10 mM CSPA in methyl tert-butyl ether and 100 mM sodium phosphate buffer (pH 8.0) was identified as a suitable stationary/mobile-phase combination. This solvent system provided an ideal compromise among stationary-phase retention, enantioselectivity, and well-balanced analyte distribution behavior. Using a commercial centrifugal partition chromatography instrument, complete enantiomer separations of up to 366 mg of racemic dichlorprop could be achieved, corresponding to a sample load being equivalent to the molar amount of CSPA employed. Comparison of the preparative performance characteristics of the CPC protocol with that of a HPLC separation using a silica-supported bis-1,4-(dihydroquinidinyl)phthalazine chiral stationary phase CSP revealed comparable loading capacities for both techniques but a significantly lower solvent consumption for CPC. With respect to productivity, HPLC was found to be superior, mainly due to inherent flow rate restrictions of the CPC instrument. Given that further progress in instrumental design and engineering of dedicated, highly enantioselective CSPAs can be achieved, CPC may offer a viable alternative to CSP-based HPLC for preparative-scale enantiomer separation.

Chiral permselectivity in surface-modified nanoporous opal films.

PubMed

Cichelli, Julie; Zharov, Ilya

2006-06-28

Nanoporous 7 mum thin opal films comprising 35 layers of 200 nm diameter SiO2 spheres were assembled on Pt electrodes and modified with chiral selector moieties on the silica surface. Diffusion of chiral redox species through the opals was studied by cyclic voltammetry. The chiral opal films demonstrate high selectivity for transport of one enantiomer over the other. This chiral permselectivity is attributed to the surface-facilitated transport utilizing noncovalent interactions between the chiral permeant molecules and surface-bound chiral selectors.

Chiral filtration-induced spin/valley polarization in silicene line defects

NASA Astrophysics Data System (ADS)

Ren, Chongdan; Zhou, Benhu; Sun, Minglei; Wang, Sake; Li, Yunfang; Tian, Hongyu; Lu, Weitao

2018-06-01

The spin/valley polarization in silicene with extended line defects is investigated according to the chiral filtration mechanism. It is shown that the inner-built quantum Hall pseudo-edge states with identical chirality can serve as a chiral filter with a weak magnetic field and that the transmission process is restrained/strengthened for chiral states with reversed/identical chirality. With two parallel line defects, which act as natural chiral filtration, the filter effect is greatly enhanced, and 100% spin/valley polarization can be achieved.

Tailoring the Variational Implicit Solvent Method for New Challenges: Biomolecular Recognition and Assembly

PubMed Central

Ricci, Clarisse Gravina; Li, Bo; Cheng, Li-Tien; Dzubiella, Joachim; McCammon, J. Andrew

2018-01-01

Predicting solvation free energies and describing the complex water behavior that plays an important role in essentially all biological processes is a major challenge from the computational standpoint. While an atomistic, explicit description of the solvent can turn out to be too expensive in large biomolecular systems, most implicit solvent methods fail to capture “dewetting” effects and heterogeneous hydration by relying on a pre-established (i.e., guessed) solvation interface. Here we focus on the Variational Implicit Solvent Method, an implicit solvent method that adds water “plasticity” back to the picture by formulating the solvation free energy as a functional of all possible solvation interfaces. We survey VISM's applications to the problem of molecular recognition and report some of the most recent efforts to tailor VISM for more challenging scenarios, with the ultimate goal of including thermal fluctuations into the framework. The advances reported herein pave the way to make VISM a uniquely successful approach to characterize complex solvation properties in the recognition and binding of large-scale biomolecular complexes. PMID:29484300

Influence of temperature and molecular structure on ionic liquid solvation layers.

PubMed

Wakeham, Deborah; Hayes, Robert; Warr, Gregory G; Atkin, Rob

2009-04-30

Atomic force microscopy (AFM) force profiling is used to investigate the structure of adsorbed and solvation layers formed on a mica surface by various room temperature ionic liquids (ILs) ethylammonium nitrate (EAN), ethanolammonium nitrate (EtAN), ethylammonium formate (EAF), propylammonium formate (PAF), ethylmethylammonium formate (EMAF), and dimethylethylammonium formate (DMEAF). At least seven layers are observed for EAN at 14 degrees C (melting point 13 degrees C), decreasing as the temperature is increased to 30 degrees C due to thermal energy disrupting solvophobic forces that lead to segregation of cation alkyl tails from the charged ammonium and nitrate moieties. The number and properties of the solvation layers can also be controlled by introducing an alcohol moiety to the cation's alkyl tail (EtAN), or by replacing the nitrate anion with formate (EAF and PAF), even leading to the detection of distinct cation and anion sublayers. Substitution of primary by secondary or tertiary ammonium cations reduces the number of solvation layers formed, and also weakens the cation layer adsorbed onto mica. The observed solvation and adsorbed layer structures are discussed in terms of the intermolecular cohesive forces within the ILs.

Computational analysis of the solvation of coffee ingredients in aqueous ionic liquid mixtures† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra24736a Click here for additional data file.

PubMed Central

Zeindlhofer, Veronika; Khlan, Diana; Bica, Katharina

2017-01-01

In this paper, we investigate the solvation of coffee ingredients including caffeine, gallic acid as representative for phenolic compounds and quercetin as representative for flavonoids in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate [C2mim][OAc] at various concentrations. Due to the anisotropy of the solutes we show that classical Kirkwood–Buff theory is not appropriate to study solvation effects with increasing ionic liquid content. However, excess coordination numbers as well as the mean residence time of solvent molecules at the surface of the solutes can be determined by Voronoi tessellation. Since the volume of the hydration shells is also available by this method, solvation free energies will be discussed as a function of the ionic liquid concentration to yield a physical meaningful picture of solvation for the anisotropic solutes. Hydrogen bonding capabilities of the solutes and their relevance for experimental extraction yields from spent coffee grounds are also discussed. PMID:28496974

Strong Stretching of Poly(ethylene glycol) Brushes Mediated by Ionic Liquid Solvation.

PubMed

Han, Mengwei; Espinosa-Marzal, Rosa M

2017-09-07

We have measured forces between mica surfaces coated with a poly(ethylene glycol) (PEG) brush solvated by a vacuum-dry ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide, with a surface forces apparatus. At high grafting density, the solvation mediated by the ionic liquid causes the brush to stretch twice as much as in water. Modeling of the steric repulsion indicates that PEG behaves as a polyelectrolyte; the hydrogen bonding between ethylene glycol and the imidazolium cation seems to effectively charge the polymer brush, which justifies the strong stretching. Importantly, under strong polymer compression, solvation layers are squeezed out at a higher rate than for the neat ionic liquid. We propose that the thermal fluctuations of the PEG chains, larger in the brush than in the mushroom configuration, maintain the fluidity of the ionic liquid under strong compression, in contrast to the solid-like squeezing-out behavior of the neat ionic liquid. This is the first experimental study of the behavior of a polymer brush solvated by an ionic liquid under nanoconfinement.

Atomic Radius and Charge Parameter Uncertainty in Biomolecular Solvation Energy Calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Xiu; Lei, Huan; Gao, Peiyuan

Atomic radii and charges are two major parameters used in implicit solvent electrostatics and energy calculations. The optimization problem for charges and radii is under-determined, leading to uncertainty in the values of these parameters and in the results of solvation energy calculations using these parameters. This paper presents a method for quantifying this uncertainty in solvation energies using surrogate models based on generalized polynomial chaos (gPC) expansions. There are relatively few atom types used to specify radii parameters in implicit solvation calculations; therefore, surrogate models for these low-dimensional spaces could be constructed using least-squares fitting. However, there are many moremore » types of atomic charges; therefore, construction of surrogate models for the charge parameter space required compressed sensing combined with an iterative rotation method to enhance problem sparsity. We present results for the uncertainty in small molecule solvation energies based on these approaches. Additionally, we explore the correlation between uncertainties due to radii and charges which motivates the need for future work in uncertainty quantification methods for high-dimensional parameter spaces.« less

Highly Stable Lithium Metal Batteries Enabled by Regulating the Solvation of Lithium Ions in Nonaqueous Electrolytes.

PubMed

Zhang, Xue-Qiang; Chen, Xiang; Cheng, Xin-Bing; Li, Bo-Quan; Shen, Xin; Yan, Chong; Huang, Jia-Qi; Zhang, Qiang

2018-05-04

Safe and rechargeable lithium metal batteries have been difficult to achieve because of the formation of lithium dendrites. Herein an emerging electrolyte based on a simple solvation strategy is proposed for highly stable lithium metal anodes in both coin and pouch cells. Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO 3 ) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions, and forming a uniform solid electrolyte interphase (SEI), with an abundance of LiF and LiN x O y on a working lithium metal anode with dendrite-free lithium deposition. Ultrahigh Coulombic efficiency (99.96 %) and long lifespans (1000 cycles) were achieved when the FEC/LiNO 3 electrolyte was applied in working batteries. The solvation chemistry of electrolyte was further explored by molecular dynamics simulations and first-principles calculations. This work provides insight into understanding the critical role of the solvation of lithium ions in forming the SEI and delivering an effective route to optimize electrolytes for safe lithium metal batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding the interplay of weak forces in [3,3]-sigmatropic rearrangement for stereospecific synthesis of diamines.

PubMed

So, Soon Mog; Mui, Leo; Kim, Hyunwoo; Chin, Jik

2012-08-21

Chiral diamines are important building blocks for constructing stereoselective catalysts, including transition metal based catalysts and organocatalysts that facilitate oxidation, reduction, hydrolysis, and C-C bond forming reactions. These molecules are also critical components in the synthesis of drugs, including antiviral agents such as Tamiflu and Relenza and anticancer agents such as oxaliplatin and nutlin-3. The diaza-Cope rearrangement reaction provides one of the most versatile methods for rapidly generating a wide variety of chiral diamines stereospecifically and under mild conditions. Weak forces such as hydrogen bonding, electronic, steric, oxyanionic, and conjugation effects can drive this equilibrium process to completion. In this Account, we examine the effect of these individual weak forces on the value of the equilibrium constant for the diaza-Cope rearrangement reaction using both computational and experimental methods. The availability of a wide variety of aldehydes and diamines allows for the facile synthesis of the diimines needed to study the weak forces. Furthermore, because the reaction generally takes place cleanly at ambient temperature, we can easily measure equilibrium constants for rearrangement of the diimines. We use the Hammett equation to further examine the electronic and oxyanionic effects. In addition, computations and experiments provide us with new insights into the origin and extent of stereospecificity for this rearrangement reaction. The diaza-Cope rearrangement, with its unusual interplay between weak forces and the equilibrium constant of the reaction, provides a rare opportunity to study the effects of the fundamental weak forces on a chemical reaction. Among these many weak forces that affect the diaza-Cope rearrangement, the anion effect is the strongest (10.9 kcal/mol) followed by the resonance-assisted hydrogen-bond effect (7.1 kcal/mol), the steric effect (5.7 kcal/mol), the conjugation effect (5.5 kcal/mol), and the electronic effect (3.2 kcal/mol). Based on both computation and experimental data, the effects of these weak forces are additive. Understanding the interplay of the weak forces in the [3,3]-sigmatropic reaction is interesting in its own right and also provides valuable insights for the synthesis of chiral diamine based drugs and catalysts in excellent yield and enantiopurity.

Chiral magnetic effect without chirality source in asymmetric Weyl semimetals

NASA Astrophysics Data System (ADS)

Kharzeev, Dmitri E.; Kikuchi, Yuta; Meyer, René

2018-05-01

We describe a new type of the chiral magnetic effect (CME) that should occur in Weyl semimetals (WSMs) with an asymmetry in the dispersion relations of the left- and right-handed (LH and RH) chiral Weyl fermions. In such materials, time-dependent pumping of electrons from a non-chiral external source can generate a non-vanishing chiral chemical potential. This is due to the different capacities of the LH and RH chiral Weyl cones arising from the difference in the density of states in the LH and RH cones. The chiral chemical potential then generates, via the chiral anomaly, a current along the direction of an applied magnetic field even in the absence of an external electric field. The source of chirality imbalance in this new setup is thus due to the band structure of the system and the presence of (non-chiral) electron source, and not due to the parallel electric and magnetic fields. We illustrate the effect by an argument based on the effective field theory, and by the chiral kinetic theory calculation for a rotationally invariant WSM with different Fermi velocities in the left and right chiral Weyl cones; we also consider the case of a WSM with Weyl nodes at different energies. We argue that this effect is generically present in WSMs with different dispersion relations for LH and RH chiral Weyl cones, such as SrSi2 recently predicted as a WSM with broken inversion and mirror symmetries, as long as the chiral relaxation time is much longer than the transport scattering time.

Nanoscale chirality in metal and semiconductor nanoparticles

PubMed Central

Thomas, K. George

2016-01-01

The field of chirality has recently seen a rejuvenation due to the observation of chirality in inorganic nanomaterials. The advancements in understanding the origin of nanoscale chirality and the potential applications of chiroptical nanomaterials in the areas of optics, catalysis and biosensing, among others, have opened up new avenues toward new concepts and design of novel materials. In this article, we review the concept of nanoscale chirality in metal nanoclusters and semiconductor quantum dots, then focus on recent experimental and theoretical advances in chiral metal nanoparticles and plasmonic chirality. Selected examples of potential applications and an outlook on the research on chiral nanomaterials are additionally provided. PMID:27752651

Nanoscale chirality in metal and semiconductor nanoparticles.

PubMed

Kumar, Jatish; Thomas, K George; Liz-Marzán, Luis M

2016-10-18

The field of chirality has recently seen a rejuvenation due to the observation of chirality in inorganic nanomaterials. The advancements in understanding the origin of nanoscale chirality and the potential applications of chiroptical nanomaterials in the areas of optics, catalysis and biosensing, among others, have opened up new avenues toward new concepts and design of novel materials. In this article, we review the concept of nanoscale chirality in metal nanoclusters and semiconductor quantum dots, then focus on recent experimental and theoretical advances in chiral metal nanoparticles and plasmonic chirality. Selected examples of potential applications and an outlook on the research on chiral nanomaterials are additionally provided.

A chiroptical switch based on supramolecular chirality transfer through alkyl chain entanglement and dynamic covalent bonding.

PubMed

Lv, Kai; Qin, Long; Wang, Xiufeng; Zhang, Li; Liu, Minghua

2013-12-14

Chirality transfer is an interesting phenomenon in Nature, which represents an important step to understand the evolution of chiral bias and the amplification of the chirality. In this paper, we report the chirality transfer via the entanglement of the alkyl chains between chiral gelator molecules and achiral amphiphilic Schiff base. We have found that although an achiral Schiff base amphiphile could not form organogels in any kind of organic solvents, it formed co-organogels when mixed with a chiral gelator molecule. Interestingly, the chirality of the gelator molecules was transferred to the Schiff base chromophore in the mixed co-gels and there was a maximum mixing ratio for the chirality transfer. Furthermore, the supramolecular chirality was also produced based on a dynamic covalent chemistry of an imine formed by the reaction between an aldehyde and an amine. Such a covalent bond of imine was formed reversibly depending on the pH variation. When the covalent bond was formed the chirality transfer occurred, when it was destroyed, the transfer stopped. Thus, a supramolecular chiroptical switch is obtained based on supramolecular chirality transfer and dynamic covalent chemistry.

Prediction of solvation enthalpy of gaseous organic compounds in propanol

NASA Astrophysics Data System (ADS)

Golmohammadi, Hassan; Dashtbozorgi, Zahra

2016-09-01

The purpose of this paper is to present a novel way for developing quantitative structure-property relationship (QSPR) models to predict the gas-to-propanol solvation enthalpy (Δ H solv) of 95 organic compounds. Different kinds of descriptors were calculated for each compound using the Dragon software package. The variable selection technique of replacement method (RM) was employed to select the optimal subset of solute descriptors. Our investigation reveals that the dependence of physical chemistry properties of solution on solvation enthalpy is nonlinear and that the RM method is unable to model the solvation enthalpy accurately. The results established that the calculated Δ H solv values by SVM were in good agreement with the experimental ones, and the performances of the SVM models were superior to those obtained by RM model.

Solvation of the fluorine containing anions and their lithium salts in propylene carbonate and dimethoxyethane.

PubMed

Chaban, Vitaly

2015-07-01

Electrolyte solutions based on the propylene carbonate (PC)-dimethoxyethane (DME) mixtures are of significant importance and urgency due to emergence of lithium-ion batteries. Solvation and coordination of the lithium cation in these systems have been recently attended in detail. However, analogous information concerning anions (tetrafluoroborate, hexafluorophosphate) is still missed. This work reports PM7-MD simulations (electronic-structure level of description) to include finite-temperature effects on the anion solvation regularities in the PC-DME mixture. The reported result evidences that the anions appear weakly solvated. This observation is linked to the absence of suitable coordination sites in the solvent molecules. In the concentrated electrolyte solutions, both BF4(-) and PF6(-) prefer to exist as neutral ion pairs (LiBF4, LiPF6).

Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O){/n -} and (NH3){/n -}

NASA Astrophysics Data System (ADS)

Lee, G. H.; Arnold, S. T.; Eaton, J. G.; Sarkas, H. W.; Bowen, K. H.; Ludewigt, C.; Haberland, H.

1991-03-01

The photodetachment spectra of (H2O){/n =2-69/-} and (NH3){/n =41-1100/-} have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly with n -1/3, extrapolating to a VDE ( n=∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons.

Solvation of Cr 3+ cation in water-acetonitrile mixture studied by IR spectroscopy: molecular penetration into the solvation shells

NASA Astrophysics Data System (ADS)

Jamróz, Dorota; Wójcik, Marek; Lindgren, Jan

2000-09-01

Infrared spectra of mixtures of water and deuteroacetonitrile containing the Cr 3+ cation have been studied as a function of concentration, time and temperature. The CN stretching vibration of CD 3CN molecules has been used as a probe of the structural environments. The CN band in the spectra of the solutions is a superposition of four subbands, which may be attributed to CD 3CN bound in the first, second, and third solvation shells of the cation and to non-bound CD 3CN. The character of changes of the integral intensities of the subbands with time for various H 2O:Cr 3+ molar ratios are explained by suggesting mechanisms of molecular replacement within the solvation shells of Cr 3+.

Significant Enhancement of the Chiral Correlation Length in Nematic Liquid Crystals by Gold Nanoparticle Surfaces Featuring Axially Chiral Binaphthyl Ligands.

PubMed

Mori, Taizo; Sharma, Anshul; Hegmann, Torsten

2016-01-26

Chirality is a fundamental scientific concept best described by the absence of mirror symmetry and the inability to superimpose an object onto its mirror image by translation and rotation. Chirality is expressed at almost all molecular levels, from single molecules to supramolecular systems, and present virtually everywhere in nature. Here, to explore how chirality propagates from a chiral nanoscale surface, we study gold nanoparticles functionalized with axially chiral binaphthyl molecules. In particular, we synthesized three enantiomeric pairs of chiral ligand-capped gold nanoparticles differing in size, curvature, and ligand density to tune the chirality transfer from nanoscale solid surfaces to a bulk anisotropic liquid crystal medium. Ultimately, we are examining how far the chirality from a nanoparticle surface reaches into a bulk material. Circular dichroism spectra of the gold nanoparticles decorated with binaphthyl thiols confirmed that the binaphthyl moieties form a cisoid conformation in isotropic organic solvents. In the chiral nematic liquid crystal phase, induced by dispersing the gold nanoparticles into an achiral anisotropic nematic liquid crystal solvent, the binaphthyl moieties on the nanoparticle surface form a transoid conformation as determined by imaging the helical twist direction of the induced cholesteric phase. This suggests that the ligand density on the nanoscale metal surfaces provides a dynamic space to alter and adjust the helicity of binaphthyl derivatives in response to the ordering of the surrounding medium. The helical pitch values of the induced chiral nematic phase were determined, and the helical twisting power (HTP) of the chiral gold nanoparticles calculated to elucidate the chirality transfer efficiency of the binaphthyl ligand capped gold nanoparticles. Remarkably, the HTP increases with increasing diameter of the particles, that is, the efficiency of the chirality transfer of the binaphthyl units bound to the nanoparticle surface is diminished as the size of the particle is reduced. However, in comparison to the free ligands, per chiral molecule all tested gold nanoparticles induce helical distortions in a 10- to 50-fold larger number of liquid crystal host molecules surrounding each particle, indicating a significantly enhanced chiral correlation length. We propose that both the helicity and the chirality transfer efficiency of axially chiral binaphthyl derivatives can be controlled at metal nanoparticle surfaces by adjusting the particle size and curvature as well as the number and density of the chiral ligands to ultimately measure and tune the chiral correlation length.

Homochiral Evolution in Self-Assembled Chiral Polymers and Block Copolymers.

PubMed

Wen, Tao; Wang, Hsiao-Fang; Li, Ming-Chia; Ho, Rong-Ming

2017-04-18

The significance of chirality transfer is not only involved in biological systems, such as the origin of homochiral structures in life but also in man-made chemicals and materials. How the chiral bias transfers from molecular level (molecular chirality) to helical chain (conformational chirality) and then to helical superstructure or phase (hierarchical chirality) from self-assembly is vital for the chemical and biological processes in nature, such as communication, replication, and enzyme catalysis. In this Account, we summarize the methodologies for the examination of homochiral evolution at different length scales based on our recent studies with respect to the self-assembly of chiral polymers and chiral block copolymers (BCPs*). A helical (H*) phase to distinguish its P622 symmetry from that of normal hexagonally packed cylinder phase was discovered in the self-assembly of BCPs* due to the chirality effect on BCP self-assembly. Enantiomeric polylactide-containing BCPs*, polystyrene-b-poly(l-lactide) (PS-PLLA) and polystyrene-b-poly(d-lactide) (PS-PDLA), were synthesized for the examination of homochiral evolution. The optical activity (molecular chirality) of constituted chiral repeating unit in the chiral polylactide is detected by electronic circular dichroism (ECD) whereas the conformational chirality of helical polylactide chain can be explicitly determined by vibrational circular dichroism (VCD). The H* phases of the self-assembled polylactide-containing BCPs* can be directly visualized by 3D transmission electron microscopy (3D TEM) technique at which the handedness (hierarchical chirality) of the helical nanostructure is thus determined. The results from the ECD, VCD, and 3D TEM for the investigated chirality at different length scales suggest the homochiral evolution in the self-assembly of the BCPs*. For chiral polylactides, twisted lamellae in crystalline banded spherulite can be formed by dense packing scheme and effective interactions upon helical chains from self-assembly. The handedness of the twisted lamella can be determined by using rotation experiment of polarized light microscopy (PLM). Similar to the self-assembly of BCPs*, the examined results suggest the homochiral evolution in the crystallized chiral polylactides. The results presented in this Account demonstrate the notable progress in the spectral and morphological determination for the examination of molecular, conformational, and hierarchical chirality in self-assembled twisted superstructures of chiral polymers and helical phases of block copolymers and suggest the attainability of homochiral evolution in the self-assembly of chiral homopolymers and BCPs*. The suggested methodologies for the understanding of the mechanisms of the chirality transfer at different length scales provide the approaches to give Supporting Information for disclosing the mysteries of the homochiral evolution from molecular level.

Spin Chirality of Cu3 and V3 Nanomagnets. 1. Rotation Behavior of Vector Chirality, Scalar Chirality, and Magnetization in the Rotating Magnetic Field, Magnetochiral Correlations.

PubMed

Belinsky, Moisey I

2016-05-02

The rotation behavior of the vector chirality κ, scalar chirality χ, and magnetization M in the rotating magnetic field H1 is considered for the V3 and Cu3 nanomagnets, in which the Dzialoshinsky-Moriya coupling is active. The polar rotation of the field H1 of the given strength H1 results in the energy spectrum characterized by different vector and scalar chiralities in the ground and excited states. The magnetochiral correlations between the vector and scalar chiralities, energy, and magnetization in the rotating field were considered. Under the uniform polar rotation of the field H1, the ground-state chirality vector κI performs sawtooth oscillations and the magnetization vector MI performs the sawtooth oscillating rotation that is accompanied by the correlated transformation of the scalar chirality χI. This demonstrates the magnetochiral effect of the joint rotation behavior and simultaneous frustrations of the spin chiralities and magnetization in the rotating field, which are governed by the correlation between the chiralities and magnetization.

Timoshenko beam model for chiral materials

NASA Astrophysics Data System (ADS)

Ma, T. Y.; Wang, Y. N.; Yuan, L.; Wang, J. S.; Qin, Q. H.

2017-12-01

Natural and artificial chiral materials such as deoxyribonucleic acid (DNA), chromatin fibers, flagellar filaments, chiral nanotubes, and chiral lattice materials widely exist. Due to the chirality of intricately helical or twisted microstructures, such materials hold great promise for use in diverse applications in smart sensors and actuators, force probes in biomedical engineering, structural elements for absorption of microwaves and elastic waves, etc. In this paper, a Timoshenko beam model for chiral materials is developed based on noncentrosymmetric micropolar elasticity theory. The governing equations and boundary conditions for a chiral beam problem are derived using the variational method and Hamilton's principle. The static bending and free vibration problem of a chiral beam are investigated using the proposed model. It is found that chirality can significantly affect the mechanical behavior of beams, making materials more flexible compared with nonchiral counterparts, inducing coupled twisting deformation, relatively larger deflection, and lower natural frequency. This study is helpful not only for understanding the mechanical behavior of chiral materials such as DNA and chromatin fibers and characterizing their mechanical properties, but also for the design of hierarchically structured chiral materials.

Timoshenko beam model for chiral materials

NASA Astrophysics Data System (ADS)

Ma, T. Y.; Wang, Y. N.; Yuan, L.; Wang, J. S.; Qin, Q. H.

2018-06-01

Natural and artificial chiral materials such as deoxyribonucleic acid (DNA), chromatin fibers, flagellar filaments, chiral nanotubes, and chiral lattice materials widely exist. Due to the chirality of intricately helical or twisted microstructures, such materials hold great promise for use in diverse applications in smart sensors and actuators, force probes in biomedical engineering, structural elements for absorption of microwaves and elastic waves, etc. In this paper, a Timoshenko beam model for chiral materials is developed based on noncentrosymmetric micropolar elasticity theory. The governing equations and boundary conditions for a chiral beam problem are derived using the variational method and Hamilton's principle. The static bending and free vibration problem of a chiral beam are investigated using the proposed model. It is found that chirality can significantly affect the mechanical behavior of beams, making materials more flexible compared with nonchiral counterparts, inducing coupled twisting deformation, relatively larger deflection, and lower natural frequency. This study is helpful not only for understanding the mechanical behavior of chiral materials such as DNA and chromatin fibers and characterizing their mechanical properties, but also for the design of hierarchically structured chiral materials.

Some recent experimental results related to nuclear chirality

NASA Astrophysics Data System (ADS)

Timár, J.; Kuti, I.; Sohler, D.; Starosta, K.; Koike, T.; Paul, E. S.

2014-09-01

Detailed band structures of three chiral-candidate nuclei, 134Pr, 132La and 103Rh have been studied. The aim of the study was twofold. First, to try to explore the reasons behind the contradiction between the theoretically predicted chirality in these nuclei and the recently observed fingerprints that suggest non-chiral interpretation for the previous chiral candidate band doublets. Second, to search for multiple chiral bands of different types in these nuclei. In 134Pr a new πh11/2vh11/2 band has been observed besides the previously known chiral-candidate πh11/2vh11/2 doublet. This new band and the yrare πh11/2vh11/2 band show the expected features of a chiral doublet structure. This fact combined with the observed similarity between the band structures of 134Pr and 132La suggests that chirality might exist in these nuclei. The detailed study of the 103Rh band structure resulted in the observation of two new chiral-doublet looking structures besides the previously known one. This is indicative of possible existence of multiple chiral doublet structure in this nucleus.

An efficient and highly stereoselective synthesis of new P-chiral 1,5-diphosphanylferrocene ligands and their use in enantioselective hydrogenation.

PubMed

Chen, Weiping; Roberts, J Stanley M; Whittall, John; Steiner, Alexander

2006-07-21

An efficient and highly stereoselective synthesis of P-chiral 1,5-diphosphanylferrocene ligands has been developed, and the introduction of P-chirality in ferrocene-based phosphine ligands enhances the enantioselective discrimination produced by the corresponding catalyst when matching of the planar chirality, the chirality at carbon and the chirality at phosphorus occurs.

Excess electron localization in solvated DNA bases.

PubMed

Smyth, Maeve; Kohanoff, Jorge

2011-06-10

We present a first-principles molecular dynamics study of an excess electron in condensed phase models of solvated DNA bases. Calculations on increasingly large microsolvated clusters taken from liquid phase simulations show that adiabatic electron affinities increase systematically upon solvation, as for optimized gas-phase geometries. Dynamical simulations after vertical attachment indicate that the excess electron, which is initially found delocalized, localizes around the nucleobases within a 15 fs time scale. This transition requires small rearrangements in the geometry of the bases.

Excess Electron Localization in Solvated DNA Bases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smyth, Maeve; Kohanoff, Jorge

2011-06-10

We present a first-principles molecular dynamics study of an excess electron in condensed phase models of solvated DNA bases. Calculations on increasingly large microsolvated clusters taken from liquid phase simulations show that adiabatic electron affinities increase systematically upon solvation, as for optimized gas-phase geometries. Dynamical simulations after vertical attachment indicate that the excess electron, which is initially found delocalized, localizes around the nucleobases within a 15 fs time scale. This transition requires small rearrangements in the geometry of the bases.

Cell Chirality Drives Left-Right Asymmetric Morphogenesis

PubMed Central

Inaki, Mikiko; Sasamura, Takeshi; Matsuno, Kenji

2018-01-01

Most macromolecules found in cells are chiral, meaning that they cannot be superimposed onto their mirror image. However, cells themselves can also be chiral, a subject that has received little attention until very recently. In our studies on the mechanisms of left-right (LR) asymmetric development in Drosophila, we discovered that cells can have an intrinsic chirality to their structure, and that this “cell chirality” is generally responsible for the LR asymmetric development of certain organs in this species. The actin cytoskeleton plays important roles in the formation of cell chirality. In addition, Myosin31DF (Myo31DF), which encodes Drosophila Myosin ID, was identified as a molecular switch for cell chirality. In other invertebrate species, including snails and Caenorhabditis elegans, chirality of the blastomeres, another type of cell chirality, determines the LR asymmetry of structures in the body. Thus, chirality at the cellular level may broadly contribute to LR asymmetric development in various invertebrate species. Recently, cell chirality was also reported for various vertebrate cultured cells, and studies suggested that cell chirality is evolutionarily conserved, including the essential role of the actin cytoskeleton. Although the biological roles of cell chirality in vertebrates remain unknown, it may control LR asymmetric development or other morphogenetic events. The investigation of cell chirality has just begun, and this new field should provide valuable new insights in biology and medicine. PMID:29666795

FATE AND EFFECTS OF THE ENANTIOMERS OF CHIRAL ENVIRONMENTAL POLLUTANTS

EPA Science Inventory

Enantiomers, the mirror image isomers of chiral compounds, are known to be selective in their interaction with other chiral molecules, including enzymes and other biochemicals. This holds true for pesticides, about 25% of which are chiral molecules, and other chiral environmental...

Chiral magnetic effect in lattice QCD with a chiral chemical potential.

PubMed

Yamamoto, Arata

2011-07-15

We perform a first lattice QCD simulation including a two-flavor dynamical fermion with a chiral chemical potential. Because the chiral chemical potential gives rise to no sign problem, we can exactly analyze a chirally imbalanced QCD matter by Monte Carlo simulation. By applying an external magnetic field to this system, we obtain a finite induced current along the magnetic field, which corresponds to the chiral magnetic effect. The obtained induced current is proportional to the magnetic field and to the chiral chemical potential, which is consistent with an analytical prediction.

[Influence of mobile phase composition on chiral separation of organic selenium racemates].

PubMed

Han, Xiao-qian; Qi, Bang-feng; Dun, Hui-juan; Zhu, Xin-yi; Na, Peng-jun; Jiang, Sheng-xiang; Chen, Li-ren

2002-05-01

The chiral separation of some chiral compounds with similar structure on the cellulose tris (3,5-dimethylphenylcarbamate) chiral stationary phase prepared by us was obtained. Ternary mobile phases influencing chiral recognition were investigated. A mode of interaction between the structural character of samples and chiral stationary phase is discussed. The results indicated that the retention and chiral separation of the analytes had a bigger change with minute addition of alcohols or acetonitrile as modifier in n-hexane/2-propanol (80/20, volume ratio) binary mobile phase.

A very simple, highly stereoselective and modular synthesis of ferrocene-based P-chiral phosphine ligands.

PubMed

Chen, Weiping; Mbafor, William; Roberts, Stanley M; Whittall, John

2006-03-29

A very simple, highly stereoselective and modular synthesis of ferrocene-based P-chiral phosphine ligands has been developed. On the basis of this new methodology, several new families of ferrocene-based phosphine ligands have been prepared coupling chirality at phosphorus with other, more standard stereogenic features. The introduction of P-chirality into ferrocene-based phosphine ligands enhances the enantioselective discrimination produced by the corresponding Rh catalyst when a matching among the planar chirality, carbon chirality, and the chirality of phosphorus is achieved.

The Denaturation Transition of DNA in Mixed Solvents

PubMed Central

Hammouda, Boualem; Worcester, David

2006-01-01

The helix-to-coil denaturation transition in DNA has been investigated in mixed solvents at high concentration using ultraviolet light absorption spectroscopy and small-angle neutron scattering. Two solvents have been used: water and ethylene glycol. The “melting” transition temperature was found to be 94°C for 4% mass fraction DNA/d-water and 38°C for 4% mass fraction DNA/d-ethylene glycol. The DNA melting transition temperature was found to vary linearly with the solvent fraction in the mixed solvents case. Deuterated solvents (d-water and d-ethylene glycol) were used to enhance the small-angle neutron scattering signal and 0.1M NaCl (or 0.0058 g/g mass fraction) salt concentration was added to screen charge interactions in all cases. DNA structural information was obtained by small-angle neutron scattering, including a correlation length characteristic of the inter-distance between the hydrogen-containing (desoxyribose sugar-amine base) groups. This correlation length was found to increase from 8.5 to 12.3 Å across the melting transition. Ethylene glycol and water mixed solvents were found to mix randomly in the solvation region in the helix phase, but nonideal solvent mixing was found in the melted coil phase. In the coil phase, solvent mixtures are more effective solvating agents than either of the individual solvents. Once melted, DNA coils behave like swollen water-soluble synthetic polymer chains. PMID:16815902

A web site for calculating the degree of chirality.

PubMed

Zayit, Amir; Pinsky, Mark; Elgavi, Hadassah; Dryzun, Chaim; Avnir, David

2011-01-01

The web site, http://www.csm.huji.ac.il/, uses the Continuous Chirality Measure to evaluate quantitatively the degree of chirality of a molecule, a structure, a fragment. The value of this measure ranges from zero, the molecule is achiral, to higher values (the upper limit is 100); the higher the chirality value, the more chiral the molecule is. The measure is based on the distance between the chiral molecule and the nearest structure that is achiral. Questions such as the following can be addressed: by how much is one molecule more chiral than the other? how does chirality change along conformational motions? is there a correlation between chirality and enantioselectivity in a series of molecules? Both elementary and advanced features are offered. Related calculation options are the symmetry measures and shape measures. Copyright © 2009 Wiley-Liss, Inc.

Thermal chiral vortical and magnetic waves: New excitation modes in chiral fluids

DOE PAGES

Kalaydzhyan, Tigran; Murchikova, Elena

2017-03-24

In certain circumstances, chiral (parity-violating) medium can be described hydrodynamically as a chiral fluid with microscopic quantum anomalies. Possible examples of such systems include strongly coupled quark–gluon plasma, liquid helium 3He-A, neutron stars and the Early Universe. Here, we study first-order hy-drodynamics of a chiral fluid on a vortex background and in an external magnetic field. We show that there are two previously undiscovered modes describing heat waves propagating along the vortex and magnetic field. We call them the Thermal Chiral Vortical Wave and Thermal Chiral Magnetic Wave. We also identify known gapless excitations of density (chiral vortical and chiralmore » magnetic waves) and transverse velocity (chiral Alfvén wave). We also demonstrate that the velocity of the chiral vortical wave is zero, when the full hydrodynamic framework is applied, and hence the wave is absent and the excitation reduces to the charge diffusion mode. We also comment on the frame-dependent contributions to the obtained propagation velocities.« less

Spin-Selective Transmission and Devisable Chirality in Two-Layer Metasurfaces.

PubMed

Li, Zhancheng; Liu, Wenwei; Cheng, Hua; Chen, Shuqi; Tian, Jianguo

2017-08-15

Chirality is a nearly ubiquitous natural phenomenon. Its minute presence in most naturally occurring materials makes it incredibly difficult to detect. Recent advances in metasurfaces indicate that they exhibit devisable chirality in novel forms; this finding offers an effective opening for studying chirality and its features in such nanostructures. These metasurfaces display vast possibilities for highly sensitive chirality discrimination in biological and chemical systems. Here, we show that two-layer metasurfaces based on twisted nanorods can generate giant spin-selective transmission and support engineered chirality in the near-infrared region. Two designed metasurfaces with opposite spin-selective transmission are proposed for treatment as enantiomers and can be used widely for spin selection and enhanced chiral sensing. Specifically, we demonstrate that the chirality in these proposed metasurfaces can be adjusted effectively by simply changing the orientation angle between the twisted nanorods. Our results offer simple and straightforward rules for chirality engineering in metasurfaces and suggest intriguing possibilities for the applications of such metasurfaces in spin optics and chiral sensing.

Biomarkers of Oxidative Stress in the Assessment of Enantioselective Toxicity of Chiral Pesticides.

PubMed

Ye, Xiaoqing; Liu, Ying; Li, Feixue

2017-01-01

In biological systems, the individual stereoisomers of chiral substances possess significantly different biochemical properties because the specific structure-activity relationships are required for a common site on biomolecules. In the past decade, there has been increasing concern over the enantioselective toxicity of environmental chiral pollutants, especially chiral pesticides. Different responses and activities of a pair of enantiomers of chiral pesticides were often observed. Therefore, assessment of the enantioselective toxicological properties of chiral pesticides is a prerequisite in application of single-isomer products and particularly important for environmental protection. The development of biomarkers that can predict enantioselective effects from chiral pesticides has recently been gained more and more attention. The biomarkers of oxidative stress have become a topic of significant interest for toxic assessments. In this review, we summarized current knowledge and advances in the understanding of enantiomeric oxidative processes in biological systems in response to chiral pesticides. The consistent results in two types of chiral insecticides (synthetic pyrethroids and organochlorine pesticides) showed the significant difference in cytotoxicity of enantiomers, suggesting the antioxidant enzymes are reliable biomarkers for the assessment of toxicity of chiral chemicals. Results indicate that antioxidant enzymes are sensitive and valid biomarkers to assess the oxidative damage caused by chiral herbicides. In addition, it can be inferred that the enantioselectivity of chiral herbicides on antioxidant enzymes exists in other species. Compared with insecticides and herbicides, researches about the enantioselectivity of oxidative stress caused by chiral fungicides are quite limited. Only two kinds of chiral fungicides has been used to study the enantioselectivity of oxidative stress by now. The current knowledge that enantioselective processes of oxidative damage occur in organisms or cells extends toxicological studies of environmental contamination by chiral chemicals. These studies indicate that oxidative biomarkers can be useful for monitoring enantioselective toxicity of chiral contaminates, while comparing enantiomer-induced responses in different species should be approached with caution because of differences in uptake, target sites, biotransformation and pharmacokinetics of the enantiomers.

Mitochondria are the primary target in the induction of apoptosis by chiral ruthenium(II) polypyridyl complexes in cancer cells.

PubMed

Wang, Jin-Quan; Zhang, Ping-Yu; Qian, Chen; Hou, Xiao-Juan; Ji, Liang-Nian; Chao, Hui

2014-03-01

A series of novel chiral ruthenium(II) polypyridyl complexes (Δ-Ru1, Λ-Ru1, Δ-Ru2, Λ-Ru2, Δ-Ru3, Λ-Ru3) were synthesized and evaluated to determine their antiproliferative activities. Colocalization, inductively coupled plasma mass spectrometry, and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay studies showed that these ruthenium(II) complexes accumulated preferentially in the mitochondria and exhibited cytotoxicity against various cancer cells in vitro. The complex Δ-Ru1 is of particular interest because it was found to have half-maximal inhibitory concentrations comparable to those of cisplatin and better activity than cisplatin against a cisplatin-resistant cell line, A549-CP/R. Δ-Ru1 induced alterations in the mitochondrial membrane potential and triggered intrinsic mitochondria-mediated apoptosis in HeLa cells, which involved the regulation of Bcl-2 family members and the activation of caspases. Taken together, these data suggest that Δ-Ru1 may be a novel mitochondria-targeting anticancer agent.

Water-Soluble Ruthenium (II) Chiral Heteroleptic Complexes with Amoebicidal in Vitro and in Vivo Activity.

PubMed

Toledano-Magaña, Yanis; García-Ramos, Juan C; Torres-Gutiérrez, Carolina; Vázquez-Gasser, Cristina; Esquivel-Sánchez, José M; Flores-Alamo, Marcos; Ortiz-Frade, Luis; Galindo-Murillo, Rodrigo; Nequiz, Mario; Gudiño-Zayas, Marco; Laclette, Juan P; Carrero, Julio C; Ruiz-Azuara, Lena

2017-02-09

Three water-soluble Ru(II) chiral heteroleptic coordination compounds [Ru(en)(pdto)]Cl 2 (1), [Ru(gly)(pdto)]Cl (2), and [Ru(acac)(pdto)]Cl (3), where pdto = 2,2'-[1,2-ethanediylbis-(sulfanediyl-2,1-ethanediyl)]dipyridine, en = ethylendiamine, gly = glycinate, and acac = acetylacetonate, have been synthezised and fully characterized. The crystal structures of compounds 1-3 are described. The IC 50 values for compounds 1-3 are within nanomolar range (14, 12, and 6 nM, respectively). The cytotoxicity for human peripheral blood lymphocytes is extremely low (>100 μM). Selectivity indexes for Ru(II) compounds are in the range 700-1300. Trophozoites exposed to Ru(II) compounds die through an apoptotic pathway triggered by ROS production. The orally administration to infected mice induces a total elimination of the parasite charge in mice faeces 1-2-fold faster than metronidazole. Besides, all compounds inhibit the trophozoite proliferation in amoebic liver abscess induced in hamster. All our results lead us to propose these compounds as promising candidates as antiparasitic agents.

In vitro DNA binding, pBR322 plasmid cleavage and molecular modeling study of chiral benzothiazole Schiff-base-valine Cu(II) and Zn(II) complexes to evaluate their enantiomeric biological disposition for molecular target DNA.

PubMed

Alizadeh, Rahman; Afzal, Mohd; Arjmand, Farukh

2014-10-15

Bicyclic heterocyclic compounds viz. benzothiazoles are key components of deoxyribonucleic acid (DNA) molecules and participate directly in the encoding of genetic information. Benzothiazoles, therefore, represent a potent and selective class of antitumor compounds. The design and synthesis of chiral antitumor chemotherapeutic agents of Cu(II) and Zn(II), L- and -D benzothiazole Schiff base-valine complexes 1a &b and 2a &b, respectively were carried out and thoroughly characterized by spectroscopic and analytical techniques. Interaction of 1a and b and 2a and b with CT DNA by employing UV-vis, florescence, circular dichroic methods and cleavage studies of 1a with pBR322 plasmid, molecular docking were done in order to demonstrate their enantiomeric disposition toward the molecular drug target DNA. Interestingly, these studies unambiguously demonstrated the greater potency of L-enantiomer in comparison to D-enantiomer. Copyright © 2014 Elsevier B.V. All rights reserved.

Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions.

PubMed

Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G

2009-05-07

We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the "D" stands for "density" to denote that the full solute electron density is used without defining partial atomic charges. "Continuum" denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where "universal" denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which a few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G, M05-2X/6-31+G, M05-2X/cc-pVTZ, B3LYP/6-31G, and HF/6-31G. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marenich, Aleksandr; Cramer, Christopher J; Truhlar, Donald G

2009-04-30

We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the “D” stands for “density” to denote that the full solute electron density is used without defining partial atomic charges. “Continuum” denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where “universal” denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which amore » few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G*, M05-2X/6-31+G**, M05-2X/cc-pVTZ, B3LYP/6-31G*, and HF/6-31G*. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G* basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.« less

Conjugated Gammadion Chiral Metamaterial with Uniaxial Optical Activity and Negative Refractive Index

DTIC Science & Technology

2011-01-10

in Fig. 4, we discuss a procedure of transmutation from the simple -particle chiral element to the conjugated gammadion chiral metamaterial. The...the transmutation from the simple -particle chiral element to the conjugated gammadion chiral metamaterial. The procedure shows how the magnetic or

Motifs for molecular recognition exploiting hydrophobic enclosure in protein-ligand binding.

PubMed

Young, Tom; Abel, Robert; Kim, Byungchan; Berne, Bruce J; Friesner, Richard A

2007-01-16

The thermodynamic properties and phase behavior of water in confined regions can vary significantly from that observed in the bulk. This is particularly true for systems in which the confinement is on the molecular-length scale. In this study, we use molecular dynamics simulations and a powerful solvent analysis technique based on inhomogenous solvation theory to investigate the properties of water molecules that solvate the confined regions of protein active sites. Our simulations and analysis indicate that the solvation of protein active sites that are characterized by hydrophobic enclosure and correlated hydrogen bonds induce atypical entropic and enthalpic penalties of hydration. These penalties apparently stabilize the protein-ligand complex with respect to the independently solvated ligand and protein, which leads to enhanced binding affinities. Our analysis elucidates several challenging cases, including the super affinity of the streptavidin-biotin system.

Mapping the Free Energy of Lithium Solvation in the Protic Ionic Liquid Ethylammonuim Nitrate: A Metadynamics Study.

PubMed

Kachmar, Ali; Carignano, Marcelo; Laino, Teodoro; Iannuzzi, Marcella; Hutter, Jürg

2017-08-10

Understanding lithium solvation and transport in ionic liquids is important due to their possible application in electrochemical devices. Using first-principles simulations aided by a metadynamics approach we study the free-energy landscape for lithium ions at infinite dilution in ethylammonium nitrate, a protic ionic liquid. We analyze the local structure of the liquid around the lithium cation and obtain a quantitative picture in agreement with experimental findings. Our simulations show that the lowest two free energy minima correspond to conformations with the lithium ion being solvated either by three or four nitrate ions with a transition barrier between them of 0.2 eV. Other less probable conformations having different solvation pattern are also investigated. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of the composition of a solution on the enthalpies of solvation of piperidine in methanol-acetonitrile and dimethylsulfoxide-acetonitrile mixed solvents

NASA Astrophysics Data System (ADS)

Kuz'mina, I. A.; Volkova, M. A.; Sitnikova, K. A.; Sharnin, V. A.

2014-01-01

Heat effects of dissolution of piperidine (ppd) are measured by calorimetry at 298.15 K over the range of composition of acetonitrile-methanol (AN-MeOH) mixed solvents. Based on the Δsol H ○(ppd)AN-MeOH values obtained using the literature data on Δsol H ○ (ppd) in acetonitrile-dimethylsulfoxide (AN-DMSO) mixed solvents and the vaporization enthalpy of ppd, the enthalpies of solvation of amine in AN-MeOH and AN-DMSO binary mixtures are calculated. A rise in the exothermicity of solvation of piperidine is observed upon the transition from AN to DMSO and MeOH, due mainly to the enhanced solvation of the amino group of ppd as a result of changes in the acid-base properties of the mixed solvent.

Electrostatic Solvation Free Energy of Amino Acid Side Chain Analogs: Implications for the Validity of Electrostatic Linear Response in Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Bin; Pettitt, Bernard M.

Electrostatic free energies of solvation for 15 neutral amino acid side chain analogs are computed. We compare three methods of varying computational complexity and accuracy for three force fields: free energy simulations, Poisson-Boltzmann (PB), and linear response approximation (LRA) using AMBER, CHARMM, and OPLSAA force fields. We find that deviations from simulation start at low charges for solutes. The approximate PB and LRA produce an overestimation of electrostatic solvation free energies for most of molecules studied here. These deviations are remarkably systematic. The variations among force fields are almost as large as the variations found among methods. Our study confirmsmore » that success of the approximate methods for electrostatic solvation free energies comes from their ability to evaluate free energy differences accurately.« less

Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion

DOE PAGES

Chaudhari, Mangesh I.; Nair, Jijeesh R.; Pratt, Lawrence R.; ...

2016-10-21

Lithium-ion solvation and diffusion properties in ethylene carbonate (EC) and propylene carbonate (PC) were studied by molecular simulation, experiments, and electronic structure calculations. Studies carried out in water provide a reference for interpretation. Classical molecular dynamics simulation results are compared to ab initio molecular dynamics to assess nonpolarizable force field parameters for solvation structure of the carbonate solvents. Quasi-chemical theory (QCT) was adapted to take advantage of fourfold occupancy of the near-neighbor solvation structure observed in simulations and used to calculate solvation free energies. The computed free energy for transfer of Li + to PC from water, based on electronicmore » structure calculations with cluster-QCT, agrees with the experimental value. The simulation-based direct-QCT results with scaled partial charges agree with the electronic structure-based QCT values. The computed Li +/PF 6 - transference numbers of 0.35/0.65 (EC) and 0.31/0.69 (PC) agree well with NMR experimental values of 0.31/0.69 (EC) and 0.34/0.66 (PC) and similar values obtained here with impedance spectroscopy. These combined results demonstrate that solvent partial charges can be scaled in systems dominated by strong electrostatic interactions to achieve trends in ion solvation and transport properties that are comparable to ab initio and experimental results. Thus, the results support the use of scaled partial charges in simple, nonpolarizable force fields in future studies of these electrolyte solutions.« less

Picosecond solvation dynamics—A potential viewer of DMSO—Water binary mixtures

NASA Astrophysics Data System (ADS)

Banik, Debasis; Kundu, Niloy; Kuchlyan, Jagannath; Roy, Arpita; Banerjee, Chiranjib; Ghosh, Surajit; Sarkar, Nilmoni

2015-02-01

In this work, we have investigated the composition dependent anomalous behavior of dimethyl sulfoxide (DMSO)-water binary mixture by collecting the ultrafast solvent relaxation response around a well known solvation probe Coumarin 480 (C480) by using a femtosecond fluorescence up-conversion spectrometer. Recent molecular dynamics simulations have predicted two anomalous regions of DMSO-water binary mixture. Particularly, these studies encourage us to investigate the anomalies from experimental background. DMSO-water binary mixture has repeatedly given evidences of its dual anomalous nature in front of our systematic investigation through steady-state and time-resolved measurements. We have calculated average solvation times of C480 by two individual well-known methods, among them first one is spectral-reconstruction method and another one is single-wavelength measurement method. The results of both the methods roughly indicate that solvation time of C480 reaches maxima in the mole fraction of DMSO XD = 0.12-0.17 and XD = 0.27-0.35, respectively. Among them, the second region (XD = 0.27-0.35) is very common as most of the thermodynamic properties exhibit deviation in this range. Most probably, the anomalous solvation trend in this region is fully guided by the shear viscosity of the medium. However, the first region is the most interesting one. In this region due to formation of strongly hydrogen bonded 1DMSO:2H2O complexes, hydration around the probe C480 decreases, as a result of which solvation time increases.

Octanol-Water Partition Coefficient from 3D-RISM-KH Molecular Theory of Solvation with Partial Molar Volume Correction.

PubMed

Huang, WenJuan; Blinov, Nikolay; Kovalenko, Andriy

2015-04-30

The octanol-water partition coefficient is an important physical-chemical characteristic widely used to describe hydrophobic/hydrophilic properties of chemical compounds. The partition coefficient is related to the transfer free energy of a compound from water to octanol. Here, we introduce a new protocol for prediction of the partition coefficient based on the statistical-mechanical, 3D-RISM-KH molecular theory of solvation. It was shown recently that with the compound-solvent correlation functions obtained from the 3D-RISM-KH molecular theory of solvation, the free energy functional supplemented with the correction linearly related to the partial molar volume obtained from the Kirkwood-Buff/3D-RISM theory, also called the "universal correction" (UC), provides accurate prediction of the hydration free energy of small compounds, compared to explicit solvent molecular dynamics [ Palmer , D. S. ; J. Phys.: Condens. Matter 2010 , 22 , 492101 ]. Here we report that with the UC reparametrized accordingly this theory also provides an excellent agreement with the experimental data for the solvation free energy in nonpolar solvent (1-octanol) and so accurately predicts the octanol-water partition coefficient. The performance of the Kovalenko-Hirata (KH) and Gaussian fluctuation (GF) functionals of the solvation free energy, with and without UC, is tested on a large library of small compounds with diverse functional groups. The best agreement with the experimental data for octanol-water partition coefficients is obtained with the KH-UC solvation free energy functional.

Enantiomer analysis of chiral carboxylic acids by AIE molecules bearing optically pure aminol groups.

PubMed

Zheng, Yan-Song; Hu, Yu-Jian; Li, Dong-Mi; Chen, Yi-Chang

2010-01-15

Pure enantiomers of carboxylic acids are a class of important biomolecules, chiral drugs, chiral reagents, etc. Analysis of the enantiomers usually needs expensive instrument or complex chiral receptors. However, to develop simple and reliable methods for the enantiomer analysis of acids is difficult. In this paper, chiral recognition of 2,3-dibenzoyltartaric acid and mandelic acid was first carried out by aggregation-induced emission molecules bearing optically pure aminol group, which was easily synthesized. The chiral recognition is not only seen by naked eyes but also measured by fluorophotometer. The difference of fluorescence intensity between the two enantiomers of the acids aroused by the aggregation-induced emission molecules was up to 598. The chiral recognition could be applied to quantitative analysis of enantiomer content of chiral acids. More chiral AIE amines need to be developed for enantiomer analysis of more carboxylic acids.

Chiral photonic crystal fibers with single mode and single polarization

NASA Astrophysics Data System (ADS)

Li, She; Li, Junqing

2015-12-01

Chiral photonic crystal fiber (PCF) with a solid core is numerically investigated by a modified chiral plane-wave expansion method. The effects of structural parameters and chirality strength are analyzed on single-polarization single-mode range and polarization states of guided modes. The simulation demonstrates that the chiral photonic crystal fiber compared to its achiral counterpart possesses another single-circular-polarization operation range, which is located in the short-wavelength region. The original single-polarization operation range in the long-wavelength region extends to the short wavelength caused by introducing chirality. Then this range becomes a broadened one with elliptical polarization from linear polarization. With increase of chirality, the two single-polarization single-mode ranges may fuse together. By optimizing the structure, an ultra-wide single-circular-polarization operation range from 0.5 μm to 1.67 μm for chiral PCF can be realized with moderate chirality strength.

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

PubMed

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.

Chiral magnetic microspheres purified by centrifugal field flow fractionation and microspheres magnetic chiral chromatography for benzoin racemate separation

PubMed Central

Tian, Ailin; Qi, Jing; Liu, Yating; Wang, Fengkang; Ito, Yoichiro; Wei, Yun

2013-01-01

Separation of enantiomers still remains a challenge due to their identical physical and chemical properties in a chiral environment, and the research on specific chiral selector along with separation techniques continues to be conducted to resolve individual enantiomers. In our laboratory the promising magnetic chiral microspheres Fe3O4@SiO2@cellulose-2, 3-bis (3, 5-dimethylphenylcarbamate) have been developed to facilitate the resolution using both its magnetic property and chiral recognition ability. In our present studies this magnetic chiral selector was first purified by centrifuge field flow fractionation, and then used to separate benzoin racemate by a chromatographic method. Uniform-sized and masking-impurity-removed magnetic chiral selector was first obtained by field flow fractionation with ethanol through a spiral column mounted on the type-J planetary centrifuge, and using the purified magnetic chiral selector, the final chromatographic separation of benzoin racemate was successfully performed by eluting with ethanol through a coiled tube (wound around the cylindrical magnet to retain the magnetic chiral selector as a stationary phase) submerged in dry ice. In addition, an external magnetic field facilitates the recycling of the magnetic chiral selector. PMID:23891368

Fluorescent probe studies of polarity and solvation within room temperature ionic liquids: a review.

PubMed

Pandey, Shubha; Baker, Sheila N; Pandey, Siddharth; Baker, Gary A

2012-09-01

Ionic liquids display an array of useful and sometimes unconventional, solvent features and have attracted considerable interest in the field of green chemistry for the potential they hold to significantly reduce environmental emissions. Some of these points have a bearing on the chemical reactivity of these systems and have also generated interest in the physical and theoretical aspects of solvation in ionic liquids. This review presents an introduction to the field of ionic liquids, followed by discussion of investigations into the solvation properties of neat ionic liquids or mixed systems including ionic liquids as a major or minor component. The ionic liquid based multicomponent systems discussed are composed of other solvents, other ionic liquids, carbon dioxide, surfactants or surfactant solutions. Although we clearly focus on fluorescence spectroscopy as a tool to illuminate ionic liquid systems, the issues discussed herein are of general relevance to discussions of polarity and solvent effects in ionic liquids. Transient solvation measurements carried out by means of time-resolved fluorescence measurements are particularly powerful for their ability to parameterize the kinetics of the solvation process in ionic liquids and are discussed as well.

Evaluation of DNA Force Fields in Implicit Solvation

PubMed Central

Gaillard, Thomas; Case, David A.

2011-01-01

DNA structural deformations and dynamics are crucial to its interactions in the cell. Theoretical simulations are essential tools to explore the structure, dynamics, and thermodynamics of biomolecules in a systematic way. Molecular mechanics force fields for DNA have benefited from constant improvements during the last decades. Several studies have evaluated and compared available force fields when the solvent is modeled by explicit molecules. On the other hand, few systematic studies have assessed the quality of duplex DNA models when implicit solvation is employed. The interest of an implicit modeling of the solvent consists in the important gain in the simulation performance and conformational sampling speed. In this study, respective influences of the force field and the implicit solvation model choice on DNA simulation quality are evaluated. To this end, extensive implicit solvent duplex DNA simulations are performed, attempting to reach both conformational and sequence diversity convergence. Structural parameters are extracted from simulations and statistically compared to available experimental and explicit solvation simulation data. Our results quantitatively expose the respective strengths and weaknesses of the different DNA force fields and implicit solvation models studied. This work can lead to the suggestion of improvements to current DNA theoretical models. PMID:22043178

Crystal structure and physicochemical characterization of ambazone monohydrate, anhydrous, and acetate salt solvate.

PubMed

Muresan-Pop, Marieta; Braga, Dario; Pop, Mihaela M; Borodi, Gheorghe; Kacso, Irina; Maini, Lucia

2014-11-01

The crystal structures of the monohydrate and anhydrous forms of ambazone were determined by single-crystal X-ray diffraction (SC-XRD). Ambazone monohydrate is characterized by an infinite three-dimensional network involving the water molecules, whereas anhydrous ambazone forms a two-dimensional network via hydrogen bonds. The reversible transformation between the monohydrate and anhydrous forms of ambazone was evidenced by thermal analysis, temperature-dependent X-ray powder diffraction and accelerated stability at elevated temperature, and relative humidity (RH). Additionally, a novel ambazone acetate salt solvate form was obtained and its nature was elucidated by SC-XRD. Powder dissolution measurements revealed a substantial solubility and dissolution rate improvement of acetate salt solvated form in water and physiological media compared with ambazone forms. Also, the acetate salt solvate displayed good thermal and solution stability but it transformed to the monohydrate on storage at elevated temperature and RH. Our study shows that despite the requirement for controlled storage conditions, the acetate salt solvated form could be an alternative to ambazone when solubility and bioavailability improvement is critical for the clinical efficacy of the drug product. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Ion solvation in polymer blends and block copolymer melts: effects of chain length and connectivity on the reorganization of dipoles.

PubMed

Nakamura, Issei

2014-05-29

We studied the thermodynamic properties of ion solvation in polymer blends and block copolymer melts and developed a dipolar self-consistent field theory for polymer mixtures. Our theory accounts for the chain connectivity of polymerized monomers, the compressibility of the liquid mixtures under electrostriction, the permanent and induced dipole moments of monomers, and the resultant dielectric contrast among species. In our coarse-grained model, dipoles are attached to the monomers and allowed to rotate freely in response to electrostatic fields. We demonstrate that a strong electrostatic field near an ion reorganizes dipolar monomers, resulting in nonmonotonic changes in the volume fraction profile and the dielectric function of the polymers with respect to those of simple liquid mixtures. For the parameter sets used, the spatial variations near an ion can be in the range of 1 nm or larger, producing significant differences in the solvation energy among simple liquid mixtures, polymer blends, and block copolymers. The solvation energy of an ion depends substantially on the chain length in block copolymers; thus, our theory predicts the preferential solvation of ions arising from differences in chain length.

Induction of Chirality in Two-Dimensional Nanomaterials: Chiral 2D MoS2 Nanostructures.

PubMed

Purcell-Milton, Finn; McKenna, Robert; Brennan, Lorcan J; Cullen, Conor P; Guillemeney, Lilian; Tepliakov, Nikita V; Baimuratov, Anvar S; Rukhlenko, Ivan D; Perova, Tatiana S; Duesberg, Georg S; Baranov, Alexander V; Fedorov, Anatoly V; Gun'ko, Yurii K

2018-02-27

Two-dimensional (2D) nanomaterials have been intensively investigated due to their interesting properties and range of potential applications. Although most research has focused on graphene, atomic layered transition metal dichalcogenides (TMDs) and particularly MoS 2 have gathered much deserved attention recently. Here, we report the induction of chirality into 2D chiral nanomaterials by carrying out liquid exfoliation of MoS 2 in the presence of chiral ligands (cysteine and penicillamine) in water. This processing resulted in exfoliated chiral 2D MoS 2 nanosheets showing strong circular dichroism signals, which were far past the onset of the original chiral ligand signals. Using theoretical modeling, we demonstrated that the chiral nature of MoS 2 nanosheets is related to the presence of chiral ligands causing preferential folding of the MoS 2 sheets. There was an excellent match between the theoretically calculated and experimental spectra. We believe that, due to their high aspect ratio planar morphology, chiral 2D nanomaterials could offer great opportunities for the development of chiroptical sensors, materials, and devices for valleytronics and other potential applications. In addition, chirality plays a key role in many chemical and biological systems, with chiral molecules and materials critical for the further development of biopharmaceuticals and fine chemicals, and this research therefore should have a strong impact on relevant areas of science and technology such as nanobiotechnology, nanomedicine, and nanotoxicology.

Enantioselectively controlled release of chiral drug (metoprolol) using chiral mesoporous silica materials

NASA Astrophysics Data System (ADS)

Guo, Zhen; Du, Yu; Liu, Xianbin; Ng, Siu-Choon; Chen, Yuan; Yang, Yanhui

2010-04-01

Chiral porous materials have attracted burgeoning attention on account of their potential applications in many areas, such as enantioseparation, chiral catalysis, chemical sensors and drug delivery. In this report, chiral mesoporous silica (CMS) materials with various pore sizes and structures were prepared using conventional achiral templates (other than chiral surfactant) and a chiral cobalt complex as co-template. The synthesized CMS materials were characterized by x-ray diffraction, nitrogen physisorption, scanning electron microscope and transmission electron microscope. These CMS materials, as carriers, were demonstrated to be able to control the enantioselective release of a representative chiral drug (metoprolol). The release kinetics, as modeled by the power law equation, suggested that the release profiles of metoprolol were remarkably dependent on the pore diameter and pore structure of CMS materials. More importantly, R- and S-enantiomers of metoprolol exhibited different release kinetics on CMS compared to the corresponding achiral mesoporous silica (ACMS), attributable to the existence of local chirality on the pore wall surface of CMS materials. The chirality of CMS materials on a molecular level was further substantiated by vibrational circular dichroism measurements.

Five chiral Cd(II) complexes with dual chiral components: Effect of positional isomerism, luminescence and SHG response

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Lin, E-mail: lcheng@seu.edu.cn; Jiangsu Province Hi-Tech Key Laboratory for Bio-medical Research, Southeast University, Nanjing 211189; Wang, Jun

2015-01-15

Five chiral Cd(II) complexes with dual chiral components have been synthesized by using a series of (1R,2R)–N{sup 1},N{sup 2}-bis(pyridinylmethyl)cyclohexane-1,2-diamine ligands with different N-positions of pyridyl rings and Cd(NO{sub 3}){sub 2}. The circular dichroism (CD) spectra and second-harmonic generation (SHG) efficiency measurements confirmed that they are of structural chirality in the bulk samples. The luminescent properties indicated that they may have potential applications as optical materials. The formation of discrete mononuclear and binuclear complexes, and one-dimensional chains may be attributed to positional isomerism of the ligands. - Graphical abstract: Five chiral Cd(II) complexes with dual chiral components have been synthesized bymore » using a series of chiral ligands with different N-positions of pyridyl rings. - Highlights: • Five chiral Cd(II) complexes with dual chiral components have been synthesized. • CD spectra and SHG efficiency of the bulk samples have been measured. • The complexes display luminescent properties.« less

Chirality and energy transfer amplified circularly polarized luminescence in composite nanohelix

PubMed Central

Yang, Dong; Duan, Pengfei; Zhang, Li; Liu, Minghua

2017-01-01

Transfer of both chirality and energy information plays an important role in biological systems. Here we show a chiral donor π-gelator and assembled it with an achiral π-acceptor to see how chirality and energy can be transferred in a composite donor–acceptor system. It is found that the individual chiral gelator can self-assemble into nanohelix. In the presence of the achiral acceptor, the self-assembly can also proceed and lead to the formation of the composite nanohelix. In the composite nanohelix, an energy transfer is realized. Interestingly, in the composite nanohelix, the achiral acceptor can both capture the supramolecular chirality and collect the circularly polarized energy from the chiral donor, showing both supramolecular chirality and energy transfer amplified circularly polarized luminescence (ETACPL). PMID:28585538

Chirality and energy transfer amplified circularly polarized luminescence in composite nanohelix

NASA Astrophysics Data System (ADS)

Yang, Dong; Duan, Pengfei; Zhang, Li; Liu, Minghua

2017-06-01

Transfer of both chirality and energy information plays an important role in biological systems. Here we show a chiral donor π-gelator and assembled it with an achiral π-acceptor to see how chirality and energy can be transferred in a composite donor-acceptor system. It is found that the individual chiral gelator can self-assemble into nanohelix. In the presence of the achiral acceptor, the self-assembly can also proceed and lead to the formation of the composite nanohelix. In the composite nanohelix, an energy transfer is realized. Interestingly, in the composite nanohelix, the achiral acceptor can both capture the supramolecular chirality and collect the circularly polarized energy from the chiral donor, showing both supramolecular chirality and energy transfer amplified circularly polarized luminescence (ETACPL).

Tunable Chiroptical Properties from the Plasmonic Band to Metal-Ligand Charge Transfer Band of the Cysteine Capped Molybdenum Oxide Nanoparticles.

PubMed

Li, Yiwen; Cheng, Jiaji; Li, Jiagen; Zhu, Xi; He, TingChao; Chen, Rui; Tang, Zikang

2018-06-25

Understanding the interactions between a semiconducting nanocrystal surface and chiral anchoring molecules could resolve the mechanism of chirality induction in nanoscale and facilitate the rational design of chiral semiconducting materials for chiroptics. Herein, we present chiral molybdenum oxide nanoparticles in which chirality is transferred via a bio-to-nano approach. With facile controlling on the amount of chiral cysteine molecules under redox treatment, circular dichroism (CD) signals are generated in plasmon region and metal-ligand charge transfer band. The obtained enhanced CD signals with tunable line-shapes illustrate the possibility of using chiral molybdenum oxide nanoparticles as potentials for chiral semiconductor nanosensors, optoelectronics and photocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chirality in molecular collision dynamics

NASA Astrophysics Data System (ADS)

Lombardi, Andrea; Palazzetti, Federico

2018-02-01

Chirality is a phenomenon that permeates the natural world, with implications for atomic and molecular physics, for fundamental forces and for the mechanisms at the origin of the early evolution of life and biomolecular homochirality. The manifestations of chirality in chemistry and biochemistry are numerous, the striking ones being chiral recognition and asymmetric synthesis with important applications in molecular sciences and in industrial and pharmaceutical chemistry. Chiral discrimination phenomena, due to the existence of two enantiomeric forms, very well known in the case of interaction with light, but still nearly disregarded in molecular collision studies. Here we review some ideas and recent advances about the role of chirality in molecular collisions, designing and illustrating molecular beam experiments for the demonstration of chiral effects and suggesting a scenario for a stereo-directional origin of chiral selection.

Field redefinitions and Plebanski formalism for GR

NASA Astrophysics Data System (ADS)

Krasnov, Kirill

2018-07-01

We point out that there exists a family of transformations acting on BF-type Lagrangians of gravity, with Lagrangians related by such a transformation corresponding to classically equivalent theories. A transformation of this type corresponds to a particular field redefinition. We discuss both the chiral and non-chiral cases. In the chiral case there is a one-parameter, and in the non-chiral case a two-parameter family of such transformations. In the chiral setup, we use these transformations to give an alternative derivation of the chiral BF plus potential formulation of general relativity that was proposed recently. In the non-chiral case, we show that there is a new BF plus potential type formulation of GR. We also make some remarks on the non-chiral pure connection formulation.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Preferential solvatation of human serum albumin in dimethylsulfoxide-H2O binary solution

NASA Astrophysics Data System (ADS)

Grigoryan, K. R.

2009-12-01

The preferential solvatation of human serum albumin (HSA) in dimethylsulfoxide (DMSO) aqueous solutions were studied using the densitometry method. It has been shown that at DMSO low concentrations HSA undergoes to preferential hydration, but at DMSO higher concentrations preferential binding of DMSO molecules to protein occurs. It has been estimated that DMSO exhibits stabilizing/destabilizing effect on HSA structure which is explained in terms of hydration/solvatation of protein, on the one hand, and the medium structure enhancement/disruption around the protein molecule, on the other hand.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOEpatents

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

2017-01-24

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Electron Solvation in Two Dimensions

NASA Astrophysics Data System (ADS)

Miller, A. D.; Bezel, I.; Gaffney, K. J.; Garrett-Roe, S.; Liu, S. H.; Szymanski, P.; Harris, C. B.

2002-08-01

Ultrafast two-photon photoemission has been used to study electron solvation at two-dimensional metal/polar-adsorbate interfaces. The molecular motion that causes the excess electron solvation is manifested as a dynamic shift in the electronic energy. Although the initially excited electron is delocalized in the plane of the interface, interactions with the adsorbate can lead to its localization. A method for determining the spatial extent of the localized electron in the plane of the interface has been developed. This spatial extent was measured to be on the order of a single adsorbate molecule.

Deep-Subwavelength Resolving and Manipulating of Hidden Chirality in Achiral Nanostructures.

PubMed

Zu, Shuai; Han, Tianyang; Jiang, Meiling; Lin, Feng; Zhu, Xing; Fang, Zheyu

2018-04-24

The chiral state of light plays a vital role in light-matter interactions and the consequent revolution of nanophotonic devices and advanced modern chiroptics. As the light-matter interaction goes into the nano- and quantum world, numerous chiroptical technologies and quantum devices require precise knowledge of chiral electromagnetic modes and chiral radiative local density of states (LDOS) distributions in detail, which directly determine the chiral light-matter interaction for applications such as chiral light detection and emission. With classical optical techniques failing to directly measure the chiral radiative LDOS, deep-subwavelength imaging and control of circular polarization (CP) light associated phenomena are introduced into the agenda. Here, we simultaneously reveal the hidden chiral electromagnetic mode and acquire its chiral radiative LDOS distribution of a single symmetric nanostructure at the deep-subwavelength scale by using CP-resolved cathodoluminescence (CL) microscopy. The chirality of the symmetric nanostructure under normally incident light excitation, resulting from the interference between the symmetric and antisymmetric modes of the V-shaped nanoantenna, is hidden in the near field with a giant chiral distribution (∼99%) at the arm-ends, which enables the circularly polarized CL emission from the radiative LDOS hot-spot and the following active helicity control at the deep-subwavelength scale. The proposed V-shaped nanostructure as a functional unit is further applied to the helicity-dependent binary encoding and the two-dimensional display applications. The proposed physical principle and experimental configuration can promote the future chiral characterization and manipulation at the deep-subwavelength scale and provide direct guidelines for the optimization of chiral light-matter interactions for future quantum studies.

Recent advances in the use of ionic liquids for electrochemical sensing.

PubMed

Silvester, Debbie S

2011-12-07

Ionic Liquids are salts that are liquid at (or just above) room temperature. They possess several advantageous properties (e.g. high intrinsic conductivity, wide electrochemical windows, low volatility, high thermal stability and good solvating ability), which make them ideal as non-volatile electrolytes in electrochemical sensors. This mini-review article describes the recent uses of ionic liquids in electrochemical sensing applications (covering the last 3 years) in the context of voltammetric sensing at solid/liquid, liquid/liquid interfaces and carbon paste electrodes, as well as their use in gas sensing, ion-selective electrodes, and for detecting biological molecules, explosives and chemical warfare agents. A comment on the future direction and challenges in this field is also presented.

Analyzing intrinsic plasmonic chirality by tracking the interplay of electric and magnetic dipole modes.

PubMed

Hu, Li; Huang, Yingzhou; Pan, Lujun; Fang, Yurui

2017-09-11

Plasmonic chirality represents significant potential for novel nanooptical devices due to its association with strong chiroptical responses. Previous reports on plasmonic chirality mechanism mainly focus on phase retardation and coupling. In this paper, we propose a model similar to the chiral molecules for explaining the intrinsic plasmonic chirality mechanism of varies 3D chiral structures quantitatively based on the interplay and mixing of electric and magnetic dipole modes (directly from electromagnetic field numerical simulations), which forms mixed electric and magnetic polarizability.

Evaluating the Free Energies of Solvation and Electronic Structures of Lithium-Ion Battery Electrolytes.

PubMed

Shakourian-Fard, Mehdi; Kamath, Ganesh; Sankaranarayanan, Subramanian K R S

2016-09-19

Adaptive biasing force molecular dynamics simulations and density functional theory calculations were performed to understand the interaction of Li(+) with pure carbonates and ethylene carbonate (EC)-based binary mixtures. The most favorable Li carbonate cluster configurations obtained from molecular dynamics simulations were subjected to detailed structural and thermochemistry calculations on the basis of the M06-2X/6-311++G(d,p) level of theory. We report the ranking of these electrolytes on the basis of the free energies of Li-ion solvation in carbonates and EC-based mixtures. A strong local tetrahedral order involving four carbonates around the Li(+) was seen in the first solvation shell. Thermochemistry calculations revealed that the enthalpy of solvation and the Gibbs free energy of solvation of the Li(+) ion with carbonates are negative and suggested the ion-carbonate complexation process to be exothermic and spontaneous. Natural bond orbital analysis indicated that Li(+) interacts with the lone pairs of electrons on the carbonyl oxygen atom in the primary solvation sphere. These interactions lead to an increase in the carbonyl (C=O) bond lengths, as evidenced by a redshift in the vibrational frequencies [ν(C=O)] and a decrease in the electron density values at the C=O bond critical points in the primary solvation sphere. Quantum theory of atoms in molecules, localized molecular orbital energy decomposition analysis (LMO-EDA), and noncovalent interaction plots revealed the electrostatic nature of the Li(+) ion interactions with the carbonyl oxygen atoms in these complexes. On the basis of LMO-EDA, the strongest attractive interaction in these complexes was found to be the electrostatic interaction followed by polarization, dispersion, and exchange interactions. Overall, our calculations predicted EC and a binary mixture of EC/dimethyl carbonate to be appropriate electrolytes for Li-ion batteries, which complies with experiments and other theoretical results. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral corrections to the Adler-Weisberger sum rule

NASA Astrophysics Data System (ADS)

Beane, Silas R.; Klco, Natalie

2016-12-01

The Adler-Weisberger sum rule for the nucleon axial-vector charge, gA , offers a unique signature of chiral symmetry and its breaking in QCD. Its derivation relies on both algebraic aspects of chiral symmetry, which guarantee the convergence of the sum rule, and dynamical aspects of chiral symmetry breaking—as exploited using chiral perturbation theory—which allow the rigorous inclusion of explicit chiral symmetry breaking effects due to light-quark masses. The original derivations obtained the sum rule in the chiral limit and, without the benefit of chiral perturbation theory, made various attempts at extrapolating to nonvanishing pion masses. In this paper, the leading, universal, chiral corrections to the chiral-limit sum rule are obtained. Using PDG data, a recent parametrization of the pion-nucleon total cross sections in the resonance region given by the SAID group, as well as recent Roy-Steiner equation determinations of subthreshold amplitudes, threshold parameters, and correlated low-energy constants, the Adler-Weisberger sum rule is confronted with experimental data. With uncertainty estimates associated with the cross-section parametrization, the Goldberger-Treimann discrepancy, and the truncation of the sum rule at O (Mπ4) in the chiral expansion, this work finds gA=1.248 ±0.010 ±0.007 ±0.013 .

Chiral magnetic microspheres purified by centrifugal field flow fractionation and microspheres magnetic chiral chromatography for benzoin racemate separation.

PubMed

Tian, Ailin; Qi, Jing; Liu, Yating; Wang, Fengkang; Ito, Yoichiro; Wei, Yun

2013-08-30

Separation of enantiomers still remains a challenge due to their identical physical and chemical properties in a chiral environment, and the research on specific chiral selector along with separation techniques continues to be conducted to resolve individual enantiomers. In our laboratory the promising magnetic chiral microspheres Fe3O4@SiO2@cellulose-2, 3-bis (3,5-dimethylphenylcarbamate) have been developed to facilitate the resolution using both its magnetic property and chiral recognition ability. In our present studies this magnetic chiral selector was first purified by centrifuge field flow fractionation, and then used to separate benzoin racemate by a chromatographic method. Uniform-sized and masking-impurity-removed magnetic chiral selector was first obtained by field flow fractionation with ethanol through a spiral column mounted on the type-J planetary centrifuge, and using the purified magnetic chiral selector, the final chromatographic separation of benzoin racemate was successfully performed by eluting with ethanol through a coiled tube (wound around the cylindrical magnet to retain the magnetic chiral selector as a stationary phase) submerged in dry ice. In addition, an external magnetic field facilitates the recycling of the magnetic chiral selector. Copyright © 2013 Elsevier B.V. All rights reserved.

A chiral self-assembled monolayer derived from a resolving agent and its performance as a crystallization template for an organic compound from organic solvents.

PubMed

Bejarano-Villafuerte, Ángela; van der Meijden, Maarten W; Lingenfelder, Magalí; Wurst, Klaus; Kellogg, Richard M; Amabilino, David B

2012-12-07

A new chiral nonracemic thiol derived from a popular acidic resolving agent that incorporates a cyclic disubstituted phosphate group (phencyphos) has been prepared in enantiomerically pure form. The stereochemistry and absolute configuration were established by performing a single-crystal X-ray structural analysis of a synthetic intermediate. The thiol compound was used for the preparation of self-assembled monolayers (SAMs) on both monocrystalline and polycrystalline metallic gold, which have very different surface roughness. The monolayers were used to promote the nucleation and growth of crystals from nonaqueous solutions of an organic molecule (the parent phencyphos) of similar structure to the compound present in the monolayer. The template layers influence the nucleation and growth of the phencyphos crystals despite the lack of two-dimensional order in the surfaces. Heterogeneous nucleation of phencyphos takes place upon evaporation of either CHCl(3) or isopropanol solutions of the compound on the SAM surfaces, where the evaporation rate merely influences the size and homogeneity of the crystals. The roughness of the surface also plays an important role; the polycrystalline gold produces more homogeneous samples because of the greater number of nucleation sites. Clear evidence for nucleation and growth on the surfaces is shown by scanning electron microscopy. The variation in crystal form achieved by using different surfaces and solvents suggests that the layers are applicable for the preparation of organic crystals from organic solutions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Broadband reflection of polymer-stabilized chiral nematic liquid crystals induced by a chiral azobenzene compound.

PubMed

Chen, Xingwu; Wang, Ling; Chen, Yinjie; Li, Chenyue; Hou, Guoyan; Liu, Xin; Zhang, Xiaoguang; He, Wanli; Yang, Huai

2014-01-21

A chiral nematic liquid crystal-photopolymerizable monomer-chiral azobenzene compound composite was prepared and then polymerized under UV irradiation. The reflection wavelength of the composite can be extended to cover the 1000-2400 nm range and also be adjusted to the visible light region by controlling the concentration of chiral compounds.

Structure and Dynamics of Solvated Polymers near a Silica Surface: On the Different Roles Played by Solvent.

PubMed

Perrin, Elsa; Schoen, Martin; Coudert, François-Xavier; Boutin, Anne

2018-04-26

Whereas it is experimentally known that the inclusion of nanoparticles in hydrogels can lead to a mechanical reinforcement, a detailed molecular understanding of the adhesion mechanism is still lacking. Here we use coarse-grained molecular dynamics simulations to investigate the nature of the interface between silica surfaces and solvated polymers. We show how differences in the nature of the polymer and the polymer-solvent interactions can lead to drastically different behavior of the polymer-surface adhesion. Comparing explicit and implicit solvent models, we conclude that this effect cannot be fully described in an implicit solvent. We highlight the crucial role of polymer solvation for the adsorption of the polymer chain on the silica surface, the significant dynamics of polymer chains on the surface, and details of the modifications in the structure solvated polymer close to the interface.

Incorporation of the TIP4P water model into a continuum solvent for computing solvation free energy

NASA Astrophysics Data System (ADS)

Yang, Pei-Kun

2014-10-01

The continuum solvent model is one of the commonly used strategies to compute solvation free energy especially for large-scale conformational transitions such as protein folding or to calculate the binding affinity of protein-protein/ligand interactions. However, the dielectric polarization for computing solvation free energy from the continuum solvent is different than that obtained from molecular dynamic simulations. To mimic the dielectric polarization surrounding a solute in molecular dynamic simulations, the first-shell water molecules was modeled using a charge distribution of TIP4P in a hard sphere; the time-averaged charge distribution from the first-shell water molecules were estimated based on the coordination number of the solute, and the orientation distribution of the first-shell waters and the intermediate water molecules were treated as that of a bulk solvent. Based on this strategy, an equation describing the solvation free energy of ions was derived.

Solvation of o-hydroxybenzoic acid in pure and modified supercritical carbon dioxide, according to numerical modeling data

NASA Astrophysics Data System (ADS)

Antipova, M. L.; Gurina, D. L.; Odintsova, E. G.; Petrenko, V. E.

2015-08-01

The dissolution of an elementary fragment of crystal structure (an o-hydroxybenzoic acid ( o-HBA) dimer) in both pure and modified supercritical (SC) carbon dioxide by adding methanol (molar fraction, 0.035) at T = 318 K, ρ = 0.7 g/cm3 is simulated. Features of the solvation mechanism in each solvent are revealed. The solvation of o-HBA in pure SC CO2 is shown to occur via electron donor-acceptor interactions. o-HBA forms a solvate complex in modified SC CO2 through hydrogen bonds between the carboxyl group and methanol. The hydroxyl group of o-HBA participates in the formation of an intramolecular hydrogen bond, and not in interactions with the solvent. It is concluded that the o-HBA-methanol complex is a stable molecular structure, and its lifetime is one order of magnitude higher than those of other hydrogen bonds in fluids.

A shell-resolved analysis of preferential solvation of coffee ingredients in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate

NASA Astrophysics Data System (ADS)

Zeindlhofer, Veronika; Berger, Magdalena; Steinhauser, Othmar; Schröder, Christian

2018-05-01

Ionic liquids increase the solubility of various coffee ingredients in aqueous solution but little is known about the underlying mechanism. Kirkwood-Buff integrals as well as the potential of mean force indicate that the imidazolium cations are accumulated at the surface of the solutes, removing water molecules from the solute surface. Although hydrogen bonding of the anions to hydroxy groups of the solutes can be detected, their concentration at the surface is less enhanced compared to the cations. The decomposition into solvation shells by Voronoi tessellation reveals that structural features are only observed in the first solvation shell. Nevertheless, the depletion of water and the excess concentration of the ions and, in particular, of the cations are visible in the next solvation shells as well. Therefore, classical arguments of hydrotropic theory fail to explain this behavior.

Water-enhanced solvation of organic solutes in ketone and ester solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, J.H.; Brunt, V. van; King, C.J.

1994-05-01

Previous research has shown that the solubilities of dicarboxylic acids in certain electron-donor solvents are substantially increased in the presence of water. Information on solubilities, liquid-liquid equilibria and maximum-boiling ternary azeotropes was screened so as to identify other systems where codissolved water appears to enhance solvation of organic solutes in solvents. Several carboxylic acids, an alcohol, diols, and phenols were selected for examination as solutes in ketone and ester solvents. Effects of water upon solute solubilities and volatilities were measured. Results showed that water-enhanced solvation is greatest for carboxylic acids. Solute activity coefficients decreased by factors of 2--3, 6--8, andmore » 7--10 due to the presence of water for mono-, di and tricarboxylic acids, respectively. Activity coefficients decreased by a factor of about 1.5 for ethanol and 1,2-propanediol as solutes. Water-enhanced solvation of phenols is small, when existent.« less

Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction.

PubMed

Zhu, Di; Zhang, Linghong; Ruther, Rose E; Hamers, Robert J

2013-09-01

The photocatalytic reduction of N₂ to NH₃ is typically hampered by poor binding of N₂ to catalytic materials and by the very high energy of the intermediates involved in this reaction. Solvated electrons directly introduced into the reactant solution can provide an alternative pathway to overcome such limitations. Here we demonstrate that illuminated hydrogen-terminated diamond yields facile electron emission into water, thus inducing reduction of N₂ to NH₃ at ambient temperature and pressure. Transient absorption measurements at 632 nm reveal the presence of solvated electrons adjacent to the diamond after photoexcitation. Experiments using inexpensive synthetic diamond samples and diamond powder show that photocatalytic activity is strongly dependent on the surface termination and correlates with the production of solvated electrons. The use of diamond to eject electrons into a reactant liquid represents a new paradigm for photocatalytic reduction, bringing electrons directly to reactants without requiring molecular adsorption to the surface.

Solvation of decane and benzene in mixtures of 1-octanol and N, N-dimethylformamide

NASA Astrophysics Data System (ADS)

Kustov, A. V.; Smirnova, N. L.

2016-09-01

The heats of dissolution of decane and benzene in a model system of octanol-1 (OctOH) and N, N-dimethylformamide (DMF) at 308 K are measured using a variable temperature calorimeter equipped with an isothermal shell. Standard enthalpies are determined and standard heat capacities of dissolution in the temperature range of 298-318 K are calculated using data obtained in [1, 2]. The state of hydrocarbon molecules in a binary mixture is studied in terms of the enhanced coordination model (ECM). Benzene is shown to be preferentially solvated by DMF over the range of physiological temperatures. The solvation shell of decane is found to be strongly enriched with 1-octanol. It is obvious that although both hydrocarbons are nonpolar, the presence of the aromatic π-system in benzene leads to drastic differences in their solvation in a lipid-protein medium.

Solvent effect on the self-assembly of salt solvates of an antihypertensive drug azilsartan and 2-methylimidazole

NASA Astrophysics Data System (ADS)

Zhang, Xian-Rui; Zhang, Lei

2017-06-01

Three salt solvates of azilsartan (AZ) with 2-methylimidazole (2MI) (namely AZ-2MI-H2O, AZ-2MI-ACE and AZ-2MI-THF) and one azilsartan solvate (AZ-DIO, ACE = acetone, THF = tetrahydrofuran, and DIO = 1,4-dioxane) were manufactured by solvent-controlled self-assembly in aqueous-organic solutions. The experimental result of AZ-DIO shows that AZ is high affinity to DIO molecule, which has a unique ability to prevent salt formation between AZ and 2MI. Thermal studies of three salt solvates exhibit poor thermodynamic stability in environmental conditions. Solubility experiments show that AZ-2MI-ACE and AZ-2MI-THF are unstable and convert to AZ-2MI-H2O in aqueous solution, and that AZ-2MI-H2O exhibits increased solubility and retention stability in an aqueous medium compared with the commercial AZ-A crystalline form.

Theoretical Foundation for Electric-Dipole-Allowed Chiral-Specific Fluorescence Optical Rotary Dispersion (F-ORD) from Interfacial Assemblies.

PubMed

Deng, Fengyuan; Ulcickas, James R W; Simpson, Garth J

2016-11-03

Fluorescence optical rotary dispersion (F-ORD) is proposed as a novel chiral-specific and interface-specific spectroscopic method. F-ORD measurements of uniaxial assemblies are predicted to be fully electric-dipole-allowed, with corresponding increases in sensitivity to chirality relative to chiral-specific measurements in isotropic assemblies that are commonly interpreted through coupling between electric and magnetic dynamic dipoles. Observations of strong chiral sensitivity in prior single-molecule fluorescence measurements of chiral interfacial molecules are in excellent qualitative agreement with the predictions of the F-ORD mechanism and challenging to otherwise explain. F-ORD may provide methods to suppress background fluorescence in studies of biological interfaces, as the detected signal requires both polar local order and interfacial chirality. In addition, the molecular-level descriptions of the mechanisms underpinning F-ORD may also potentially apply to aid in interpreting chiral-specific Raman and surface-enhanced Raman spectroscopy measurements of uniaxially oriented assemblies, opening up opportunities for chiral-specific and interface-specific vibrational spectroscopy.

Role of Achiral Nucleobases in Multicomponent Chiral Self-Assembly: Purine-Triggered Helix and Chirality Transfer.

PubMed

Deng, Ming; Zhang, Li; Jiang, Yuqian; Liu, Minghua

2016-11-21

Chiral self-assembly is a basic process in biological systems, where many chiral biomolecules such as amino acids and sugars play important roles. Achiral nucleobases usually covalently bond to saccharides and play a significant role in the formation of the double helix structure. However, it remains unclear how the achiral nucleobases can function in chiral self-assembly without the sugar modification. Herein, we have clarified that purine nucleobases could trigger N-(9-fluorenylmethox-ycarbonyl) (Fmoc)-protected glutamic acid to self-assemble into helical nanostructures. Moreover, the helical nanostructure could serve as a matrix and transfer the chirality to an achiral fluorescence probe, thioflavin T (ThT). Upon chirality transfer, the ThT showed not only supramolecular chirality but also circular polarized fluorescence (CPL). Without the nucleobase, the self-assembly processes cannot happen, thus providing an example where achiral molecules played an essential role in the expression and transfer of the chirality. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral superconductors.

PubMed

Kallin, Catherine; Berlinsky, John

2016-05-01

Chiral superconductivity is a striking quantum phenomenon in which an unconventional superconductor spontaneously develops an angular momentum and lowers its free energy by eliminating nodes in the gap. It is a topologically non-trivial state and, as such, exhibits distinctive topological modes at surfaces and defects. In this paper we discuss the current theory and experimental results on chiral superconductors, focusing on two of the best-studied systems, Sr2RuO4, which is thought to be a chiral triplet p-wave superconductor, and UPt3, which has two low-temperature superconducting phases (in zero magnetic field), the lower of which is believed to be chiral triplet f-wave. Other systems that may exhibit chiral superconductivity are also discussed. Key signatures of chiral superconductivity are surface currents and chiral Majorana modes, Majorana states in vortex cores, and the possibility of half-flux quantum vortices in the case of triplet pairing. Experimental evidence for chiral superconductivity from μSR, NMR, strain, polar Kerr effect and Josephson tunneling experiments are discussed.

Acylation of Chiral Alcohols: A Simple Procedure for Chiral GC Analysis.

PubMed

Oromí-Farrús, Mireia; Torres, Mercè; Canela, Ramon

2012-01-01

The use of iodine as a catalyst and either acetic or trifluoroacetic acid as a derivatizing reagent for determining the enantiomeric composition of acyclic and cyclic aliphatic chiral alcohols was investigated. Optimal conditions were selected according to the molar ratio of alcohol to acid, the reaction time, and the reaction temperature. Afterwards, chiral stability of chiral carbons was studied. Although no isomerization was observed when acetic acid was used, partial isomerization was detected with the trifluoroacetic acid. A series of chiral alcohols of a widely varying structural type were then derivatized with acetic acid using the optimal conditions. The resolution of the enantiomeric esters and the free chiral alcohols was measured using a capillary gas chromatograph equipped with a CP Chirasil-DEX CB column. The best resolutions were obtained with 2-pentyl acetates (α = 3.00) and 2-hexyl acetates (α = 1.95). This method provides a very simple and efficient experimental workup procedure for analyzing chiral alcohols by chiral-phase GC.

Enantiomeric Profiling of Chiral Pharmacologically Active Compounds in the Environment with the Usage of Chiral Liquid Chromatography 
Coupled with Tandem Mass Spectrometry

PubMed Central

Camacho-Muñoz, Dolores; Petrie, Bruce; Castrignanò, Erika; Kasprzyk-Hordern, Barbara

2016-01-01

The issue of drug chirality is attracting increasing attention among the scientific community. The phenomenon of chirality has been overlooked in environmental research (environmental occurrence, fate and toxicity) despite the great impact that chiral pharmacologically active compounds (cPACs) can provoke on ecosystems. The aim of this paper is to introduce the topic of chirality and its implications in environmental contamination. Special attention has been paid to the most recent advances in chiral analysis based on liquid chromatography coupled with mass spectrometry and the most popular protein based chiral stationary phases. Several groups of cPACs of environmental relevance, such as illicit drugs, human and veterinary medicines were discussed. The increase in the number of papers published in the area of chiral environmental analysis indicates that researchers are actively pursuing new opportunities to provide better understanding of environmental impacts resulting from the enantiomerism of cPACs. PMID:27713682

Topological chiral phonons in center-stacked bilayer triangle lattices

NASA Astrophysics Data System (ADS)

Xu, Xifang; Zhang, Wei; Wang, Jiaojiao; Zhang, Lifa

2018-06-01

Since chiral phonons were found in an asymmetric two-dimensional hexagonal lattice, there has been growing interest in the study of phonon chirality, which were experimentally verified very recently in monolayer tungsten diselenide (2018 Science 359 579). In this work, we find chiral phonons with nontrivial topology in center-stacked bilayer triangle lattices. At the Brillouin-zone corners, (), circularly polarized phonons and nonzero phonon Berry curvature are observed. Moreover, we find that the phonon chirality remain robust with changing sublattice mass ratio and interlayer coupling. The chiral phonons at the valleys are demonstrated in doubler-layer sodium chloride along the [1 1 1] direction. We believe that the findings on topological chiral phonons in triangle lattices will give guidance in the study of chiral phonons in real materials and promote the phononic applications.

Enhanced Chiral Discriminatory van der Waals Interactions Mediated by Chiral Surfaces

NASA Astrophysics Data System (ADS)

Barcellona, Pablo; Safari, Hassan; Salam, A.; Buhmann, Stefan Yoshi

2017-05-01

We predict a discriminatory interaction between a chiral molecule and an achiral molecule which is mediated by a chiral body. To achieve this, we generalize the van der Waals interaction potential between two ground-state molecules with electric, magnetic, and chiral response to nontrivial environments. The force is evaluated using second-order perturbation theory with an effective Hamiltonian. Chiral media enhance or reduce the free interaction via many-body interactions, making it possible to measure the chiral contributions to the van der Waals force with current technology. The van der Waals interaction is discriminatory with respect to enantiomers of different handedness and could be used to separate enantiomers. We also suggest a specific geometric configuration where the electric contribution to the van der Waals interaction is zero, making the chiral component the dominant effect.

No chiral truncation of quantum log gravity?

NASA Astrophysics Data System (ADS)

Andrade, Tomás; Marolf, Donald

2010-03-01

At the classical level, chiral gravity may be constructed as a consistent truncation of a larger theory called log gravity by requiring that left-moving charges vanish. In turn, log gravity is the limit of topologically massive gravity (TMG) at a special value of the coupling (the chiral point). We study the situation at the level of linearized quantum fields, focussing on a unitary quantization. While the TMG Hilbert space is continuous at the chiral point, the left-moving Virasoro generators become ill-defined and cannot be used to define a chiral truncation. In a sense, the left-moving asymptotic symmetries are spontaneously broken at the chiral point. In contrast, in a non-unitary quantization of TMG, both the Hilbert space and charges are continuous at the chiral point and define a unitary theory of chiral gravity at the linearized level.

Micropatterning of cells reveals chiral morphogenesis

PubMed Central

2013-01-01

Invariant left-right (LR) patterning or chirality is critical for embryonic development. The loss or reversal of LR asymmetry is often associated with malformations and disease. Although several theories have been proposed, the exact mechanism of the initiation of the LR symmetry has not yet been fully elucidated. Recently, chirality has been detected within single cells as well as multicellular structures using several in vitro approaches. These studies demonstrated the universality of cell chirality, its dependence on cell phenotype, and the role of physical boundaries. In this review, we discuss the theories for developmental LR asymmetry, compare various in vitro cell chirality model systems, and highlight possible roles of cell chirality in stem cell differentiation. We emphasize that the in vitro cell chirality systems have great promise for helping unveil the nature of chiral morphogenesis in development. PMID:23672821

Cooperative expression of atomic chirality in inorganic nanostructures.

PubMed

Wang, Peng-Peng; Yu, Shang-Jie; Govorov, Alexander O; Ouyang, Min

2017-02-02

Cooperative chirality phenomena extensively exist in biomolecular and organic systems via intra- and inter-molecular interactions, but study of inorganic materials has been lacking. Here we report, experimentally and theoretically, cooperative chirality in colloidal cinnabar mercury sulfide nanocrystals that originates from chirality interplay between the crystallographic lattice and geometric morphology at different length scales. A two-step synthetic scheme is developed to allow control of critical parameters of these two types of handedness, resulting in different chiral interplays expressed as observables through materials engineering. Furthermore, we adopt an electromagnetic model with the finite element method to elucidate cooperative chirality in inorganic systems, showing excellent agreement with experimental results. Our study enables an emerging class of nanostructures with tailored cooperative chirality that is vital for fundamental understanding of nanoscale chirality as well as technology applications based on new chiroptical building blocks.

Cooperative expression of atomic chirality in inorganic nanostructures

PubMed Central

Wang, Peng-peng; Yu, Shang-Jie; Govorov, Alexander O; Ouyang, Min

2017-01-01

Cooperative chirality phenomena extensively exist in biomolecular and organic systems via intra- and inter-molecular interactions, but study of inorganic materials has been lacking. Here we report, experimentally and theoretically, cooperative chirality in colloidal cinnabar mercury sulfide nanocrystals that originates from chirality interplay between the crystallographic lattice and geometric morphology at different length scales. A two-step synthetic scheme is developed to allow control of critical parameters of these two types of handedness, resulting in different chiral interplays expressed as observables through materials engineering. Furthermore, we adopt an electromagnetic model with the finite element method to elucidate cooperative chirality in inorganic systems, showing excellent agreement with experimental results. Our study enables an emerging class of nanostructures with tailored cooperative chirality that is vital for fundamental understanding of nanoscale chirality as well as technology applications based on new chiroptical building blocks. PMID:28148957

Application of L-proline derivatives as chiral shift reagents for enantiomeric recognition of carboxylic acids.

PubMed

Naziroglu, Hayriye Nevin; Durmaz, Mustafa; Bozkurt, Selahattin; Sirit, Abdulkadir

2011-07-01

Four proline-derived chiral receptors 5-8 were readily synthesized starting from L-proline. The enantiomeric recognition ability of chiral receptors was examined with a series of carboxylic acids by (1) H NMR spectroscopy. The molar ratio and the association constants of the chiral compounds with each of the enantiomers of guest molecules were determined by using Job plots and a nonlinear least-squares fitting method, respectively. The Job plots indicate that the hosts form 1:1 instantaneous complexes with all guests. The receptors exhibited different chiral recognition abilities toward the enantiomers of racemic guests. Among the chiral receptors used in this study, prolinamide 6 was found to be the best chiral shift reagent and is effective for the determination of the enantiomeric excess of chiral carboxylic acids. Copyright © 2011 Wiley-Liss, Inc.

Chirality-dependent cellular uptake of chiral nanocarriers and intracellular delivery of different amounts of guest molecules

NASA Astrophysics Data System (ADS)

Kehr, Nermin Seda; Jose, Joachim

2017-12-01

We demonstrate the organic molecules loaded and chiral polymers coated periodic mesoporous organosilica (PMO) to generate chiral nanocarriers that we used to study chirality-dependent cellular uptake in serum and serum-free media and the subsequent delivery of different amounts of organic molecules into cells. Our results show that the amount of internalized PMO and thus the transported amount of organic molecules by nanocarrier PMO into cells was chirality dependent and controlled by hard/soft protein corona formation on the PMO surfaces. Therefore, this study demonstrate that chiral porous nanocarriers could potentially be used as advanced drug delivery systems which are able to use the specific chiral surface-protein interactions to influence/control the amount of (bio)active molecules delivered to cells in drug delivery and/or imaging applications.

More on asymptotically anti-de Sitter spaces in topologically massive gravity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henneaux, Marc; Physique theorique et mathematique, Universite Libre de Bruxelles and International Solvay Institutes, ULB Campus Plaine C.P. 231, B-1050 Bruxelles; Martinez, Cristian

2010-09-15

Recently, the asymptotic behavior of three-dimensional anti-de Sitter (AdS) gravity with a topological mass term was investigated. Boundary conditions were given that were asymptotically invariant under the two dimensional conformal group and that included a falloff of the metric sufficiently slow to consistently allow pp-wave type of solutions. Now, pp waves can have two different chiralities. Above the chiral point and at the chiral point, however, only one chirality can be considered, namely, the chirality that has the milder behavior at infinity. The other chirality blows up faster than AdS and does not define an asymptotically AdS spacetime. By contrast,more » both chiralities are subdominant with respect to the asymptotic behavior of AdS spacetime below the chiral point. Nevertheless, the boundary conditions given in the earlier treatment only included one of the two chiralities (which could be either one) at a time. We investigate in this paper whether one can generalize these boundary conditions in order to consider simultaneously both chiralities below the chiral point. We show that this is not possible if one wants to keep the two-dimensional conformal group as asymptotic symmetry group. Hence, the boundary conditions given in the earlier treatment appear to be the best possible ones compatible with conformal symmetry. In the course of our investigations, we provide general formulas controlling the asymptotic charges for all values of the topological mass (not just below the chiral point).« less

Effect of molecular structure of tartrates on chiral recognition of tartrate-boric acid complex chiral selectors in chiral microemulsion electrokinetic chromatography.

PubMed

Hu, Shao-Qiang; Chen, Yong-Lei; Zhu, Hua-Dong; Shi, Hai-Jun; Yan, Na; Chen, Xing-Guo

2010-08-20

Eight l-tartrates and a d-tartrate with different alcohol moieties were used as chiral oils to prepare chiral microemulsions, which were utilized in conjunction with borate buffer to separate the enantiomers of beta-blockers or structurally related compounds by the chiral microemulsion electrokinetic chromatography (MEEKC) method. Among them, six were found to have a relatively good chiral separation performance and their chiral recognition effect in terms of both enantioselectivity and resolution increases linearly with the number of carbon atoms in the alkyl group of alcohol moiety. The tartrates containing alkyl groups of different structures but the same number of carbon atoms, i.e. one of straight chain and one of branched chain, provide similar enantioseparations. The trend was elucidated according to the changes in the difference of the steric matching between the molecules of two enantiomers and chiral selector. Furthermore, it was demonstrated for the first time that a water insoluble solid compound, di-i-butyl l-tartrate (mp. 73.5 degrees C), can be used as an oil to prepare a stable microemulsion to be used in the chiral MEEKC successfully. And a critical effect of the microemulsion for chiral separation, which has never been reported before, was found in this experiment, namely providing a hydrophobic environment to strengthen the interactions between the chiral selector and enantiomers. Copyright 2010 Elsevier B.V. All rights reserved.

Intelligent chiral sensing based on supramolecular and interfacial concepts.

PubMed

Ariga, Katsuhiko; Richards, Gary J; Ishihara, Shinsuke; Izawa, Hironori; Hill, Jonathan P

2010-01-01

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.

Anatomy of the chiral magnetic effect in and out of equilibrium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kharzeev, Dmitri; Stephanov, Mikhail; Yee, Ho-Ung

Here, we identify a new contribution to the chiral magnetic conductivity at finite frequencies—the magnetization current. This allows us to quantitatively reproduce the known field-theoretic time-dependent (AC) chiral magnetic response in terms of kinetic theory. We also evaluate the corresponding AC chiral magnetic conductivity in two-flavor QCD plasma at weak coupling. The magnetization current results from the spin response of chiral quasiparticles to magnetic field, and is thus proportional to the quasiparticle’s g -factor. Furthemrore, in condensed matter systems, where the chiral quasiparticles are emergent and the g -factor can significantly differ from 2, this opens up the possibility ofmore » tuning the AC chiral magnetic response.« less

Anatomy of the chiral magnetic effect in and out of equilibrium

DOE PAGES

Kharzeev, Dmitri; Stephanov, Mikhail; Yee, Ho-Ung

2017-03-28

Here, we identify a new contribution to the chiral magnetic conductivity at finite frequencies—the magnetization current. This allows us to quantitatively reproduce the known field-theoretic time-dependent (AC) chiral magnetic response in terms of kinetic theory. We also evaluate the corresponding AC chiral magnetic conductivity in two-flavor QCD plasma at weak coupling. The magnetization current results from the spin response of chiral quasiparticles to magnetic field, and is thus proportional to the quasiparticle’s g -factor. Furthemrore, in condensed matter systems, where the chiral quasiparticles are emergent and the g -factor can significantly differ from 2, this opens up the possibility ofmore » tuning the AC chiral magnetic response.« less

Active chiral fluids.

PubMed

Fürthauer, S; Strempel, M; Grill, S W; Jülicher, F

2012-09-01

Active processes in biological systems often exhibit chiral asymmetries. Examples are the chirality of cytoskeletal filaments which interact with motor proteins, the chirality of the beat of cilia and flagella as well as the helical trajectories of many biological microswimmers. Here, we derive constitutive material equations for active fluids which account for the effects of active chiral processes. We identify active contributions to the antisymmetric part of the stress as well as active angular momentum fluxes. We discuss four types of elementary chiral motors and their effects on a surrounding fluid. We show that large-scale chiral flows can result from the collective behavior of such motors even in cases where isolated motors do not create a hydrodynamic far field.

Competitive lithium solvation of linear and cyclic carbonates from quantum chemistry

DOE PAGES

Kent, Paul R. C.; Ganesh, Panchapakesan; Borodin, Oleg; ...

2015-11-17

The composition of the lithium cation (Li+) solvation shell in mixed linear and cyclic carbonate-based electrolytes has been re-examined using Born–Oppenheimer molecular dynamics (BOMD) as a function of salt concentration and cluster calculations with ethylene carbonate:dimethyl carbonate (EC:DMC)–LiPF 6 as a model system. A coordination preference for EC over DMC to a Li+ was found at low salt concentrations, while a slightly higher preference for DMC over EC was found at high salt concentrations. Analysis of the relative binding energies of the (EC) n(DMC) m–Li+ and (EC) n(DMC) m–LiPF 6 solvates in the gas-phase and for an implicit solvent (asmore » a function of the solvent dielectric constant) indicated that the DMC-containing Li+ solvates were stabilized relative to (EC 4)–Li+ and (EC) 3–LiPF 6 by immersing them in the implicit solvent. Such stabilization was more pronounced in the implicit solvents with a high dielectric constant. Results from previous Raman and IR experiments were reanalyzed and reconciled by correcting them for changes of the Raman activities, IR intensities and band shifts for the solvents which occur upon Li+ coordination. After these correction factors were applied to the results of BOMD simulations, the composition of the Li+ solvation shell from the BOMD simulations was found to agree well with the solvation numbers extracted from Raman experiments. Finally, the mechanism of the Li+ diffusion in the dilute (EC:DMC)LiPF 6 mixed solvent electrolyte was studied using the BOMD simulations.« less

The kinetics of chirality assignment in catalytic single-walled carbon nanotube growth and the routes towards selective growth.

PubMed

Xu, Ziwei; Qiu, Lu; Ding, Feng

2018-03-21

Depending on its specific structure, or so-called chirality, a single-walled carbon nanotube (SWCNT) can be either a conductor or a semiconductor. This feature ensures great potential for building ∼1 nm sized electronics if chirality-selected SWCNTs could be achieved. However, due to the limited understanding of the growth mechanism of SWCNTs, reliable methods for chirality-selected SWCNTs are still pending. Here we present a theoretical model on the chirality assignment and control of SWCNTs during the catalytic growth. This study reveals that the chirality of a SWCNT is determined by the kinetic incorporation of pentagons, especially the last (6 th ) one, during the nucleation stage. Our analysis showed that the chirality of a SWCNT is randomly assigned on a liquid or liquid-like catalyst surface, and two routes of synthesizing chirality-selected SWCNTs, which are verified by recent experimental achievements, are demonstrated. They are (i) by using high melting point crystalline catalysts, such as Ta, W, Re, Os, or their alloys, and (ii) by frequently changing the chirality of SWCNTs during their growth. This study paves the way for achieving chirality-selective SWCNT growth for high performance SWCNT based electronics.

Chemical chiral pollution: Impact on the society and science and need of the regulations in the 21st century.

PubMed

Basheer, Al Arsh

2018-04-01

The chiral pollution is a serious issue for our health and environment due to the enantio-selective biodegradation of the chiral pollutants. It has adverse impact on our society and science. There is a big loss of our economy due to the use of racemic agrochemicals. The most notorious chiral pollutants are pesticides, polychloro biphenyls, polyaromatic hydrocarbons, brominated flame retardants, drugs, and pharmaceuticals. More than 1500 chiral pollutants are present in the environment. Unfortunately, there is no regulation and control of the chiral pollutants. Therefore, it is an urgent need of the present 21st century to develop a data bank on the chiral pollutants, guidelines for controlling the production, sale and use of the racemic agrochemicals and the other industrial products. The Governments of the different countries should come forward to initiate the regulations. US, FDA, US EPA, and WHO are the most important regulatory authorities and should think about the chiral pollutants. The present article highlights the impact of the chiral pollution on the society and science. Besides, the efforts have also been made to emphasize the need of the regulations to control the chiral pollution. © 2017 Wiley Periodicals, Inc.

Laminar and Turbulent Dynamos in Chiral Magnetohydrodynamics. I. Theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rogachevskii, Igor; Kleeorin, Nathan; Ruchayskiy, Oleg

2017-09-10

The magnetohydrodynamic (MHD) description of plasmas with relativistic particles necessarily includes an additional new field, the chiral chemical potential associated with the axial charge (i.e., the number difference between right- and left-handed relativistic fermions). This chiral chemical potential gives rise to a contribution to the electric current density of the plasma ( chiral magnetic effect ). We present a self-consistent treatment of the chiral MHD equations , which include the back-reaction of the magnetic field on a chiral chemical potential and its interaction with the plasma velocity field. A number of novel phenomena are exhibited. First, we show that themore » chiral magnetic effect decreases the frequency of the Alfvén wave for incompressible flows, increases the frequencies of the Alfvén wave and of the fast magnetosonic wave for compressible flows, and decreases the frequency of the slow magnetosonic wave. Second, we show that, in addition to the well-known laminar chiral dynamo effect, which is not related to fluid motions, there is a dynamo caused by the joint action of velocity shear and chiral magnetic effect. In the presence of turbulence with vanishing mean kinetic helicity, the derived mean-field chiral MHD equations describe turbulent large-scale dynamos caused by the chiral alpha effect, which is dominant for large fluid and magnetic Reynolds numbers. The chiral alpha effect is due to an interaction of the chiral magnetic effect and fluctuations of the small-scale current produced by tangling magnetic fluctuations (which are generated by tangling of the large-scale magnetic field by sheared velocity fluctuations). These dynamo effects may have interesting consequences in the dynamics of the early universe, neutron stars, and the quark–gluon plasma.« less

Enzymatic synthesis of chiral amino-alcohols by coupling transketolase and transaminase-catalyzed reactions in a cascading continuous-flow microreactor system.

PubMed

Gruber, Pia; Carvalho, Filipe; Marques, Marco P C; O'Sullivan, Brian; Subrizi, Fabiana; Dobrijevic, Dragana; Ward, John; Hailes, Helen C; Fernandes, Pedro; Wohlgemuth, Roland; Baganz, Frank; Szita, Nicolas

2018-03-01

Rapid biocatalytic process development and intensification continues to be challenging with currently available methods. Chiral amino-alcohols are of particular interest as they represent key industrial synthons for the production of complex molecules and optically pure pharmaceuticals. (2S,3R)-2-amino-1,3,4-butanetriol (ABT), a building block for the synthesis of protease inhibitors and detoxifying agents, can be synthesized from simple, non-chiral starting materials, by coupling a transketolase- and a transaminase-catalyzed reaction. However, until today, full conversion has not been shown and, typically, long reaction times are reported, making process modifications and improvement challenging. In this contribution, we present a novel microreactor-based approach based on free enzymes, and we report for the first time full conversion of ABT in a coupled enzyme cascade for both batch and continuous-flow systems. Using the compartmentalization of the reactions afforded by the microreactor cascade, we overcame inhibitory effects, increased the activity per unit volume, and optimized individual reaction conditions. The transketolase-catalyzed reaction was completed in under 10 min with a volumetric activity of 3.25 U ml -1 . Following optimization of the transaminase-catalyzed reaction, a volumetric activity of 10.8 U ml -1 was attained which led to full conversion of the coupled reaction in 2 hr. The presented approach illustrates how continuous-flow microreactors can be applied for the design and optimization of biocatalytic processes. © 2017 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc.

Synthesis of Novel Chiral Sulfonamide-Bearing 1,2,4-Triazole-3-thione Analogs Derived from D- and L-Phenylalanine Esters as Potential Anti-Influenza Agents.

PubMed

Başaran, Eyüp; Karaküçük-Iyidoğan, Ayşegül; Schols, Dominique; Oruç-Emre, Emine Elçin

2016-06-01

Novel enantiopure 1,2,4-trizole-3-thiones containing a benzensulfonamide moiety were synthesized via multistep reaction sequence starting with D-phenylalanine methyl ester and L-phenylalanine ethyl ester as a source of chirality. The chemical structures of all compounds were characterized by elemental analysis, UV, IR, (1) H NMR, (13) C NMR, 2D NMR (HETCOR), and mass spectral data. All compounds were tested in vitro antiviral activity against a broad variety of DNA and RNA viruses and in vitro cytostatic activity against murine leukemia (L1210), human T-lymphocyte (CEM) and human cervix carcinoma (HeLa) cell lines. Although enantiopure 1,2,4-triazole-3-thione analogs in (R) configuration emerged as promising anti-influenza A H1N1 subtype in Madin Darby canine kidney cell cultures (MDCK), their enantiomers exhibited no activity. Especially compounds , , , , and (EC50 : 6.5, 6.1, 2.4, 1.6, 1.7 μM, respectively) had excellent activity against influenza A H1N1 subtype compared to the reference drug ribavirin (EC50 : 8.0 μM). Several compounds have been found to inhibit proliferation of L1210, CEM and HeLa cell cultures with IC50 in the 12-53 μM range. Compound and in (R) configuration were the most active compounds (IC50 : 12-22 μM for and IC50 : 19-23 μM for ). Chirality 28:495-513, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Enantioselective micellar electrokinetic chromatography of dl-amino acids using (+)-1-(9-fluorenyl)-ethyl chloroformate derivatization and UV-induced fluorescence detection.

PubMed

Prior, Amir; van de Nieuwenhuijzen, Erik; de Jong, Gerhardus J; Somsen, Govert W

2018-05-22

Chiral analysis of dl-amino acids was achieved by micellar electrokinetic chromatography coupled with UV-excited fluorescence detection. The fluorescent reagent (+)-1-(9-fluorenyl)ethyl chloroformate was employed as chiral amino acid derivatizing agent and sodium dodecyl sulfate served as pseudo-stationary phase for separating the formed amino acid diastereomers. Sensitive analysis of (+)-1-(9-fluorenyl)ethyl chloroformate-amino acids was achieved applying a xenon-mercury lamp for ultraviolet excitation, and a spectrograph and charge-coupled device for wavelength-resolved emission detection. Applying signal integration over a 30-nm emission wavelength interval, signal-to-noise ratios for derivatized amino acids were up to 23 times higher as obtained using a standard photomultiplier for detection. The background electrolyte composition (electrolyte, pH, sodium dodecyl sulfate concentration, and organic solvent) was studied in order to attain optimal chemo- and enantioseparation. Enantioseparation of twelve proteinogenic dl-amino acids was achieved with chiral resolutions between 1.2 and 7.9, and detection limits for most derivatized amino acids in the 13-60 nM range (injected concentration). Linearity (coefficients of determination > 0.985) and peak-area and migration-time repeatabilities (relative standard deviations lower than 2.6 and 1.9%, respectively) were satisfactory. The employed fluorescence detection system provided up to 100-times better signal-to-noise ratios for (+)-1-(9-fluorenyl)ethyl chloroformate-amino acids than ultraviolet absorbance detection, showing good potential for d-amino acid analysis. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Ions in water: Free energies, surface effects, and geometrical constraints

NASA Astrophysics Data System (ADS)

Herce, Henry David

In this work, we present our results for ion solvation in finite and infinite water clusters. Molecular Dynamic simulations are used to connect the fundamental macroscopic quantities such as free energy, internal energy and entropy with the underlying microscopic description. Molecular dynamics studies complement experimental results and lead to a deeper insight into the solvation and diffusion of ionic species. Beyond its intrinsic interest, the ion solvation problem has practical relevance because of its role as ideal model system with which to construct and test ion-water interaction potentials. The ionic charging free energy is a very sensitive probe for the treatment of electrostatics in any given simulation setting. In this work, we present methods to compute the ionic charging free energy in systems characterized by atomic charges, and higher-order multipoles, mainly dipoles and quadrupoles. The results of these methods under periodic boundary conditions and spherical boundary conditions are then compared. For the treatment of spherical boundary conditions, we introduce a generalization of Gauss' law that links the microscopic variables to the relevant thermodynamic quantities. Ionic solvation in finite clusters is a problem relevant for many areas of chemistry and biology, such as the gas-liquid interface of tropospheric aerosol particles, or the interphase between water and proteins, membranes, etc. Careful evaluations of the free energy, internal energy and entropy are used to address controversial or unresolved issues, related to the underlying physical cause of surface solvation, and the basic assumptions that go with it. Our main conclusions are the following: (i) The main cause of surface solvation of a single ion in a water cluster is both water and ion polarization, coupled to the charge and size of the ion. Interestingly, the total energy of the ion increases near the cluster surface, while the total energy of water decreases. Also, our analysis clearly shows that the cause of surface solvation is not the size of the total water dipole (unless this is too small). (ii) The entropic contribution is the same order of magnitude as the energetic contribution, and therefore cannot be neglected for quantitative results. (iii) A pure energetic analysis can give a qualitative description of the ion position at room temperature. (iv) We have observed surface solvation of a large positive iodine-like ion in a polarizable water cluster, but not in a non-polarizable water cluster.

Determining the orientation of a chiral substrate using full-hemisphere angle-resolved photoelectron spectroscopy.

PubMed

Tadich, A; Riley, J; Thomsen, L; Cowie, B C C; Gladys, M J

2011-10-21

Chiral interfaces and substrates are of increasing importance in the field of enantioselective chemistry. To fully understand the enantiospecific interactions between chiral adsorbate molecules and the chiral substrate, it is vital that the chiral orientation of the substrate is known. In this Letter we demonstrate that full-hemisphere angle-resolved photoemission permits straightforward identification of the orientation of a chiral surface. The technique can be applied to any solid state system for which photoemission measurements are possible. © 2011 American Physical Society

Disordered two-dimensional electron systems with chiral symmetry

NASA Astrophysics Data System (ADS)

Markoš, P.; Schweitzer, L.

2012-10-01

We review the results of our recent numerical investigations on the electronic properties of disordered two dimensional systems with chiral unitary, chiral orthogonal, and chiral symplectic symmetry. Of particular interest is the behavior of the density of states and the logarithmic scaling of the smallest Lyapunov exponents in the vicinity of the chiral quantum critical point in the band center at E=0. The observed peaks or depressions in the density of states, the distribution of the critical conductances, and the possible non-universality of the critical exponents for certain chiral unitary models are discussed.

Chiral Symmetry Breaking and Complete Chiral Purity by Thermodynamic-Kinetic Feedback Near Equilibrium: Implications for the Origin of Biochirality

NASA Astrophysics Data System (ADS)

Viedma, Cristobal

2007-05-01

Chiral symmetry breaking occurs when a physical or chemical process spontaneously generates a large excess of one of the two enantiomers-left-handed (L) or right-handed (D)--with no preference as to which of the two enantiomers is produced. From the viewpoint of energy, these two enantiomers can exist with an equal probability, and inorganic processes that involve chiral products commonly yield a racemic mixture of both. The fact that biologically relevant molecules exist only as one of the two enantiomers is a fascinating example of complete symmetry breaking in chirality and has long intrigued the science community. The origin of this selective chirality has remained a fundamental enigma with regard to the origin of life since the time of Pasteur, some 140 years ago. Here, it is shown that two populations of chiral crystals of left and right hand cannot coexist in solution: one of the chiral populations disappears in an irreversible autocatalytic process that nurtures the other one. Final and complete chiral purity seems to be an inexorable fate in the course of the common process of growth-dissolution. This unexpected chiral symmetry breaking can be explained by the feedback between the thermodynamic control of dissolution and the kinetics of the growth process near equilibrium. This ``thermodynamic-kinetic feedback near equilibrium'' is established as a mechanism to achieve complete chiral purity in solid state from a previously solid racemic medium. The way in which this mechanism could operate in solutions of chiral biomolecules is described. Finally, based on this mechanism, experiments designed to search for chiral purity in a new way are proposed: chiral purity of amino acids or biopolymers is predicted in solid phase from a previously solid racemic medium. This process may have played a key role in the origin of biochirality.

Free-standing mesoporous silica films with tunable chiral nematic structures.

PubMed

Shopsowitz, Kevin E; Qi, Hao; Hamad, Wadood Y; Maclachlan, Mark J

2010-11-18

Chirality at the molecular level is found in diverse biological structures, such as polysaccharides, proteins and DNA, and is responsible for many of their unique properties. Introducing chirality into porous inorganic solids may produce new types of materials that could be useful for chiral separation, stereospecific catalysis, chiral recognition (sensing) and photonic materials. Template synthesis of inorganic solids using the self-assembly of lyotropic liquid crystals offers access to materials with well-defined porous structures, but only recently has chirality been introduced into hexagonal mesostructures through the use of a chiral surfactant. Efforts to impart chirality at a larger length scale using self-assembly are almost unknown. Here we describe the development of a photonic mesoporous inorganic solid that is a cast of a chiral nematic liquid crystal formed from nanocrystalline cellulose. These materials may be obtained as free-standing films with high surface area. The peak reflected wavelength of the films can be varied across the entire visible spectrum and into the near-infrared through simple changes in the synthetic conditions. To the best of our knowledge these are the first materials to combine mesoporosity with long-range chiral ordering that produces photonic properties. Our findings could lead to the development of new materials for applications in, for example, tuneable reflective filters and sensors. In addition, this type of material could be used as a hard template to generate other new materials with chiral nematic structures.

ENANTIOMER-SPECIFIC EFFECTS OF CHIRAL POLLUTANTS

EPA Science Inventory

Enantiomers, the mirror image isomers of chiral pollutants, are known to be selective in their interaction with other chiral molecules, including enzymes and other biochemicals. Considerable research has shown, for example, that chiral pesticides are degraded selectively by micr...

Coordinative Alignment of Chiral Molecules to Control over the Chirality Transfer in Spontaneous Resolution and Asymmetric Catalysis.

PubMed

Xia, Zhengqiang; Jing, Xu; He, Cheng; Wang, Xiaoge; Duan, Chunying

2017-11-13

The production and availability of enantiomerically pure compounds that spurred the development of chiral technologies and materials are very important to the fine chemicals and pharmaceutical industries. By coordinative alignment of enantiopure guests in the metal‒organic frameworks, we reported an approach to control over the chirality of homochiral crystallization and asymmetric transformation. Synthesized by achiral triphenylamine derivatives, the chirality of silver frameworks was determined by the encapsulated enantiopure azomethine ylides, from which clear interaction patterns were observed to explore the chiral induction principles. With the changing of addition sequence of substrates, the enantioselectivity of asymmetric cycloaddition was controlled to verify the determinant on the chirality of the bulky MOF materials. The economical chirality amplification that merges a series of complicated self-inductions, bulk homochiral crystallization and enantioselective catalysis opens new avenues for enantiopure chemical synthesis and provides a promising path for the directional design and development of homochiral materials.

[From symmetries to the laws of evolution. I. Chirality as a means of active media stratification].

PubMed

Tverdislov, V A; Sidorova, A É; Iakovenko, L V

2012-01-01

Features of the hypothetical evolution of a hierarchy of chiral objects formed by active media are discussed. On the basis of experimental facts a new synergetic generalization is made: an evolving system can repeatedly broaden the spectrum of its symmetry types within one level of organization which increases its complexity and change the sign of chirality during transition to a higher level. Switching the chirality sign of macroscopic objects provides irreversibility of stratification. The known chirality of biological structures at different levels suggests that the chiral L/D-stratification should be universal and the hierarchical paths are stable and determined. A high level enantiomorph with reciprocal chirality demonstrates a wider spectrum of functionality. A fractal description of natural hierarchical systems is pointed out to be inadequate because it implicates invariance of the chirality sign of the objects at different scales.

Chirality correlation in double-wall carbon nanotubes as studied by electron diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hirahara, Kaori; Bandow, Shunji; Kociak, Mathieu

2006-05-15

Structural correlation between two adjacent graphitic layers in double-wall carbon nanotubes (DWNTs) was systematically examined by using electron diffraction. Chiral angles and tube diameters were carefully measured, and the chiral indices of individual DWNTs were accurately determined. As a result, it was found that the interlayer distances of DWNTs were widely distributed in the range between 0.34 and 0.38 nm. Chiralities of the inner and outer tubes tended to be distributed at higher chiral angles, approaching 30 deg., for the tubes with diameter D<{approx}3 nm. On the other hand, for the tubes with D>{approx}3 nm, the chiral angles were widelymore » distributed, covering the chiral map entirely. Therefore, we consider that tubes with small diameters have a tendency to form armchair type. Correlation of chiralities between the inner and outer tubes was found to be random.« less

Chirality effect in disordered graphene ribbon junctions

NASA Astrophysics Data System (ADS)

Long, Wen

2012-05-01

We investigate the influence of edge chirality on the electronic transport in clean or disordered graphene ribbon junctions. By using the tight-binding model and the Landauer-Büttiker formalism, the junction conductance is obtained. In the clean sample, the zero-magnetic-field junction conductance is strongly chirality-dependent in both unipolar and bipolar ribbons, whereas the high-magnetic-field conductance is either chirality-independent in the unipolar or chirality-dependent in the bipolar ribbon. Furthermore, we study the disordered sample in the presence of magnetic field and find that the junction conductance is always chirality-insensitive for both unipolar and bipolar ribbons with adequate disorders. In addition, the disorder-induced conductance plateaus can exist in all chiral bipolar ribbons provided the disorder strength is moderate. These results suggest that we can neglect the effect of edge chirality in fabricating electronic devices based on the magnetotransport in a disordered graphene ribbon.

Molecular description of the propagation of chirality from molecules to complex systems: different mechanisms controlled by hydrophobic interactions.

PubMed

Marinelli, Fabrizio; Sorrenti, Alessandro; Corvaglia, Valentina; Leone, Vanessa; Mancini, Giovanna

2012-11-12

In this work a combined theoretical and experimental approach was used to elucidate and describe at the molecular level the basic interactions that drive the transfer of the chiral information from chiral surfactant molecules to dye/surfactant assemblies. It was found that both hydrophobic interactions and relative concentrations strongly influence the chiroptical features of the heteroaggregates. In particular it was observed that, depending on the length of the surfactant hydrophobic chain, the chiral information is transferred to the dye by stabilizing an enantiomer either of a chiral conformer or of a chiral topological arrangement. These findings underline the role of hydrophobic interactions in the transfer of chirality and provide an example of the potential of in silico simulations for providing an accurate description of the process of chirality propagation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chirality detection of enantiomers using twisted optical metamaterials

NASA Astrophysics Data System (ADS)

Zhao, Yang; Askarpour, Amir N.; Sun, Liuyang; Shi, Jinwei; Li, Xiaoqin; Alù, Andrea

2017-01-01

Many naturally occurring biomolecules, such as amino acids, sugars and nucleotides, are inherently chiral. Enantiomers, a pair of chiral isomers with opposite handedness, often exhibit similar physical and chemical properties due to their identical functional groups and composition, yet show different toxicity to cells. Detecting enantiomers in small quantities has an essential role in drug development to eliminate their unwanted side effects. Here we exploit strong chiral interactions with plasmonic metamaterials with specifically designed optical response to sense chiral molecules down to zeptomole levels, several orders of magnitude smaller than what is typically detectable with conventional circular dichroism spectroscopy. In particular, the measured spectra reveal opposite signs in the spectral regime directly associated with different chiral responses, providing a way to univocally assess molecular chirality. Our work introduces an ultrathin, planarized nanophotonic interface to sense chiral molecules with inherently weak circular dichroism at visible and near-infrared frequencies.

Transfer of chirality from light to a Disperse Red 1 molecular glass surface.

PubMed

Mazaheri, Leila; Lebel, Olivier; Nunzi, Jean-Michel

2017-12-01

Chiral structures and materials interact with light in well-documented ways, but light can also interact with achiral materials to generate chirality by inscribing its asymmetric configuration on photoresponsive materials, such as azobenzene derivatives. While it is thus possible to generate both two-dimensional (2D) and three-dimensional (3D) chirality, 2D chirality is especially attractive because of its non-reciprocity. Herein, 2D chirality is induced on the surface of a glass-forming Disperse Red 1 derivative by irradiation with a single laser beam, yielding crossed spontaneous surface relief gratings with different pitches. Azimuth rotations up to 10° have been observed, and the absence of 3D chirality has been confirmed. This method thus allows generating non-reciprocal planar chiral objects by a simple, single irradiation process on a thin film of a material that can easily be processed over large areas or onto small objects.

Chirality detection of enantiomers using twisted optical metamaterials

PubMed Central

Zhao, Yang; Askarpour, Amir N.; Sun, Liuyang; Shi, Jinwei; Li, Xiaoqin; Alù, Andrea

2017-01-01

Many naturally occurring biomolecules, such as amino acids, sugars and nucleotides, are inherently chiral. Enantiomers, a pair of chiral isomers with opposite handedness, often exhibit similar physical and chemical properties due to their identical functional groups and composition, yet show different toxicity to cells. Detecting enantiomers in small quantities has an essential role in drug development to eliminate their unwanted side effects. Here we exploit strong chiral interactions with plasmonic metamaterials with specifically designed optical response to sense chiral molecules down to zeptomole levels, several orders of magnitude smaller than what is typically detectable with conventional circular dichroism spectroscopy. In particular, the measured spectra reveal opposite signs in the spectral regime directly associated with different chiral responses, providing a way to univocally assess molecular chirality. Our work introduces an ultrathin, planarized nanophotonic interface to sense chiral molecules with inherently weak circular dichroism at visible and near-infrared frequencies. PMID:28120825

Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study

PubMed Central

Barker, Graeme; Johnson, David G; Young, Paul C; Macgregor, Stuart A; Lee, Ai-Lan

2015-01-01

Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au–allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that erode the efficiency of chirality transfer become competitive. PMID:26248980

Synergistic Enhancement of Microwave Absorption Using Hybridized Polyaniline@helical CNTs with Dual Chirality.

PubMed

Tian, Xin; Meng, Fanbin; Meng, Fanchen; Chen, Xiangnan; Guo, Yifan; Wang, Ying; Zhu, Wenjun; Zhou, Zuowan

2017-05-10

In this study, we designed a dual-chirality hierarchical structure to achieve a synergistically enhanced effect in microwave absorption via the hybridization of nanomaterials. Herein, polyaniline (PANi) nanorods with tunable chirality are grown on helical carbon nanotubes (HCNTs), a typical nanoscale chiral structure, through in situ polymerization. The experimental results show that the hierarchical hybrids (PANi@HCNTs) exhibit distinctly dual chirality and a significant enhancement in electromagnetic (EM) losses compared to those of either pure PANi or HCNTs. The maximum reflection loss of the as-prepared hybrids can reach -32.5 dB at 8.9 GHz. Further analysis demonstrates that combinations of chiral acid-doped PANi and coiled HCNTs with molecular and nanoscale chirality lead to synergistic effects resulting from the dual chirality. The so-called cross-polarization may result in additional interactions with induced EM waves in addition to multiscaled relaxations from functional groups and interfacial polarizations, which can benefit EM absorption.

Chiral recognition and selection during the self-assembly process of protein-mimic macroanions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yin, Panchao; Zhang, Zhi-Ming; Lv, Hongjin

The research on chiral recognition and chiral selection is not only fundamental in resolving the puzzle of homochirality, but also instructive in chiral separation and stereoselective catalysis. Here we report the chiral recognition and chiral selection during the self-assembly process of two enantiomeric wheel-shaped macroanions, [Fe28(μ3-O)8(Tart)16(HCOO)24]20- (Tart=D- or L-tartaric acid tetra-anion). The enantiomers are observed to remain self-sorted and self-assemble into their individual assemblies in their racemic mixture solution. The addition of chiral co-anions can selectively suppress the self-assembly process of the enantiomeric macroanions, which is further used to separate the two enantiomers from their mixtures on the basis ofmore » the size difference between the monomers and the assemblies. We believe that delicate long-range electrostatic interactions could be responsible for such high-level chiral recognition and selection.« less

Interaction of collagen with chlorosulphonated paraffin tanning agents: Fourier transform infrared spectroscopic analysis and molecular dynamics simulations.

PubMed

Monti, Susanna; Bramanti, Emilia; Della Porta, Valentina; Onor, Massimo; D'Ulivo, Alessandro; Barone, Vincenzo

2013-09-21

The binding of chlorosulphonated paraffins to collagen triple helices is studied by means of classical molecular dynamics simulations and experimental spectroscopic techniques in order to disclose the principal characteristics of their interaction during the leather fattening process. Indeed, collagen is the main target to develop new leather modifying agents with specific characteristics, and an accurate design of the collagen binders, supported by predictive computational strategies, could be a successful tool to obtain new effective eco-compatible compounds able to impart to the leather the required functionalities and distinctive mechanical properties. Possible effects caused by the tanning agents on the collagen matrix have been identified from both experimental and theoretical points of view. Computational data in agreement with experiment have revealed that chlorosulphonated paraffins can interact favorably with the collagen residues having amine groups in their side chains (Arg, Lys, Asn and Gln) and reduce the tendency of the solvated collagen matrix to swell. However, the interference of chlorosulphonated paraffins with the unfolding process, which is operated mainly by the action of water, can be due both to covalent cross-linking of the collagen chains and intermolecular hydrogen bonding interactions involving also the hydroxyl groups of Hyp, Ser and Thr residues.

Polarimetry as a tool for the study of solutions of chiral solutes.

PubMed

Orlova, Anna V; Andrade, Renato R; da Silva, Clarissa O; Zinin, Alexander I; Kononov, Leonid O

2014-01-13

Optical rotation of aqueous solutions of D-levoglucosan was studied experimentally in the 0.03-4.0 mol L(-1) concentration range and a nonlinear concentration dependence of specific optical rotation (SR) was revealed. Discontinuities observed in the concentration plot of SR (at 0.1, 0.3, 0.5, 1.0, and 2.0 mol L(-1)) are well correlated with those found by static and dynamic light scattering and identify concentration ranges in which different solution domains (supramers) may exist. The average SR experimental value for a D-levoglucosan aqueous solution ([α]D(28) -58.5±8.7 deg dm(-1) cm(-3) g(-1)) was found to be in good agreement with values obtained by theoretical calculation (TD-DFT/GIAO) of SR for 15 different conformers revealed by conformational sampling at the PCM/B3LYP/6-311++G(2d,2p)//B3LYP/6-31+G(d,p) level, which were shown to be strongly affected by the solvation microenvironment (0, 1, 2, and 3 explicit solvent molecules considered) due to local geometrical changes induced in the solute molecule. This exceptionally high sensitivity of SR makes polarimetry a unique method capable of sensing changes in the structure of supramers detected in this study. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembly of crystalline nanotubes from monodisperse amphiphilic diblock copolypeptoid tiles

DOE PAGES

Sun, Jing; Jiang, Xi; Lund, Reidar; ...

2016-03-28

The folding and assembly of sequence-defined polymers into precisely ordered nanostructures promises a class of well-defined biomimetic architectures with specific function. Amphiphilic diblock copolymers are known to self-assemble in water to form a variety of nanostructured morphologies including spheres, disks, cylinders, and vesicles. In all of these cases, the predominant driving force for assembly is the formation of a hydrophobic core that excludes water, whereas the hydrophilic blocks are solvated and extend into the aqueous phase. However, such polymer systems typically have broad molar mass distributions and lack the purity and sequence-defined structure often associated with biologically derived polymers. Here,more » we demonstrate that purified, monodisperse amphiphilic diblock copolypeptoids, with chemically distinct domains that are congruent in size and shape, can behave like molecular tile units that spontaneously assemble into hollow, crystalline nanotubes in water. The nanotubes consist of stacked, porous crystalline rings, and are held together primarily by side-chain van der Waals interactions. The peptoid nanotubes form without a central hydrophobic core, chirality, a hydrogen bond network, and electrostatic or π-π interactions. These results demonstrate the remarkable structure-directing influence of n-alkane and ethyleneoxy side chains in polymer self-assembly. More broadly, this work suggests that flexible, low-molecular-weight sequence-defined polymers can serve as molecular tile units that can assemble into precision supramolecular architectures.« less

Electronic properties of functionalized (5,5) beryllium oxide nanotubes.

PubMed

Chigo Anota, Ernesto; Cocoletzi, Gregorio Hernández

2013-05-01

Using the density functional theory (DFT) we study the structural and electronic properties of functionalized (5,5) chirality single wall beryllium oxide nanotubes (SW-BeONTs), i.e. armchair nanotubes. The nanotube surface and ends are functionalized by the hydroxyl (OH) functional group. Our calculations consider the Hamprecht-Cohen-Tozer-Handy functional in the generalized gradient approximation (HCTH-GGA) to deal with the exchange-correlation energies, and the base function with double polarization (DNP). The geometry optimization of both defects free and with point defects nanotubes is done applying the criterion of minimum energy. Six configurations are considered: The OH oriented toward the Be (on the surface and at the end), toward the O (on the surface and at the end) and placed at the nanotube ends. Simulation results show that the nanotube functionalization takes place at the nanotube ends with the BeO bond displaying hydrogen-like bridge bonds. Moreover the nanotube semiconductor behavior remains unchanged. The polarity is high (it shows a transition from covalent to ionic) favoring solvatation. On the other hand, the work function low value suggests this to be a good candidate for the device fabrication. When the nanotube contains surface point defects the work function is reduced which provides excellent possibilities for the use of this material in the electronic industry. Copyright © 2013 Elsevier Inc. All rights reserved.

Self-assembly of crystalline nanotubes from monodisperse amphiphilic diblock copolypeptoid tiles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Jing; Jiang, Xi; Lund, Reidar

The folding and assembly of sequence-defined polymers into precisely ordered nanostructures promises a class of well-defined biomimetic architectures with specific function. Amphiphilic diblock copolymers are known to self-assemble in water to form a variety of nanostructured morphologies including spheres, disks, cylinders, and vesicles. In all of these cases, the predominant driving force for assembly is the formation of a hydrophobic core that excludes water, whereas the hydrophilic blocks are solvated and extend into the aqueous phase. However, such polymer systems typically have broad molar mass distributions and lack the purity and sequence-defined structure often associated with biologically derived polymers. Here,more » we demonstrate that purified, monodisperse amphiphilic diblock copolypeptoids, with chemically distinct domains that are congruent in size and shape, can behave like molecular tile units that spontaneously assemble into hollow, crystalline nanotubes in water. The nanotubes consist of stacked, porous crystalline rings, and are held together primarily by side-chain van der Waals interactions. The peptoid nanotubes form without a central hydrophobic core, chirality, a hydrogen bond network, and electrostatic or π-π interactions. These results demonstrate the remarkable structure-directing influence of n-alkane and ethyleneoxy side chains in polymer self-assembly. More broadly, this work suggests that flexible, low-molecular-weight sequence-defined polymers can serve as molecular tile units that can assemble into precision supramolecular architectures.« less

Chiral Cliffs: Investigating the Influence of Chirality on Binding Affinity.

PubMed

Schneider, Nadine; Lewis, Richard A; Fechner, Nikolas; Ertl, Peter

2018-05-11

Chirality is understood by many as a binary concept: a molecule is either chiral or it is not. In terms of the action of a structure on polarized light, this is indeed true. When examined through the prism of molecular recognition, the answer becomes more nuanced. In this work, we investigated chiral behavior on protein-ligand binding: when does chirality make a difference in binding activity? Chirality is a property of the 3D structure, so recognition also requires an appreciation of the conformation. In many situations, the bioactive conformation is undefined. We set out to address this by defining and using several novel 2D descriptors to capture general characteristic features of the chiral center. Using machine-learning methods, we built different predictive models to estimate if a chiral pair (a set of two enantiomers) might exhibit a chiral cliff in a binding assay. A set of about 3800 chiral pairs extracted from the ChEMBL23 database was used to train and test our models. By achieving an accuracy of up to 75 %, our models provide good performance in discriminating chiral cliffs from non-cliffs. More importantly, we were able to derive some simple guidelines for when one can reasonably use a racemate and when an enantiopure compound is needed in an assay. We critically discuss our results and show detailed examples of using our guidelines. Along with this publication we provide our dataset, our novel descriptors, and the Python code to rebuild the predictive models. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Blue phase liquid crystal phase transition for cyano compound chiral nematic liquid crystal mixtures with three two-ring core structures and chiral dopant concentrations

NASA Astrophysics Data System (ADS)

Shin, Jaesun; Kim, Beomjong; Jung, Wansu; Fahad, Mateen; Park, SangJin; Hong, Sung-Kyu

2017-05-01

Blue phase (BP) temperature range of a chiral nematic liquid crystal (LC) mixture is dependent upon the host nematic LC chemical structure and chiral dopant concentration. In this study, we investigated BP phase transition behaviour and helical twisting power (HTP) using three chiral dopant concentrations of cyano compound chiral nematic LC mixtures incorporating three two-ring core structures in the host nematic LCs. The effect of the host nematic LC core structure, HTP and chiral dopant concentrations were considered on BP temperature ranges, for two types of complete BPI and BPII without isotropic phase (Iso) and two types of coexistence state of BPI+Iso and BPII+Iso.

Solvation thermodynamics of L-cystine, L-tyrosine, and L-leucine in aqueous-electrolyte media

NASA Astrophysics Data System (ADS)

Roy, Sanjay; Guin, Partha Sarathi; Mahali, Kalachand; Dolui, Bijoy Krishna

2017-12-01

Solubilities of L-cystine, L-tyrosine, and L-leucine in aqueous NaCl media at 298.15 K have been studied. Indispensable and related solvent parameters such as molar mass, molar volume, etc., were also determined. The results are used to evaluate the standard transfer Gibbs free energy, cavity forming enthalpy of transfer, cavity forming transfer Gibbs free energy and dipole-dipole interaction effects during the course of solvation. Various weak interactions involving solute-solvent or solvent-solvent molecules were characterized in order to find their role on the solvation of these amino acids.

Phase Equilibria and Ionic Solvation in the Lithium Tetrafluoroborate-Dimethylsulfoxide System

NASA Astrophysics Data System (ADS)

Gafurov, M. M.; Kirillov, S. A.; Gorobets, M. I.; Rabadanov, K. Sh.; Ataev, M. B.; Tretyakov, D. O.; Aydemirov, K. M.

2015-01-01

The phase diagram and electrical conductivity isotherms for the lithium tetrafluoroborate (LiBF4)-dimethylsulfoxide (DMSO) system and Raman spectra of DMSO and the LiBF4-DMSO solution were studied. Spectroscopic signatures of a H-bond between DMSO and BF4 - ions were found. The bonds of Li+ ions to the solvent were stronger than the bonds in DMSO dimers because formation of the solvate destroyed dimeric DMSO molecules. The τω values for DMSO molecules in the Li+-ion solvate shell of the LiBF4-DMSO system were similar to those for associated solvent molecules.

Angle-Resolved Photoemission of Solvated Electrons in Sodium-Doped Clusters.

PubMed

West, Adam H C; Yoder, Bruce L; Luckhaus, David; Saak, Clara-Magdalena; Doppelbauer, Maximilian; Signorell, Ruth

2015-04-16

Angle-resolved photoelectron spectroscopy of the unpaired electron in sodium-doped water, methanol, ammonia, and dimethyl ether clusters is presented. The experimental observations and the complementary calculations are consistent with surface electrons for the cluster size range studied. Evidence against internally solvated electrons is provided by the photoelectron angular distribution. The trends in the ionization energies seem to be mainly determined by the degree of hydrogen bonding in the solvent and the solvation of the ion core. The onset ionization energies of water and methanol clusters do not level off at small cluster sizes but decrease slightly with increasing cluster size.

Predictions of the physicochemical properties of amino acid side chain analogs using molecular simulation.

PubMed

Ahmed, Alauddin; Sandler, Stanley I

2016-03-07

A candidate drug compound is released for clinical trails (in vivo activity) only if its physicochemical properties meet desirable bioavailability and partitioning criteria. Amino acid side chain analogs play vital role in the functionalities of protein and peptides and as such are important in drug discovery. We demonstrate here that the predictions of solvation free energies in water, in 1-octanol, and self-solvation free energies computed using force field-based expanded ensemble molecular dynamics simulation provide good accuracy compared to existing empirical and semi-empirical methods. These solvation free energies are then, as shown here, used for the prediction of a wide range of physicochemical properties important in the assessment of bioavailability and partitioning of compounds. In particular, we consider here the vapor pressure, the solubility in both water and 1-octanol, and the air-water, air-octanol, and octanol-water partition coefficients of amino acid side chain analogs computed from the solvation free energies. The calculated solvation free energies using different force fields are compared against each other and with available experimental data. The protocol here can also be used for a newly designed drug and other molecules where force field parameters and charges are obtained from density functional theory.

Solvation free energies and partition coefficients with the coarse-grained and hybrid all-atom/coarse-grained MARTINI models.

PubMed

Genheden, Samuel

2017-10-01

We present the estimation of solvation free energies of small solutes in water, n-octanol and hexane using molecular dynamics simulations with two MARTINI models at different resolutions, viz. the coarse-grained (CG) and the hybrid all-atom/coarse-grained (AA/CG) models. From these estimates, we also calculate the water/hexane and water/octanol partition coefficients. More than 150 small, organic molecules were selected from the Minnesota solvation database and parameterized in a semi-automatic fashion. Using either the CG or hybrid AA/CG models, we find considerable deviations between the estimated and experimental solvation free energies in all solvents with mean absolute deviations larger than 10 kJ/mol, although the correlation coefficient is between 0.55 and 0.75 and significant. There is also no difference between the results when using the non-polarizable and polarizable water model, although we identify some improvements when using the polarizable model with the AA/CG solutes. In contrast to the estimated solvation energies, the estimated partition coefficients are generally excellent with both the CG and hybrid AA/CG models, giving mean absolute deviations between 0.67 and 0.90 log units and correlation coefficients larger than 0.85. We analyze the error distribution further and suggest avenues for improvements.

Computing pKa Values in Different Solvents by Electrostatic Transformation.

PubMed

Rossini, Emanuele; Netz, Roland R; Knapp, Ernst-Walter

2016-07-12

We introduce a method that requires only moderate computational effort to compute pKa values of small molecules in different solvents with an average accuracy of better than 0.7 pH units. With a known pKa value in one solvent, the electrostatic transform method computes the pKa value in any other solvent if the proton solvation energy is known in both considered solvents. To apply the electrostatic transform method to a molecule, the electrostatic solvation energies of the protonated and deprotonated molecular species are computed in the two considered solvents using a dielectric continuum to describe the solvent. This is demonstrated for 30 molecules belonging to 10 different molecular families by considering 77 measured pKa values in 4 different solvents: water, acetonitrile, dimethyl sulfoxide, and methanol. The electrostatic transform method can be applied to any other solvent if the proton solvation energy is known. It is exclusively based on physicochemical principles, not using any empirical fetch factors or explicit solvent molecules, to obtain agreement with measured pKa values and is therefore ready to be generalized to other solute molecules and solvents. From the computed pKa values, we obtained relative proton solvation energies, which agree very well with the proton solvation energies computed recently by ab initio methods, and used these energies in the present study.

Implicit Solvation Parameters Derived from Explicit Water Forces in Large-Scale Molecular Dynamics Simulations

PubMed Central

2012-01-01

Implicit solvation is a mean force approach to model solvent forces acting on a solute molecule. It is frequently used in molecular simulations to reduce the computational cost of solvent treatment. In the first instance, the free energy of solvation and the associated solvent–solute forces can be approximated by a function of the solvent-accessible surface area (SASA) of the solute and differentiated by an atom–specific solvation parameter σiSASA. A procedure for the determination of values for the σiSASA parameters through matching of explicit and implicit solvation forces is proposed. Using the results of Molecular Dynamics simulations of 188 topologically diverse protein structures in water and in implicit solvent, values for the σiSASA parameters for atom types i of the standard amino acids in the GROMOS force field have been determined. A simplified representation based on groups of atom types σgSASA was obtained via partitioning of the atom–type σiSASA distributions by dynamic programming. Three groups of atom types with well separated parameter ranges were obtained, and their performance in implicit versus explicit simulations was assessed. The solvent forces are available at http://mathbio.nimr.mrc.ac.uk/wiki/Solvent_Forces. PMID:23180979

Water Lone Pair Delocalization in Classical and Quantum Descriptions of the Hydration of Model Ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Remsing, Richard C.; Duignan, Timothy T.; Baer, Marcel D.

Understanding the nature of ionic hydration at a fundamental level has eluded scientists despite intense interest for nearly a century. In particular, the microscopic origins of the asymmetry of ion solvation thermodynamics with respect to the sign of the ionic charge remains a mystery. Here, we determine the response of accurate quantum mechanical water models to strong nanoscale solvation forces arising from excluded volumes and ionic electrostatic fields. This is compared to the predictions of two important limiting classes of classical models of water with fixed point changes, differing in their treatment of "lone-pair" electrons. Using the quantum water modelmore » as our standard of accuracy, we find that a single fixed classical treatment of lone pair electrons cannot accurately describe solvation of both apolar and cationic solutes, underlining the need for a more flexible description of local electronic effects in solvation processes. However, we explicitly show that all water models studied respond to weak long-ranged electrostatic perturbations in a manner that follows macroscopic dielectric continuum models, as would be expected. We emphasize the importance of these findings in the context of realistic ion models, using density functional theory and empirical models, and discuss the implications of our results for quantitatively accurate reduced descriptions of solvation in dielectric media.« less

Are mixed explicit/implicit solvation models reliable for studying phosphate hydrolysis? A comparative study of continuum, explicit and mixed solvation models.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kamerlin, Shina C. L.; Haranczyk, Maciej; Warshel, Arieh

2009-05-01

Phosphate hydrolysis is ubiquitous in biology. However, despite intensive research on this class of reactions, the precise nature of the reaction mechanism remains controversial. In this work, we have examined the hydrolysis of three homologous phosphate diesters. The solvation free energy was simulated by means of either an implicit solvation model (COSMO), hybrid quantum mechanical / molecular mechanical free energy perturbation (QM/MM-FEP) or a mixed solvation model in which N water molecules were explicitly included in the ab initio description of the reacting system (where N=1-3), with the remainder of the solvent being implicitly modelled as a continuum. Here, bothmore » COSMO and QM/MM-FEP reproduce Delta Gobs within an error of about 2kcal/mol. However, we demonstrate that in order to obtain any form of reliable results from a mixed model, it is essential to carefully select the explicit water molecules from short QM/MM runs that act as a model for the true infinite system. Additionally, the mixed models tend to be increasingly inaccurate the more explicit water molecules are placed into the system. Thus, our analysis indicates that this approach provides an unreliable way for modelling phosphate hydrolysis in solution.« less

Aqueous TMAO solutions as seen by theoretical THz spectroscopy: hydrophilic versus hydrophobic water.

PubMed

Imoto, Sho; Forbert, Harald; Marx, Dominik

2018-02-28

Solvation of trimethylamine-N-oxide (TMAO) by water is of great fundamental interest because this small molecule has both strongly hydrophilic and large hydrophobic groups at its opposite ends and, furthermore, stabilizes proteins against temperature and pressure denaturation. Since hydrophilic and hydrophobic groups affect the structural dynamics of the respective solvation water molecules in vastly different ways, we dissect their distinct influences on the THz spectrum of TMAO(aq) by using ab initio molecular dynamics simulations. In particular, we demonstrate that exclusively electronic polarization and charge transfer effects, being absent in the usual fixed-charge biomolecular force fields, are responsible for the significant enhancement of the effective molecular dipole moment of hydrophilic solvation water. This, in turn, leads to pronounced solute-solvent couplings and thus to specific THz modes that involve well-defined H-bond bending and stretching motion being characteristic to hydrophilic solvation. The THz response of individual H-bonded pairs of water molecules involving hydrophobic solvation water, in stark contrast, is nearly indistinguishable from such pairs in bulk water. Transcending the specific case, THz spectroscopy is suggested to be an ideal experimental approach to unravel the controversial piezolytic properties of TMAO including its counteracting effect on pressure-induced denaturation of proteins.

Microcalorimetric study of thermal unfolding of lysozyme in water/glycerol mixtures: An analysis by solvent exchange model

NASA Astrophysics Data System (ADS)

Spinozzi, Francesco; Ortore, Maria Grazia; Sinibaldi, Raffaele; Mariani, Paolo; Esposito, Alessandro; Cinelli, Stefania; Onori, Giuseppe

2008-07-01

Folded protein stabilization or destabilization induced by cosolvent in mixed aqueous solutions has been studied by differential scanning microcalorimetry and related to difference in preferential solvation of native and denatured states. In particular, the thermal denaturation of a model system formed by lysozyme dissolved in water in the presence of the stabilizing cosolvent glycerol has been considered. Transition temperatures and enthalpies, heat capacity, and standard free energy changes have been determined when applying a two-state denaturation model to microcalorimetric data. Thermodynamic parameters show an unexpected, not linear, trend as a function of solvent composition; in particular, the lysozyme thermodynamic stability shows a maximum centered at water molar fraction of about 0.6. Using a thermodynamic hydration model based on the exchange equilibrium between glycerol and water molecules from the protein solvation layer to the bulk, the contribution of protein-solvent interactions to the unfolding free energy and the changes of this contribution with solvent composition have been derived. The preferential solvation data indicate that lysozyme unfolding involves an increase in the solvation surface, with a small reduction of the protein-preferential hydration. Moreover, the derived changes in the excess solvation numbers at denaturation show that only few solvent molecules are responsible for the variation of lysozyme stability in relation to the solvent composition.

Distinctive Solvation Patterns Make Renal Osmolytes Diverse

PubMed Central

Jackson-Atogi, Ruby; Sinha, Prem Kumar; Rösgen, Jörg

2013-01-01

The kidney uses mixtures of five osmolytes to counter the stress induced by high urea and NaCl concentrations. The individual roles of most of the osmolytes are unclear, and three of the five have not yet been thermodynamically characterized. Here, we report partial molar volumes and activity coefficients of glycerophosphocholine (GPC), taurine, and myo-inositol. We derive their solvation behavior from the experimental data using Kirkwood-Buff theory. We also provide their solubility data, including solubility data for scyllo-inositol. It turns out that renal osmolytes fall into three distinct classes with respect to their solvation. Trimethyl-amines (GPC and glycine-betaine) are characterized by strong hard-sphere-like self-exclusion; urea, taurine, and myo-inositol have a tendency toward self-association; sorbitol and most other nonrenal osmolytes have a relatively constant, intermediate solvation that has components of both exclusion and association. The data presented here show that renal osmolytes are quite diverse with respect to their solvation patterns, and they can be further differentiated based on observations from experiments examining their effect on macromolecules. It is expected, based on the available surface groups, that each renal osmolyte has distinct effects on various classes of biomolecules. This likely allows the kidney to use specific combinations of osmolytes independently to fine-tune the chemical activities of several types of molecules. PMID:24209862

Solvation free energies and partition coefficients with the coarse-grained and hybrid all-atom/coarse-grained MARTINI models

NASA Astrophysics Data System (ADS)

Genheden, Samuel

2017-10-01

We present the estimation of solvation free energies of small solutes in water, n-octanol and hexane using molecular dynamics simulations with two MARTINI models at different resolutions, viz. the coarse-grained (CG) and the hybrid all-atom/coarse-grained (AA/CG) models. From these estimates, we also calculate the water/hexane and water/octanol partition coefficients. More than 150 small, organic molecules were selected from the Minnesota solvation database and parameterized in a semi-automatic fashion. Using either the CG or hybrid AA/CG models, we find considerable deviations between the estimated and experimental solvation free energies in all solvents with mean absolute deviations larger than 10 kJ/mol, although the correlation coefficient is between 0.55 and 0.75 and significant. There is also no difference between the results when using the non-polarizable and polarizable water model, although we identify some improvements when using the polarizable model with the AA/CG solutes. In contrast to the estimated solvation energies, the estimated partition coefficients are generally excellent with both the CG and hybrid AA/CG models, giving mean absolute deviations between 0.67 and 0.90 log units and correlation coefficients larger than 0.85. We analyze the error distribution further and suggest avenues for improvements.

Chiralities of spiral waves and their transitions.

PubMed

Pan, Jun-ting; Cai, Mei-chun; Li, Bing-wei; Zhang, Hong

2013-06-01

The chiralities of spiral waves usually refer to their rotation directions (the turning orientations of the spiral temporal movements as time elapses) and their curl directions (the winding orientations of the spiral spatial geometrical structures themselves). Traditionally, they are the same as each other. Namely, they are both clockwise or both counterclockwise. Moreover, the chiralities are determined by the topological charges of spiral waves, and thus they are conserved quantities. After the inwardly propagating spirals were experimentally observed, the relationship between the chiralities and the one between the chiralities and the topological charges are no longer preserved. The chiralities thus become more complex than ever before. As a result, there is now a desire to further study them. In this paper, the chiralities and their transition properties for all kinds of spiral waves are systemically studied in the framework of the complex Ginzburg-Landau equation, and the general relationships both between the chiralities and between the chiralities and the topological charges are obtained. The investigation of some other models, such as the FitzHugh-Nagumo model, the nonuniform Oregonator model, the modified standard model, etc., is also discussed for comparison.

Theoretical Prediction of Am(III)/Eu(III) Selectivity to Aid the Design of Actinide-Lanthanide Separation Agents

DOE PAGES

Bryantsev, Vyacheslav S.; Hay, Benjamin P.

2015-03-20

Selective extraction of minor actinides from lanthanides is a critical step in the reduction of radiotoxicity of spent nuclear fuels. However, the design of suitable ligands for separating chemically similar 4f- and 5f-block trivalent metal ions poses a significant challenge. Furthermore, first-principles calculations should play an important role in the design of new separation agents, but their ability to predict metal ion selectivity has not been systematically evaluated. We examine the ability of several density functional theory methods to predict selectivity of Am(III) and Eu(III) with oxygen, mixed oxygen–nitrogen, and sulfur donor ligands. The results establish a computational method capablemore » of predicting the correct order of selectivities obtained from liquid–liquid extraction and aqueous phase complexation studies. To allow reasonably accurate predictions, it was critical to employ sufficiently flexible basis sets and provide proper account of solvation effects. The approach is utilized to estimate the selectivity of novel amide-functionalized diazine and 1,2,3-triazole ligands.« less

Synthesis and Evaluation of Chirally Defined Side Chain Variants of 7-Chloro-4-Aminoquinoline To Overcome Drug Resistance in Malaria Chemotherapy

PubMed Central

Dola, Vasantha Rao; Soni, Awakash; Agarwal, Pooja; Ahmad, Hafsa; Raju, Kanumuri Siva Rama; Rashid, Mamunur; Wahajuddin, Muhammad; Srivastava, Kumkum; Haq, W.; Dwivedi, A. K.; Puri, S. K.

2016-01-01

ABSTRACT A novel 4-aminoquinoline derivative [(S)-7-chloro-N-(4-methyl-1-(4-methylpiperazin-1-yl)pentan-2-yl)-quinolin-4-amine triphosphate] exhibiting curative activity against chloroquine-resistant malaria parasites has been identified for preclinical development as a blood schizonticidal agent. The lead molecule selected after detailed structure-activity relationship (SAR) studies has good solid-state properties and promising activity against in vitro and in vivo experimental malaria models. The in vitro absorption, distribution, metabolism, and excretion (ADME) parameters indicate a favorable drug-like profile. PMID:27956423

Effects of Fluctuations on Inhomogeneous Chiral Transitions

NASA Astrophysics Data System (ADS)

Lee, Tong-Gyu; Yoshiike, Ryo; Tatsumi, Toshitaka

We discuss the features of the order-parameter fluctuations in the normal phase near the phase boundary and their effects on the phase transition from the normal to the inhomogeneous phase with spatially modulated order parameter. Focusing on the chiral symmetry breaking, i.e., inhomogeneous chiral transition, we consider the fluctuation of the chiral pair consisting of quark-antiquark or quark-hole pair within the two-flavor Nambu-Jona-Lasinio model in the chiral limit. We clarify the roles of quantum and thermal fluctuations and also argue that anomalies for thermodynamic quantities in the inhomogeneous chiral transition should lead to phenomenological implications.

Dispersion relations for electromagnetic wave propagation in chiral plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, M. X.; Guo, B., E-mail: binguo@whut.edu.cn; Peng, L.

2014-11-15

The dispersion relations for electromagnetic wave propagation in chiral plasmas are derived using a simplified method and investigated in detail. With the help of the dispersion relations for each eignwave, we explore how the chiral plasmas exhibit negative refraction and investigate the frequency region for negative refraction. The results show that chirality can induce negative refraction in plasmas. Moreover, both the degree of chirality and the external magnetic field have a significant effect on the critical frequency and the bandwidth of the frequency for negative refraction in chiral plasmas. The parameter dependence of the effects is calculated and discussed.

Chiral helimagnetic state in a Kondo lattice model with the Dzyaloshinskii-Moriya interaction

NASA Astrophysics Data System (ADS)

Okumura, Shun; Kato, Yasuyuki; Motome, Yukitoshi

2018-05-01

Monoaxial chiral magnets can form a noncollinear twisted spin structure called the chiral helimagnetic state. We study magnetic properties of such a chiral helimagnetic state, with emphasis on the effect of itinerant electrons. Modeling a monoaxial chiral helimagnet by a one-dimensional Kondo lattice model with the Dzyaloshinskii-Moriya interaction, we perform a variational calculation to elucidate the stable spin configuration in the ground state. We obtain a chiral helimagnetic state as a candidate for the ground state, whose helical pitch is modulated by the model parameters: the Kondo coupling, the Dzyaloshinski-Moriya interaction, and electron filling.

Chirality-specific lift forces of helix under shear flows: Helix perpendicular to shear plane.

PubMed

Zhang, Qi-Yi

2017-02-01

Chiral objects in shear flow experience a chirality-specific lift force. Shear flows past helices in a low Reynolds number regime were studied using slender-body theory. The chirality-specific lift forces in the vorticity direction experienced by helices are dominated by a set of helix geometry parameters: helix radius, pitch length, number of turns, and helix phase angle. Its analytical formula is given. The chirality-specific forces are the physical reasons for the chiral separation of helices in shear flow. Our results are well supported by the latest experimental observations. © 2016 Wiley Periodicals, Inc.

Review on Polarization Selective Terahertz Metamaterials: from Chiral Metamaterials to Stereometamaterials

NASA Astrophysics Data System (ADS)

Philip, Elizabath; Zeki Güngördü, M.; Pal, Sharmistha; Kung, Patrick; Kim, Seongsin Margaret

2017-09-01

In this article, recent progress and development of terahertz chiral metamaterials including stereometamaterials are thoroughly reviewed. This review mainly focuses on the fundamental principles of design and arrangement of meta-atoms in metamaterials exhibiting chirality with various asymmetry and symmetry and 2D and 3D configuration. Related optical and propagation properties in chiral metamaterials, such as optical activity, circular dichroism, and negative refraction for each different chiral metamaterials, are compared and investigated. Finally, comparison between chiral metamaterials with stereometamaterials in terms of the polarization selective operation along with the similarity and the distinction is addressed as well.

Enantiomeric separation of six chiral pesticides that contain chiral sulfur/phosphorus atoms by supercritical fluid chromatography.

PubMed

Zhang, Lijun; Miao, Yelong; Lin, Chunmian

2018-03-01

Six chiral pesticides containing chiral sulfur/phosphorus atoms were separated by supercritical fluid chromatography with supercritical CO 2 as the main mobile phase component. The effect of the chiral stationary phase, different type and concentration of modifiers, column temperature, and backpressure on the separation efficiency was investigated to obtain the appropriate separation condition. Five chiral pesticides (isofenphos-methyl, isocarbophos, flufiprole, fipronil, and ethiprole) were baseline separated under experimental conditions, while isofenphos only obtained partial separation. The Chiralpak AD-3 column showed a better chiral separation ability than others for chiral pesticides containing chiral sulfur/phosphorus atoms. When different modifiers at the same concentration were used, the retention factor of pesticides except flufiprole decreased in the order of isopropanol, ethanol, methanol; meanwhile, the retention factor of flufiprole increased in the order of isopropanol, ethanol, methanol. For a given modifier, the retention factor and resolution decreased on the whole with the increase of its concentration. The enantiomer separation of five chiral pesticides was an "enthalpy-driven" process, and the separation factor decreased as the temperature increased. The backpressure of the mobile phase had little effect on the separation factor and resolution. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Corolla chirality does not contribute to directed pollen movement in Hypericum perforatum (Hypericaceae): mirror image pinwheel flowers function as radially symmetric flowers in pollination.

PubMed

Diller, Carolina; Fenster, Charles B

2016-07-01

Corolla chirality, the pinwheel arrangement of petals within a flower, is found throughout the core eudicots. In 15 families, different chiral type flowers (i.e., right or left rotated corolla) exist on the same plant, and this condition is referred to as unfixed/enantiomorphic corolla chirality. There are no investigations on the significance of unfixed floral chirality on directed pollen movement even though analogous mirror image floral designs, for example, enantiostyly, has evolved in response to selection to direct pollinator and pollen movement. Here, we examine the role of corolla chirality on directing pollen transfer, pollinator behavior, and its potential influence on disassortative mating. We quantified pollen transfer and pollinator behavior and movement for both right and left rotated flowers in two populations of Hypericum perforatum. In addition, we quantified the number of right and left rotated flowers at the individual level. Pollinators were indifferent to corolla chirality resulting in no difference in pollen deposition between right and left flowers. Corolla chirality had no effect on pollinator and pollen movement between and within chiral morphs. Unlike other mirror image floral designs, corolla chirality appears to play no role in promoting disassortative mating in this species.

Synergistic effects on enantioselectivity of zwitterionic chiral stationary phases for separations of chiral acids, bases, and amino acids by HPLC.

PubMed

Hoffmann, Christian V; Pell, Reinhard; Lämmerhofer, Michael; Lindner, Wolfgang

2008-11-15

In an attempt to overcome the limited applicability scope of earlier proposed Cinchona alkaloid-based chiral weak anion exchangers (WAX) and recently reported aminosulfonic acid-based chiral strong cation exchangers (SCX), which are conceptionally restricted to oppositely charged solutes, their individual chiral selector (SO) subunits have been fused in a combinatorial synthesis approach into single, now zwitterionic, chiral SO motifs. The corresponding zwitterionic ion-exchange-type chiral stationary phases (CSPs) in fact combined the applicability spectra of the parent chiral ion exchangers allowing for enantioseparations of chiral acids and amine-type solutes in liquid chromatography using polar organic mode with largely rivaling separation factors as compared to the parent WAX and SCX CSPs. Furthermore, the application spectrum could be remarkably expanded to various zwitterionic analytes such as alpha- and beta-amino acids and peptides. A set of structurally related yet different CSPs consisting of either a quinine or quinidine alkaloid moiety as anion-exchange subunit and various chiral or achiral amino acids as cation-exchange subunits enabled us to derive structure-enantioselectivity relationships, which clearly provided strong unequivocal evidence for synergistic effects of the two oppositely charged ion-exchange subunits being involved in molecular recognition of zwitterionic analytes by zwitterionic SOs driven by double ionic coordination.

Chiral pharmaceuticals: A review on their environmental occurrence and fate processes.

PubMed

Sanganyado, Edmond; Lu, Zhijiang; Fu, Qiuguo; Schlenk, Daniel; Gan, Jay

2017-11-01

More than 50% of pharmaceuticals in current use are chiral compounds. Enantiomers of the same pharmaceutical have identical physicochemical properties, but may exhibit differences in pharmacokinetics, pharmacodynamics and toxicity. The advancement in separation and detection methods has made it possible to analyze trace amounts of chiral compounds in environmental media. As a result, interest on chiral analysis and evaluation of stereoselectivity in environmental occurrence, phase distribution and degradation of chiral pharmaceuticals has grown substantially in recent years. Here we review recent studies on the analysis, occurrence, and fate of chiral pharmaceuticals in engineered and natural environments. Monitoring studies have shown ubiquitous presence of chiral pharmaceuticals in wastewater, surface waters, sediments, and sludge, particularly β-receptor antagonists, analgesics, antifungals, and antidepressants. Selective sorption and microbial degradation have been demonstrated to result in enrichment of one enantiomer over the other. The changes in enantiomer composition may also be caused by biologically catalyzed chiral inversion. However, accurate evaluation of chiral pharmaceuticals as trace environmental pollutants is often hampered by the lack of identification of the stereoconfiguration of enantiomers. Furthermore, a systematic approach including occurrence, fate and transport in various environmental matrices is needed to minimize uncertainties in risk assessment of chiral pharmaceuticals as emerging environmental contaminants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chirality transition in the epoxidation of (-)-alpha-pinene and successive hydrolysis studied by Raman optical activity and DFT.

PubMed

Qiu, Shi; Li, Guanna; Liu, Peng; Wang, Changhao; Feng, Zhaochi; Li, Can

2010-03-28

Characterization of the chirality evolution involved in chemical and biochemical reaction processes is extremely important to the understanding of the chiral catalysis mechanism. In this work, the chiral transition from the epoxidation of (-)-alpha-pinene to alpha-pinene oxide and successive hydrolysis to (-)-pinanediol has been studied as an archetype of the asymmetric catalysis by Raman optical activity (ROA) and the DFT calculation. Minor changes of the absolute configuration of the chiral products from (-)-alpha-pinene to (-)-pinanediol lead to the dramatic variation in ROA spectra indicating that the chirality is delocalized in the whole molecule rather than only concentrated on the chiral centers. The oxygen atom of alpha-pinene oxide contributes strong ROA signals while the two hydroxyl groups of (-)-pinanediol give no apparent contribution to the chirality in terms of ROA signals. Isolation of the two symmetric anisotropic invariants shows that the predominant contribution to the ROA signals stems from the electric dipole-magnetic dipole invariant, and the bond polarizability model is indeed found to be a good approximation for molecules composed of entirely axially-symmetric bonds in alpha-pinene oxide and (-)-pinanediol. This study demonstrates the feasibility of using ROA to sensitively monitor the variation of the chirality transition during the chiral reactions either in the chemical or biological system.

Natural terpene derivatives as new structural task-specific ionic liquids to enhance the enantiorecognition of acidic enantiomers on teicoplanin-based stationary phase by high-performance liquid chromatography.

PubMed

Flieger, Jolanta; Feder-Kubis, Joanna; Tatarczak-Michalewska, Małgorzata; Płazińska, Anita; Madejska, Anna; Swatko-Ossor, Marta

2017-06-01

We present the specific cooperative effect of a semisynthetic glycopeptide antibiotic teicoplanin and chiral ionic liquids containing the (1R,2S,5R)-(-)-menthol moiety on the chiral recognition of enantiomers of mandelic acid, vanilmandelic acid, and phenyllactic acid. Experiments were performed chromatographically on an Astec Chirobiotic T chiral stationary phase applying the mobile phase with the addition of the chiral ionic liquids. The stereoselective binding of enantiomers to teicoplanin in presence of new chiral ionic liquids were evaluated applying thermodynamic measurements and the docking simulations. Both the experimental and theoretical methods revealed that the chiral recognition of enantiomers in the presence of new chiral ionic liquids was enthalpy driven. The changes of the teicoplanin conformation occurring upon binding of the chiral ionic liquids are responsible for the differences in the standard changes in Gibbs energy (ΔG 0 ) values obtained for complexes formed by the R and S enantiomers and teicoplanin. Docking simulations revealed the steric adjustment between the chiral ionic liquids cyclohexane ring (chair conformation) and the β-d-glucosamine ring of teicoplanin and additionally hydrophobic interactions between the decanoic aliphatic chain of teicoplanin and the alkyl group of the tested salts. The obtained terpene derivatives can be considered as "structural task-specific ionic liquids" responsible for enhancing the chiral resolution in synergistic systems with two chiral selectors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ENANTIOMERIC RATIOS OF CHIRAL PCB ATROPISOMERS IN RADIODATED SEDIMENT CORES

EPA Science Inventory

Enantiomeric ratios (ERs)) of chiral polychlorinated biphenyl (PCB) atropisomers were quantified in radiodated sediment cores of Lake Hartwell SC, a reservoir heavily impacted by PCBS, to study spatial and temporal changes in chirality. A chiral analysis of cores showed accumulat...

Spectrum of the Wilson Dirac operator at finite lattice spacings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akemann, G.; Damgaard, P. H.; Splittorff, K.

2011-04-15

We consider the effect of discretization errors on the microscopic spectrum of the Wilson Dirac operator using both chiral perturbation theory and chiral random matrix theory. A graded chiral Lagrangian is used to evaluate the microscopic spectral density of the Hermitian Wilson Dirac operator as well as the distribution of the chirality over the real eigenvalues of the Wilson Dirac operator. It is shown that a chiral random matrix theory for the Wilson Dirac operator reproduces the leading zero-momentum terms of Wilson chiral perturbation theory. All results are obtained for a fixed index of the Wilson Dirac operator. The low-energymore » constants of Wilson chiral perturbation theory are shown to be constrained by the Hermiticity properties of the Wilson Dirac operator.« less

Chiral nanoparticles in singular light fields

PubMed Central

Vovk, Ilia A.; Baimuratov, Anvar S.; Zhu, Weiren; Shalkovskiy, Alexey G.; Baranov, Alexander V.; Fedorov, Anatoly V.; Rukhlenko, Ivan D.

2017-01-01

The studying of how twisted light interacts with chiral matter on the nanoscale is paramount for tackling the challenging task of optomechanical separation of nanoparticle enantiomers, whose solution can revolutionize the entire pharmaceutical industry. Here we calculate optical forces and torques exerted on chiral nanoparticles by Laguerre–Gaussian beams carrying a topological charge. We show that regardless of the beam polarization, the nanoparticles are exposed to both chiral and achiral forces with nonzero reactive and dissipative components. Longitudinally polarized beams are found to produce chirality densities that can be 109 times higher than those of transversely polarized beams and that are comparable to the chirality densities of beams polarized circularly. Our results and analytical expressions prove useful in designing new strategies for mechanical separation of chiral nanoobjects with the help of highly focussed beams. PMID:28378842

Chiral nanoparticles in singular light fields

NASA Astrophysics Data System (ADS)

Vovk, Ilia A.; Baimuratov, Anvar S.; Zhu, Weiren; Shalkovskiy, Alexey G.; Baranov, Alexander V.; Fedorov, Anatoly V.; Rukhlenko, Ivan D.

2017-04-01

The studying of how twisted light interacts with chiral matter on the nanoscale is paramount for tackling the challenging task of optomechanical separation of nanoparticle enantiomers, whose solution can revolutionize the entire pharmaceutical industry. Here we calculate optical forces and torques exerted on chiral nanoparticles by Laguerre-Gaussian beams carrying a topological charge. We show that regardless of the beam polarization, the nanoparticles are exposed to both chiral and achiral forces with nonzero reactive and dissipative components. Longitudinally polarized beams are found to produce chirality densities that can be 109 times higher than those of transversely polarized beams and that are comparable to the chirality densities of beams polarized circularly. Our results and analytical expressions prove useful in designing new strategies for mechanical separation of chiral nanoobjects with the help of highly focussed beams.

Effects of nonadditive interactions on ion solvation at the water/vapor interface: a molecular dynamics study.

PubMed

Yagasaki, Takuma; Saito, Shinji; Ohmine, Iwao

2010-12-09

The solvation of halide ions at the water/vapor interface is investigated by using molecular dynamics simulations with nonpolarizable molecular mechanical (MM), polarizable MM, and quantum mechanical (QM)/MM methods. The free energy profile of the ion solvation is decomposed into the energy and the entropic contributions along the ion displacement from inside to the surface of water. It is found that the surface affinity of the ion, relative to the bulk value, is determined by a subtle balance between the energetic destabilization and the entropic stabilization with the ion displacement. The amount of energetic destabilization is found to be reduced when nonadditive interactions are included, as in the polarizable MM and QM/MM models. The structure of water around the ion at the interface is also largely modified when the higher order effects are considered. For example, the induced dipole effect enhances the solvation structure around the ion at the interface significantly and thus reduces the amount of entropic stabilization at the interface, relative to in the bulk. It is found that this induced dipole effect causes the slowing in the ion-water hydrogen bond dynamics at the interface. On the other hand, the higher order induced multipole effects in the QM/MM method suppress both the excessive enhancement of the solvation structure and the slowing of the ion-water hydrogen bond dynamics at the interface. The present study demonstrates that not only the induced dipole moment but also the higher order induced multipole moments, which are neglected in standard empirical models, are essential for the correct description of the ion solvation at the water/vapor interface.

Advanced dielectric continuum model of preferential solvation

NASA Astrophysics Data System (ADS)

Basilevsky, Mikhail; Odinokov, Alexey; Nikitina, Ekaterina; Grigoriev, Fedor; Petrov, Nikolai; Alfimov, Mikhail

2009-01-01

A continuum model for solvation effects in binary solvent mixtures is formulated in terms of the density functional theory. The presence of two variables, namely, the dimensionless solvent composition y and the dimensionless total solvent density z, is an essential feature of binary systems. Their coupling, hidden in the structure of the local dielectric permittivity function, is postulated at the phenomenological level. Local equilibrium conditions are derived by a variation in the free energy functional expressed in terms of the composition and density variables. They appear as a pair of coupled equations defining y and z as spatial distributions. We consider the simplest spherically symmetric case of the Born-type ion immersed in the benzene/dimethylsulfoxide (DMSO) solvent mixture. The profiles of y(R ) and z(R ) along the radius R, which measures the distance from the ion center, are found in molecular dynamics (MD) simulations. It is shown that for a given solute ion z(R ) does not depend significantly on the composition variable y. A simplified solution is then obtained by inserting z(R ), found in the MD simulation for the pure DMSO, in the single equation which defines y(R ). In this way composition dependences of the main solvation effects are investigated. The local density augmentation appears as a peak of z(R ) at the ion boundary. It is responsible for the fine solvation effects missing when the ordinary solvation theories, in which z =1, are applied. These phenomena, studied for negative ions, reproduce consistently the simulation results. For positive ions the simulation shows that z ≫1 (z =5-6 at the maximum of the z peak), which means that an extremely dense solvation shell is formed. In such a situation the continuum description fails to be valid within a consistent parametrization.

The solvation structure of Mg ions in dichloro complex solutions from first-principles molecular dynamics and simulated X-ray absorption spectra.

PubMed

Wan, Liwen F; Prendergast, David

2014-10-15

The knowledge of Mg solvation structure in the electrolyte is requisite to understand the transport behavior of Mg ions and their dissolution/deposition mechanism at electrolyte/electrode interfaces. In the first established rechargeable Mg-ion battery system [D. Aurbach et al. Nature 2000, 407, 724], the electrolyte is of the dichloro complex (DCC) solution family, Mg(AlCl2BuEt)2/THF, resulting from the reaction of Bu2Mg and EtAlCl2 with a molar ratio of 1:2. There is disagreement in the literature regarding the exact solvation structure of Mg ions in such solutions, i.e., whether Mg(2+) is tetra- or hexacoordinated by a combination of Cl(-) and THF. In this work, theoretical insight into the solvation complexes present is provided based on first-principles molecular dynamics simulations (FPMD). Both Mg monomer and dimer structures are considered in both neutral and positively charged states. We found that, at room temperature, the Mg(2+) ion tends to be tetracoordinated in the THF solution phase instead of hexacoordinated, which is the predominant solid-phase coordination. Simulating the X-ray absorption spectra (XAS) at the Mg K-edge by sampling our FPMD trajectories, our predicted solvation structure can be readily compared with experimental measurements. It is found that when changing from tetra- to hexacoordination, the onset of X-ray absorption should exhibit at least a 1 eV blue shift. We propose that this energy shift can be used to monitor changes in the Mg solvation sphere as it migrates through the electrolyte to electrolyte/electrode interfaces and to elucidate the mechanism of Mg dissolution/deposition.

Solvation Thermodynamic Properties of Hydrogen Sulfide in [C4mim][PF6], [C4mim][BF4], and [C4mim][Cl] Ionic Liquids, Determined by Molecular Simulations.

PubMed

Sánchez-Badillo, Joel; Gallo, Marco; Alvarado, Sandra; Glossman-Mitnik, Daniel

2015-08-20

Removal of hydrogen sulfide (H2S) and acid gases from natural gas is accomplished by absorption processes using a solvent. The gas solubility in a liquid can be used to measure the degree of removal of the gas and is quantified by the Henry's constant, the free energy of solvation at infinite dilution, or the excess chemical potential. In this work, Henry's constants and thermodynamic properties of solvation of H2S were calculated in three ionic liquids: [C4mim][PF6], [C4mim][BF4], and [C4mim][Cl] ([C4mim], 1-butyl-3-methyl imidazolium). The first step in this work was the evaluation of the force fields for the gas and condensed phases in order to obtain accurate values for the excess chemical potential for H2S on each ionic liquid using free energy perturbation techniques. In the H2S-[C4mim][PF6] and H2S-[C4mim][BF4] systems, the results obtained by molecular simulation agree with the experimental values reported in the literature. However, the solvation free energy calculated for the H2S-[C4mim][Cl] system can be considered predictive because of the lack of experimental data at the simulated conditions. Based on these results, the best solvent for removing H2S is [C4mim][Cl] because it has the highest affinity for this species (lowest value of the Henry's constant). Also, solvation thermodynamic properties such as enthalpy and entropy were calculated in order to evaluate their contribution to the free energy of solvation.

Chirality: a relational geometric-physical property.

PubMed

Gerlach, Hans

2013-11-01

The definition of the term chirality by Lord Kelvin in 1893 and 1904 is analyzed by taking crystallography at that time into account. This shows clearly that chirality is a relational geometric-physical property, i.e., two relations between isometric objects are possible: homochiral or heterochiral. In scientific articles the relational term chirality is often mistaken for the two valued measure for the individual (absolute) sense of chirality, an arbitrary attributive term. © 2013 Wiley Periodicals, Inc.

Study on the determination and chiral inversion of R-salbutamol in human plasma and urine by liquid chromatography-tandem mass spectrometry.

PubMed

Zhou, Ting; Zeng, Jing; Liu, Shan; Zhao, Ting; Wu, Jie; Lai, Wenshi; He, Mingzhi; Xu, Beining; Qu, Shanshan; Xu, Ling; Tan, Wen

2015-10-01

The chiral inversion has been a concerned issue during the research and development of a chiral drug. In this study, a sensitive chiral liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for determination of salbutamol enantiomers in human plasma and urine. The chiral inversion mechanism of R-salbutamol was fully investigated for the first time by studying the effects of physicochemical factors, including pH, temperature and time. A fitted model to predict the chiral inversion ratio of R-salbutamol was proposed using a Box-Behnken design. All the samples were separated on an Astec Chirobiotic T column and detected by a tandem mass spectrometer in multiple reaction monitoring mode. Lower limit of quantification of 0.100ng/mL was achieved under the optimized conditions. The method was fully validated and successfully applied to the clinical pharmacokinetic study of R-salbutamol in healthy volunteers. Chiral inversion of R-salbutamol to S-salbutamol has been detected in urine samples. The results indicated that pH and temperature were two dominant factors that caused the chiral inversion of R-salbutamol, which should be taken into consideration during the analysis of chiral drugs. The chiral inversion of R-salbutamol determined in this study was confirmed resulted from the gastric acid in stomach rather than caused by the analysis conditions. Moreover, the calculated results of the fitted model matched very well with the enantioselective pharmacokinetic study of R-salbutamol, and the individual difference of the chiral inversion ratio of R-salbutamol was related to the individual gastric environment. On the basis of the results, this study provides important and concrete information not only for the chiral analysis but also for the metabolism research of chiral drugs. Copyright © 2015 Elsevier B.V. All rights reserved.

Enantioselective Biotransformation of Chiral Persistent Organic Pollutants.

PubMed

Zhang, Ying; Ye, Jing; Liu, Min

2017-01-01

Enantiomers of chiral compounds commonly undergo enantioselective transformation in most biologically mediated processes. As chiral persistent organic pollutants (POPs) are extensively distributed in the environment, differences between enantiomers in biotransformation should be carefully considered to obtain exact enrichment and specific health risks. This review provides an overview of in vivo biotransformation of chiral POPs currently indicated in the Stockholm Convention and their chiral metabolites. Peer-reviewed journal articles focused on the research question were thoroughly searched. A set of inclusion and exclusion criteria were developed to identify relevant studies. We mainly compared the results from different animal models under controlled laboratory conditions to show the difference between enantiomers in terms of distinct transformation potential. Interactions with enzymes involved in enantioselective biotransformation, especially cytochrome P450 (CYP), were discussed. Further research areas regarding this issue were proposed. Limited evidence for a few POPs has been found in 30 studies. Enantioselective biotransformation of α-hexachlorocyclohexane (α-HCH), chlordane, dichlorodiphenyltrichloroethane (DDT), heptachlor, hexabromocyclododecane (HBCD), polychlorinated biphenyls (PCBs), and toxaphene, has been investigated using laboratory mammal, fish, bird, and worm models. Tissue and excreta distributions, as well as bioaccumulation and elimination kinetics after administration of racemate and pure enantiomers, have been analyzed in these studies. Changes in enantiomeric fractions have been considered as an indicator of enantioselective biotransformation of chiral POPs in most studies. Results of different laboratory animal models revealed that chiral POP biotransformation is seriously affected by chirality. Pronounced results of species-, tissue-, gender-, and individual-dependent differences are observed in in vivo biotransformation of chiral POPs. Enantioselective biotransformation of chiral POPs is dependent on enzyme amounts and activities. However, the role of cytochrome P450 in enantioselective biotransformation has not yet been confirmed. Currently available data on biotransformation of chiral POPs provide a preliminary understanding of the fate of chiral compounds in organisms. Further detailed studies of species-dependent biotransformation pathway and molecular mechanism in various animal models should be performed to comprehensively understand chiral POP biotransformation.

Investigating the nature of chiral near-field interactions

NASA Astrophysics Data System (ADS)

Barr, Lauren E.; Horsley, Simon A. R.; Hooper, Ian R.; Eager, Jake K.; Gallagher, Cameron P.; Hornett, Samuel M.; Hibbins, Alastair P.; Hendry, Euan

2018-04-01

In recent years, there have been reports of enhanced chiroptical interactions in the near-fields of antennas, postulated to be mediated by high spatial gradients in the electromagnetic fields. Here, using gigahertz experimentation, we investigate the nature of the chiral near-field generated by an array of staggered-rod antennas through its interaction with an array of aligned, subwavelength metallic helices. This allows us to eliminate many potential origins of enhancements, such as those associated with plasmon-exciton interactions, and search solely for enhancements due to the high spatial gradients in the chirality of the fields around chiral antennas (so-called `superchiral fields'). By comparing the strength of the chiral interaction with our helices to that of a homogeneous chiral layer with effective material parameters, we find that the strength of this chiral interaction can be predicted using a completely local effective medium approximation. This suggests no obvious enhancement in the chiral interaction in the near-field and indicates that nonlocal interactions are negligible in this system.

Industrial-scale separation of high-purity single-chirality single-wall carbon nanotubes for biological imaging

PubMed Central

Yomogida, Yohei; Tanaka, Takeshi; Zhang, Minfang; Yudasaka, Masako; Wei, Xiaojun; Kataura, Hiromichi

2016-01-01

Single-chirality, single-wall carbon nanotubes are desired due to their inherent physical properties and performance characteristics. Here, we demonstrate a chromatographic separation method based on a newly discovered chirality-selective affinity between carbon nanotubes and a gel containing a mixture of the surfactants. In this system, two different selectivities are found: chiral-angle selectivity and diameter selectivity. Since the chirality of nanotubes is determined by the chiral angle and diameter, combining these independent selectivities leads to high-resolution single-chirality separation with milligram-scale throughput and high purity. Furthermore, we present efficient vascular imaging of mice using separated single-chirality (9,4) nanotubes. Due to efficient absorption and emission, blood vessels can be recognized even with the use of ∼100-fold lower injected dose than the reported value for pristine nanotubes. Thus, 1 day of separation provides material for up to 15,000 imaging experiments, which is acceptable for industrial use. PMID:27350127

Transfer and Dynamic Inversion of Coassembled Supramolecular Chirality through 2D-Sheet to Rolled-Up Tubular Structure.

PubMed

Choi, Heekyoung; Cho, Kang Jin; Seo, Hyowon; Ahn, Junho; Liu, Jinying; Lee, Shim Sung; Kim, Hyungjun; Feng, Chuanliang; Jung, Jong Hwa

2017-12-13

Transfer and inversion of supramolecular chirality from chiral calix[4]arene analogs (3D and 3L) with an alanine moiety to an achiral bipyridine derivative (1) with glycine moieties in a coassembled hydrogel are demonstrated. Molecular chirality of 3D and 3L could transfer supramolecular chirality to an achiral bipyridine derivative 1. Moreover, addition of 0.6 equiv of 3D or 3L to 1 induced supramolecular chirality inversion of 1. More interestingly, the 2D-sheet structure of the coassembled hydrogels formed with 0.2 equiv of 3D or 3L changed to a rolled-up tubular structure in the presence of 0.6 equiv of 3D or 3L. The chirality inversion and morphology change are mainly mediated by intermolecular hydrogen-bonding interactions between the achiral and chiral molecules, which might be induced by reorientations of the assembled molecules, confirmed by density functional theory calculations.

Strong-field control and enhancement of chiral response in bi-elliptical high-order harmonic generation: an analytical model

NASA Astrophysics Data System (ADS)

Ayuso, David; Decleva, Piero; Patchkovskii, Serguei; Smirnova, Olga

2018-06-01

The generation of high-order harmonics in a medium of chiral molecules driven by intense bi-elliptical laser fields can lead to strong chiroptical response in a broad range of harmonic numbers and ellipticities (Ayuso et al 2018 J. Phys. B: At. Mol. Opt. Phys. 51 06LT01). Here we present a comprehensive analytical model that can describe the most relevant features arising in the high-order harmonic spectra of chiral molecules driven by strong bi-elliptical fields. Our model recovers the physical picture underlying chiral high-order harmonic generation (HHG) based on ultrafast chiral hole motion and identifies the rotationally invariant molecular pseudoscalars responsible for chiral dynamics. Using the chiral molecule propylene oxide as an example, we show that one can control and enhance the chiral response in bi-elliptical HHG by tailoring the driving field, in particular by tuning its frequency, intensity and ellipticity, exploiting a suppression mechanism of achiral background based on the linear Stark effect.

Charge/spin supercurrent and the Fulde-Ferrell state induced by crystal deformation in Weyl/Dirac superconductors

NASA Astrophysics Data System (ADS)

Matsushita, Taiki; Liu, Tianyu; Mizushima, Takeshi; Fujimoto, Satoshi

2018-04-01

It has been predicted that emergent chiral magnetic fields can be generated by crystal deformation in Weyl/Dirac metals and superconductors. The emergent fields give rise to chiral anomaly phenomena as in the case of Weyl semimetals with usual electromagnetic fields. Here, we clarify effects of the chiral magnetic field on Cooper pairs in Weyl/Dirac superconductors on the basis of the Ginzburg-Landau equation microscopically derived from the quasiclassical Eilenberger formalism. It is found that Cooper pairs are affected by the emergent chiral magnetic field in a dramatic way, and the pseudo-Lorentz force due to the chiral magnetic field stabilizes the Fulde-Ferrell state and causes a charge/spin supercurrent, which flows parallel to the chiral magnetic field in the case of Weyl/Dirac superconductors. This effect is in analogy with the chiral magnetic effect of Weyl semimetals. In addition, we elucidate that neither Meissner effect nor vortex state due to chiral magnetic fields occurs.

Enantioseparation by Capillary Electrophoresis Using Ionic Liquids as Chiral Selectors.

PubMed

Greño, Maider; Marina, María Luisa; Castro-Puyana, María

2018-11-02

Capillary electrophoresis (CE) is one of the most widely employed analytical techniques to achieve enantiomeric separations. In spite of the fact that there are many chiral selectors commercially available to perform enantioseparations by CE, one of the most relevant topics in this field is the search for new selectors capable of providing high enantiomeric resolutions. Chiral ionic liquids (CILs) have interesting characteristics conferring them a high potential in chiral separations although only some of them are commercially available. The aim of this article is to review all the works published on the use of CILs as chiral selectors in the development of enantioselective methodologies by CE, covering the period from 2006 (when the first research work on this topic was published) to 2017. The use of CILs as sole chiral selectors, as chiral selectors in dual systems or as chiral ligands will be considered. This review also provides detailed analytical information on the experimental conditions used to carry out enantioseparations in different fields as well as on the separation mechanism involved.

Second-order dissipative hydrodynamics for plasma with chiral asymmetry and vorticity

NASA Astrophysics Data System (ADS)

Gorbar, E. V.; Rybalka, D. O.; Shovkovy, I. A.

2017-05-01

By making use of the chiral kinetic theory in the relaxation-time approximation, we derive an Israel-Stewart type formulation of the hydrodynamic equations for a chiral relativistic plasma made of neutral particles (e.g., neutrinos). The effects of chiral asymmetry are captured by including an additional continuity equation for the axial charge, as well as the leading-order quantum corrections due to the spin of particles. In a formulation of the chiral kinetic theory used, we introduce a symmetric form of the energy-momentum tensor that is suitable for the description of a weakly nonuniform chiral plasma. By construction, the energy and momentum are conserved to the same leading order in the Planck constant as the kinetic equation itself. By making use of such a chiral kinetic theory and the Chapman-Enskog approach, we obtain a set of second-order dissipative hydrodynamic equations. The effects of the fluid vorticity and velocity fluctuations on the dispersion relations of chiral vortical waves are analyzed.

DESTRUCTION OF HALOGENATED HYDROCARBONS WITH SOLVATED ELECTRONS IN THE PRESENCE OF WATER. (R826180)

EPA Science Inventory

Model halogenated aromatic and aliphatic hydrocarbons and halogenated phenols were dehalogenated in seconds by solvated electrons generated from sodium in both anhydrous liquid ammonia and ammonia/water solutions. The minimum sodium required to completely dehalogenate these mo...

Preferential Solvation of an Asymmetric Redox Molecule

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Kee Sung; Rajput, Nav Nidhi; Vijayakumar, M.

2016-12-15

The fundamental correlations between inter-molecular interactions, solvation structure and functionality of electrolytes are in many cases unknown, particularly for multi-component liquid systems. In this work, we explore such correlations by investigating the complex interplay between solubility and solvation structure for the electrolyte system comprising N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethylsulfonimide (Fc1N112-TFSI) dissolved in a ternary carbonate solvent mixture using combined NMR relaxation and computational analyses. Probing the evolution of the solvent-solvent, ion-solvent and ion-ion interactions with an increase in solute concentration provides a molecular level understanding of the solubility limit of the Fc1N112-TFSI system. An increase in solute con-centration leads to pronounced Fc1N112-TFSI contact-ionmore » pair formation by diminishing solvent-solvent and ion-solvent type interactions. At the solubility limit, the precipitation of solute is initiated through agglomeration of contact-ion pairs due to overlapping solvation shells.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vijayakumar, M.; Nie, Zimin; Walter, Eric D.

Redox flow battery (RFB) is a promising candidate for energy storage component in designing resilient grid scale power supply due to the advantage of the separation of power and energy. However, poorly understood chemical and thermal stability issues of electrolytes currently limit the performance of RFB. Designing of high performance stable electrolytes requires comprehensive knowledge about the molecular level solvation structure and dynamics of their redox active species. The molecular level understanding of detrimental V2O5 precipitation process led to successful designing of mixed acid based electrolytes for vanadium redox flow batteries (VRFB). The higher stability of mixed acid based electrolytesmore » is attributed to the choice of hydrochloric acid as optimal co-solvent, which provides chloride anions for ligand exchange process in vanadium solvation structure. The role of chloride counter anion on solvation structure and dynamics of vanadium species were studied using combined magnetic resonance spectroscopy and DFT based theoretical methods. Finally, the solvation phenomenon of multiple vanadium species and their impact on VRFB electrolyte chemical stability were discussed.« less

Corrosion Thermodynamics of Magnesium and Alloys from First Principles as a Function of Solvation

NASA Astrophysics Data System (ADS)

Limmer, Krista; Williams, Kristen; Andzelm, Jan

Thermodynamics of corrosion processes occurring on magnesium surfaces, such as hydrogen evolution and water dissociation, have been examined with density functional theory (DFT) to evaluate the effect of impurities and dilute alloying additions. The modeling of corrosion thermodynamics requires examination of species in a variety of chemical and electronic states in order to accurately represent the complex electrochemical corrosion process. In this study, DFT calculations for magnesium corrosion thermodynamics were performed with two DFT codes (VASP and DMol3), with multiple exchange-correlation functionals for chemical accuracy, as well as with various levels of implicit and explicit solvation for surfaces and solvated ions. The accuracy of the first principles calculations has been validated against Pourbaix diagrams constructed from solid, gas and solvated charged ion calculations. For aqueous corrosion, it is shown that a well parameterized implicit solvent is capable of accurately representing all but the first coordinating layer of explicit water for charged ions.

Solvent-driven reductive activation of carbon dioxide by gold anions.

PubMed

Knurr, Benjamin J; Weber, J Mathias

2012-11-14

Catalytic activation and electrochemical reduction of CO(2) for the formation of chemically usable feedstock and fuel are central goals for establishing a carbon neutral fuel cycle. The role of solvent molecules in catalytic processes is little understood, although solvent-solute interactions can strongly influence activated intermediate species. We use vibrational spectroscopy of mass-selected Au(CO(2))(n)(-) cluster ions to probe the solvation of AuCO(2)(-) as a model for a reactive intermediate in the reductive activation of a CO(2) ligand by a single-atom catalyst. For the first few solvent molecules, solvation of the complex preferentially occurs at the CO(2) moiety, enhancing reductive activation through polarization of the excess charge onto the partially reduced ligand. At higher levels of solvation, direct interaction of additional solvent molecules with the Au atom diminishes reduction. The results show how the solvation environment can enhance or diminish the effects of a catalyst, offering design criteria for single-atom catalyst engineering.

Free Energy Wells and Barriers to Ion Transport Across Membranes

NASA Astrophysics Data System (ADS)

Rempe, Susan

2014-03-01

The flow of ions across cellular membranes is essential to many biological processes. Ion transport is also important in synthetic materials used as battery electrolytes. Transport often involves specific ions and fast conduction. To achieve those properties, ion conduction pathways must solvate specific ions by just the ``right amount.'' The right amount of solvation avoids ion traps due to deep free energy wells, and avoids ion block due to high free energy barriers. Ion channel proteins in cellular membranes demonstrate this subtle balance in solvation of specific ions. Using ab initio molecular simulations, we have interrogated the link between binding site structure and ion solvation free energies in biological ion binding sites. Our results emphasize the surprisingly important role of the environment that surrounds ion-binding sites for fast transport of specific ions. We acknowledge support from Sandia's LDRD program. Sandia National Labs is a multi-program laboratory operated by Sandia Corp., a wholly owned subsidiary of Lockheed Martin Corp., for the US DOE's NNSA under contract DE-AC04-94AL85000.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

PubMed Central

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-01-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level. PMID:28272396

Quantitative measurement of solvation shells using frequency modulated atomic force microscopy

NASA Astrophysics Data System (ADS)

Uchihashi, T.; Higgins, M.; Nakayama, Y.; Sader, J. E.; Jarvis, S. P.

2005-03-01

The nanoscale specificity of interaction measurements and additional imaging capability of the atomic force microscope make it an ideal technique for measuring solvation shells in a variety of liquids next to a range of materials. Unfortunately, the widespread use of atomic force microscopy for the measurement of solvation shells has been limited by uncertainties over the dimensions, composition and durability of the tip during the measurements, and problems associated with quantitative force calibration of the most sensitive dynamic measurement techniques. We address both these issues by the combined use of carbon nanotube high aspect ratio probes and quantifying the highly sensitive frequency modulation (FM) detection technique using a recently developed analytical method. Due to the excellent reproducibility of the measurement technique, additional information regarding solvation shell size as a function of proximity to the surface has been obtained for two very different liquids. Further, it has been possible to identify differences between chemical and geometrical effects in the chosen systems.

Assessing implicit models for nonpolar mean solvation forces: The importance of dispersion and volume terms

PubMed Central

Wagoner, Jason A.; Baker, Nathan A.

2006-01-01

Continuum solvation models provide appealing alternatives to explicit solvent methods because of their ability to reproduce solvation effects while alleviating the need for expensive sampling. Our previous work has demonstrated that Poisson-Boltzmann methods are capable of faithfully reproducing polar explicit solvent forces for dilute protein systems; however, the popular solvent-accessible surface area model was shown to be incapable of accurately describing nonpolar solvation forces at atomic-length scales. Therefore, alternate continuum methods are needed to reproduce nonpolar interactions at the atomic scale. In the present work, we address this issue by supplementing the solvent-accessible surface area model with additional volume and dispersion integral terms suggested by scaled particle models and Weeks–Chandler–Andersen theory, respectively. This more complete nonpolar implicit solvent model shows very good agreement with explicit solvent results and suggests that, although often overlooked, the inclusion of appropriate dispersion and volume terms are essential for an accurate implicit solvent description of atomic-scale nonpolar forces. PMID:16709675

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

NASA Astrophysics Data System (ADS)

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion...carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

Significance of solvated electrons (e(aq)-) as promoters of life on earth.

PubMed

Getoff, Nikola

2014-01-01

Based on the present state of knowledge a new hypothesis concerning the origin of life on Earth is presented, and emphasizes the particular significance of solvated electrons (e(aq)(-)). Solvated electrons are produced in seawater, mainly by (40)K radiation and in atmospheric moisture by VUV light, electrical discharges and cosmic ray. Solvated electrons are involved in primary chemical processes and in biological processes. The conversion of aqueous CO2 and CO into simple organic substances, the generation of ammonia from N2 and water, the formation of amines, amino acids and simple proteins under the action of e(aq)(-) has been experimentally proven. Furthermore, it is supposed that the generation of the primitive cell and equilibria of primitive enzymes are also realized due to the strong reducing property of e(aq)(-). The presented hypothesis is mainly founded on recently obtained experimental results. The involvement of e(aq)(-) in such mechanisms, as well as their action as an initiator of life is also briefly discussed.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery.

PubMed

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-08

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

Exit channel dynamics in a micro-hydrated SN2 reaction of the hydroxyl anion.

PubMed

Otto, R; Brox, J; Trippel, S; Stei, M; Best, T; Wester, R

2013-08-29

We report on the reaction dynamics of the monosolvated SN2 reaction of cold OH(-)(H2O) with CH3I that have been studied using crossed beam ion imaging. Two SN2 reaction channels are possible for this reaction: Formation of unsolvated I(-) and of solvated I(-)(H2O) products. We find a strong preference for the formation of unsolvated I(-) reaction products with respect to the energetically favored reaction toward solvated I(-)(H2O). Angle differential cross section measurements reveal similar velocity and angular distributions for all solvated and parts of the unsolvated reaction products. We furthermore find that the contribution of these two products to the total product flux can be described by the same collision energy dependence. We interpret our findings in terms of a joint reaction mechanism in which a CH3OH(H2O)···I(-) complex is formed that decays into either solvated or unsolvated products. Quantum chemical calculation are used to support this assumption.

Atomistic characterization of the active-site solvation dynamics of a model photocatalyst

DOE PAGES

van Driel, Tim B.; Kjær, Kasper S.; Hartsock, Robert W.; ...

2016-11-28

The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynamics following excitation of a model photocatalytic molecular system [Ir 2(dimen) 4] 2+, where dimen is para-diisocyanomenthane. The time-dependent structural changes in this model photocatalyst, as well as the changes in the solvation shell structure, have been measured with ultrafast diffuse X-ray scattering and simulated with Born-Oppenheimer Molecular Dynamics. Both methods provide direct access to the solute–solvent pair distribution function, enabling themore » solvation dynamics around the catalytically active iridium sites to be robustly characterized. Our results provide evidence for the coordination of the iridium atoms by the acetonitrile solvent and demonstrate the viability of using diffuse X-ray scattering at free-electron laser sources for studying the dynamics of photocatalysis.« less

Molecular dynamics study of thermodynamic stability and dynamics of [Li(glyme)]+ complex in lithium-glyme solvate ionic liquids

NASA Astrophysics Data System (ADS)

Shinoda, Wataru; Hatanaka, Yuta; Hirakawa, Masashi; Okazaki, Susumu; Tsuzuki, Seiji; Ueno, Kazuhide; Watanabe, Masayoshi

2018-05-01

Equimolar mixtures of glymes and organic lithium salts are known to produce solvate ionic liquids, in which the stability of the [Li(glyme)]+ complex plays an important role in determining the ionic dynamics. Since these mixtures have attractive physicochemical properties for application as electrolytes, it is important to understand the dependence of the stability of the [Li(glyme)]+ complex on the ion dynamics. A series of microsecond molecular dynamics simulations has been conducted to investigate the dynamic properties of these solvate ionic liquids. Successful solvate ionic liquids with high stability of the [Li(glyme)]+ complex have been shown to have enhanced ion dynamics. Li-glyme pair exchange rarely occurs: its characteristic time is longer than that of ion diffusion by one or two orders of magnitude. Li-glyme pair exchange most likely occurs through cluster formation involving multiple [Li(glyme)]+ pairs. In this process, multiple exchanges likely take place in a concerted manner without the production of energetically unfavorable free glyme or free Li+ ions.

Asymmetric Michael Addition Mediated by Chiral Ionic Liquids.

PubMed

Suzuki, Yumiko

2018-06-01

Chiral ionic liquids with a focus on their applications in asymmetric Michael additions and related reactions were reviewed. The examples were classified on the basis of the mode of asymmetric induction (e.g., external induction/non-covalent interaction or internal induction/covalent bond formation), the roles in reactions (as a solvent or catalyst), and their structural features (e.g., imidazolium-based chiral cations, other chiral oniums; proline derivatives). Most of the reactions with high chiral induction are Michael addition of ketones or aldehydes to chalcones or nitrostyrenes where proline-derived chiral ionic liquids catalyze the reaction through enamine/ iminium formation. Many reports demonstrate the recyclability of ionic liquid-tagged pyrrolidines.

Chiral-selective nonlinear optical generation and emission control with plasmonic metamaterials (Conference Presentation)

NASA Astrophysics Data System (ADS)

Cai, Wenshan

2016-09-01

Metamaterials can be designed to exhibit extraordinarily strong chiral responses. Here we present a chiral metamaterial that produces both distinguishable linear and nonlinear features in the visible to near-infrared range. In additional to the gigantic chiral effects in the linear regime, the metamaterial demonstrates a pronounced contrast between second harmonic responses from the two circular polarizations. Linear and nonlinear images probed with circularly polarized lights show strongly defined contrast. Moreover, the chiral centers of the nanometallic structures with enhanced hotspots can be purposely opened for direct access, where emitters occupying the light-confining regions produce chiral-selective enhancement of two-photon luminescence.

Chiral magnetic effect in condensed matter systems

DOE PAGES

Li, Qiang; Kharzeev, Dmitri E.

2016-12-01

The chiral magnetic effect is the generation of electrical current induced by chirality imbalance in the presence of magnetic field. It is a macroscopic manifestation of the quantum anomaly in relativistic field theory of chiral fermions. In the quark-gluon plasma, the axial anomaly induces topological charge changing transition that results in the generation of electrical current along the magnetic field. In condensed matter systems, the chiral magnetic effect was first predicted in the gapless semiconductors with tow energy bands having pointlike degeneracies. In addition, thirty years later after this prediction, the chiral magnetic effect was finally observed in the 3Dmore » Dirac/Weyl semimetals.« less

Split Octonion Reformulation for Electromagnetic Chiral Media of Massive Dyons

NASA Astrophysics Data System (ADS)

Chanyal, B. C.

2017-12-01

In an explicit, unified, and covariant formulation of an octonion algebra, we study and generalize the electromagnetic chiral fields equations of massive dyons with the split octonionic representation. Starting with 2×2 Zorn’s vector matrix realization of split-octonion and its dual Euclidean spaces, we represent the unified structure of split octonionic electric and magnetic induction vectors for chiral media. As such, in present paper, we describe the chiral parameter and pairing constants in terms of split octonionic matrix representation of Drude-Born-Fedorov constitutive relations. We have expressed a split octonionic electromagnetic field vector for chiral media, which exhibits the unified field structure of electric and magnetic chiral fields of dyons. The beauty of split octonionic representation of Zorn vector matrix realization is that, the every scalar and vector components have its own meaning in the generalized chiral electromagnetism of dyons. Correspondingly, we obtained the alternative form of generalized Proca-Maxwell’s equations of massive dyons in chiral media. Furthermore, the continuity equations, Poynting theorem and wave propagation for generalized electromagnetic fields of chiral media of massive dyons are established by split octonionic form of Zorn vector matrix algebra.

Emergence of Chiral Phases in Active Torque Dipole Systems

NASA Astrophysics Data System (ADS)

Fialho, Ana; Tjhung, Elsen; Cates, Michael; Marenduzzo, Davide

The common description of active particles as active force dipoles fails to take into account that active processes in biological systems often exhibit chiral asymmetries, generating active chiral processes and torque dipoles. Examples of such systems include cytoskeleton filaments which interact with motor proteins and beating cilia and flagella. In particular, the generation of active torques by the actomyosin cytoskeleton has been linked to the break of chiral symmetry at a cellular level. This phenomenon could constitute the primary determinant for the break of left-right symmetry in many living organisms, e.g. the position of the human heart within the human body. In order to account for the effects of chirality, we consider active torque dipoles which generate a chiral active stress. We characterize quasi-1D and 2D systems of torque dipoles, using a combination of linear stability analysis and numerical simulations (Lattice Boltzmann). Our results show that activity drives a spontaneous breaking of chiral symmetry, leading to the self-assembly of a chiral phase, in the absence of any thermodynamic interactions favoring cholesteric ordering. At high values of activity, we also observe labyrinthine patterns where the activity-induced chiral ordering is highly frustrated.

Circularly Polarized Luminescence from Inorganic Materials: Encapsulating Guest Lanthanide Oxides in Chiral Silica Hosts.

PubMed

Sugimoto, Masumi; Liu, Xin-Ling; Tsunega, Seiji; Nakajima, Erika; Abe, Shunsuke; Nakashima, Takuya; Kawai, Tsuyoshi; Jin, Ren-Hua

2018-05-02

Recently, circularly polarized luminescence (CPL)-active systems have become a very hot and interesting subject in chirality- and optics-related areas. The CPL-active systems are usually available by two approaches: covalently combining a luminescent centre to chiral motif or associating the guest of luminescent probe to a chiral host. However, all the chiral components in CPL materials were organic, although the luminescent components were alternatively organics or inorganics. Herein, the first totally inorganic CPL-active system by "luminescent guest-chiral host" strategy is proposed. Luminescent sub-10 nm lanthanide oxides (Eu 2 O 3 or Tb 2 O 3 ) nanoparticles (guests) were encapsulated into chiral non-helical SiO 2 nanofibres (host) through calcination of chiral SiO 2 hybrid nanofibres, trapping Eu 3+ (or Tb 3+ ). These lanthanide oxides display circular dichroism (CD) optical activity in the ultraviolet wavelength and CPL signals around at 615 nm for Eu 3+ and 545 nm for Tb 3+ . This work has implications for inorganic-based CPL-active systems by incorporation of various luminescent guests within chiral inorganic hosts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorescent Phthalocyanine Assembly Distinguishes Chiral Isomers of Different Types of Amino Acids and Sugars.

PubMed

Jiang, Yuying; Liu, Chenxi; Wang, Xiqian; Wang, Tianyu; Jiang, Jianzhuang

2017-07-25

The functions of some natural supramolecular architectures, such as ribosomes, are dependent on the recognition of different types of chiral biomolecules. However, the recognition of different types of chiral molecules (multiobject chiral recognition), such as amino acids and sugars, by independent and identically artificial supramolecular assembly, was rarely achieved. In this article, simple amphiphilic achiral phthalocyanine was found to form supramolecular chiral assemblies with charged water-soluble polymers upon host-guest interactions at the air/water interface. Among these systems, one identical phthalocyanine/poly(l-lysine) assembly not only can distinguish enantiomers of different amino acids but also can recognize several epimers of monose. The chiral recognitions were achieved by comparing either the steady-state fluorescence intensity or fluorescence quenching rate of phthalocyanine/poly(l-lysine) assemblies, before and after interaction with different small chiral molecules. It was demonstrated that the interactions between poly(l-lysine) and different small chiral molecules could change the aggregation of phthalocyanines. And the sensitivity of fluorescence and the excellent multiobject chiral recognition properties of the phthalocyanine/poly(l-lysine) assembly are dependent on the subtle molecular packing mode and the cooperation of different noncovalent interactions.

Multiaxial Polarity Determines Individual Cellular and Nuclear Chirality

PubMed Central

Raymond, Michael J.; Ray, Poulomi; Kaur, Gurleen; Fredericks, Michael; Singh, Ajay V.; Wan, Leo Q.

2016-01-01

Intrinsic cell chirality has been implicated in the left-right (LR) asymmetry of embryonic development. Impaired cell chirality could lead to severe birth defects in laterality. Previously, we detected cell chirality with an in vitro micropatterning system. Here, we demonstrate for the first time that chirality can be quantified as the coordination of multiaxial polarization of individual cells and nuclei. Using an object labeling, connected component based method, we characterized cell chirality based on cell and nuclear shape polarization and nuclear positioning of each cell in multicellular patterns of epithelial cells. We found that the cells adopted a LR bias the boundaries by positioning the sharp end towards the leading edge and leaving the nucleus at the rear. This behavior is consistent with the directional migration observed previously on the boundary of micropatterns. Although the nucleus is chirally aligned, it is not strongly biased towards or away from the boundary. As the result of the rear positioning of nuclei, the nuclear positioning has an opposite chirality to that of cell alignment. Overall, our results have revealed deep insights of chiral morphogenesis as the coordination of multiaxial polarization at the cellular and subcellular levels. PMID:28360944

Multiaxial Polarity Determines Individual Cellular and Nuclear Chirality.

PubMed

Raymond, Michael J; Ray, Poulomi; Kaur, Gurleen; Fredericks, Michael; Singh, Ajay V; Wan, Leo Q

2017-02-01

Intrinsic cell chirality has been implicated in the left-right (LR) asymmetry of embryonic development. Impaired cell chirality could lead to severe birth defects in laterality. Previously, we detected cell chirality with an in vitro micropatterning system. Here, we demonstrate for the first time that chirality can be quantified as the coordination of multiaxial polarization of individual cells and nuclei. Using an object labeling, connected component based method, we characterized cell chirality based on cell and nuclear shape polarization and nuclear positioning of each cell in multicellular patterns of epithelial cells. We found that the cells adopted a LR bias the boundaries by positioning the sharp end towards the leading edge and leaving the nucleus at the rear. This behavior is consistent with the directional migration observed previously on the boundary of micropatterns. Although the nucleus is chirally aligned, it is not strongly biased towards or away from the boundary. As the result of the rear positioning of nuclei, the nuclear positioning has an opposite chirality to that of cell alignment. Overall, our results have revealed deep insights of chiral morphogenesis as the coordination of multiaxial polarization at the cellular and subcellular levels.

In situ synthesis of di-n-butyl l-tartrate-boric acid complex chiral selector and its application in chiral microemulsion electrokinetic chromatography.

PubMed

Hu, Shaoqiang; Chen, Yonglei; Zhu, Huadong; Zhu, Jinhua; Yan, Na; Chen, Xingguo

2009-11-06

A novel procedure for in situ assembling a complex chiral selector, di-n-butyl l-tartrate-boric acid complex, by the reaction of di-n-butyl l-tartrate with boric acid in a running buffer was reported and its application in the enantioseparation of beta-blockers and structural related compounds by chiral microemulsion electrokinetic chromatography (MEEKC) has been demonstrated. In order to achieve a good enantioseparation, the effect of dibutyl l-tartrate and sodium tetraborate concentration, surfactant identity and concentration, cosurfactant, buffer pH and composition, organic modifiers, as well as applied voltage and capillary length were investigated. Ten pairs of enantiomers that could not be separated with only dibutyl l-tartrate, obtained good chiral separation using the complex chiral selector; among them, seven pairs could be baseline resolved under optimized experimental conditions. The fixation of chiral centers by the formation of five-membered rings, and being oppositely charged with basic analytes were thought to be the key factors giving the complex chiral selector a superior chiral recognition capability. The effect of the molecular structure of analytes on enantioseparation was discussed in terms of molecular interaction.

ENANTIOMERIC OCCURRENCE AND DISTRIBUTION OF CHIRAL ORGANOCHLORINE COMPOUNDS IN U.S. RIVER SEDIMENT AND BIOTA

EPA Science Inventory

River sediment and biota (fish, bivalves) from throughout the continental U.S. were analyzed for chiral organochlorine compounds (o,p'-DDT and DDD, some chlordane compounds, PCB atropisomers) to assess spatial trends in environmental chirality. Chiral PCB enantiomers were racemic...

Corrigendum to "Co-occurrence of linear and circular dichroism in chiral sculptured ZrO2 thin films" [Opt. Mater. 75 (January 2018) 319-324

NASA Astrophysics Data System (ADS)

Muhammad, Zahir; Wali, Faiz; Song, Li

2018-05-01

The authors regret .

Enantiomeric distribution of some linalool containing essential oils and their biological activities

USDA-ARS?s Scientific Manuscript database

The enantiomeric composition of linalool was determined in 42 essential oils using chiral columns. Essential oils were analyzed by multidimentional gas chromatography-mass spectrometry using a non-chiral and chiral FSC column combination with modified '-cyclodextrine (Lipodex E) as the chiral statio...

Anion photoelectron spectroscopy of acid-base systems, solvated molecules and MALDI matrix molecules

NASA Astrophysics Data System (ADS)

Eustis, Soren Newman

Gas phase, mass-selected, anion photoelectron spectroscopic studies were performed on a variety of molecular systems. These studies can be grouped into three main themes: acid-base interactions, solvation, and ions of analytical interest. Acid-base interactions represent some of the most fundamental processes in chemistry. The study of these processes elucidates elementary principles such as inner and outer sphere complexes, hard and soft ions, and salt formation---to name a few. Apart from their appeal from a pedagogical standpoint, the ubiquity of chemical reactions which involve acids, bases or the resulting salts makes the study of their fundamental interactions both necessary and fruitful. With this in mind, the neutral and anionic series (NH3···HX) (X= F, Cl, Br, I) were examined experimentally and theoretically. The relatively small size of these systems, combined with the advances in computational methods, allowed our experimental results to be compared with very high level ab initio theoretical results. The synergy between theory and experiment yielded an understanding of the nature of the complexes that could not be achieved with either method in isolation. The second theme present in this body or work is molecular solvation. Solvation is a phenomenon which is present in biology, chemistry and physics. Many biological molecules do not become 'active' until they are solvated by water. Thus, the study of biologically relevant species solvated by water is one step in a bottom up approach to studying the biochemical interactions in living organisms. Furthermore, the hydration of acidic molecules in the atmosphere is what drives the formation of 'free' protons or hydronium ions which are the key players in acid driven chemistry. Here are presented two unique solvation studies, Adenine(H2O)-n and C6F6(H2O)-n, these systems are very distinct, but show somewhat similar responses to hydration. The last theme presented in this work is the electronic properties of molecules relevant to analytical chemistry, or more specifically, Matrix Assisted Laser Desorption Interaction (MALDI) chemistry. For the first time electron affinities are presented for many of the common MALDI matrix compounds.

Incorporation of Hydrogen Bond Angle Dependency into the Generalized Solvation Free Energy Density Model.

PubMed

Ma, Songling; Hwang, Sungbo; Lee, Sehan; Acree, William E; No, Kyoung Tai

2018-04-23

To describe the physically realistic solvation free energy surface of a molecule in a solvent, a generalized version of the solvation free energy density (G-SFED) calculation method has been developed. In the G-SFED model, the contribution from the hydrogen bond (HB) between a solute and a solvent to the solvation free energy was calculated as the product of the acidity of the donor and the basicity of the acceptor of an HB pair. The acidity and basicity parameters of a solute were derived using the summation of acidities and basicities of the respective acidic and basic functional groups of the solute, and that of the solvent was experimentally determined. Although the contribution of HBs to the solvation free energy could be evenly distributed to grid points on the surface of a molecule, the G-SFED model was still inadequate to describe the angle dependency of the HB of a solute with a polarizable continuum solvent. To overcome this shortcoming of the G-SFED model, the contribution of HBs was formulated using the geometric parameters of the grid points described in the HB coordinate system of the solute. We propose an HB angle dependency incorporated into the G-SFED model, i.e., the G-SFED-HB model, where the angular-dependent acidity and basicity densities are defined and parametrized with experimental data. The G-SFED-HB model was then applied to calculate the solvation free energies of organic molecules in water, various alcohols and ethers, and the log P values of diverse organic molecules, including peptides and a protein. Both the G-SFED model and the G-SFED-HB model reproduced the experimental solvation free energies with similar accuracy, whereas the distributions of the SFED on the molecular surface calculated by the G-SFED and G-SFED-HB models were quite different, especially for molecules having HB donors or acceptors. Since the angle dependency of HBs was included in the G-SFED-HB model, the SFED distribution of the G-SFED-HB model is well described as compared to that of the G-SFED model.

Investigation of efflorescence of inorganic aerosols using fluorescence spectroscopy.

PubMed

Choi, Man Yee; Chan, Chak K

2005-02-17

The phase transition is one of the most fundamental phenomena affecting the physical and chemical properties of atmospheric aerosols. Efflorescence, in particular, is not well understood, partly because the molecular interactions between the solute and water molecules of saturated or supersaturated solution droplets have not been well characterized. Recently, we developed a technique that combines the use of an electrodynamic balance and a fluorescence dye, 8-hydroxyl-1,3,6-pyrenetrisulfonate (pyranine), to study the distributions of solvated and free water in aqueous droplets (Choi, M. Y.; Chan, C. K.; Zhang, Y. H. J. Phys. Chem. A 2004, 108, 1133). We found that the equality of the amounts of solvated and free water is a necessary but not sufficient condition for efflorescence. For efflorescing compounds such as Na2SO4, (NH4)2SO4, and a mixture of NaCl and Na2SO4, the amount of free water decreases, while that of solvated water is roughly constant in bulk measurements and decreases less dramatically than that of free water in single-particle measurements as the relative humidity (RH) decreases. Efflorescence of the supersaturated droplets of these solutions occurs when the amounts of free and solvated water are equal, which is consistent with our previous observation for NaCl. For nonefflorescing compounds in single-particle levitation experiments such as MgSO4 and Mg(NO3)2, the amounts of free and solvated water are equal at a water-to-solute molar ratio of about 6, at which spectral changes due to the formation of contact ion pairs between magnesium and the anions occur as shown by Raman spectroscopy. Fluorescence imaging shows that the droplets of diluted Mg(NO3)2 (at 80% RH) and MgSO4 are homogeneous but those of NaCl, Na2SO4, (NH4)2SO4, and supersaturated Mg(NO3)2 (at 10% RH) are heterogeneous in terms of the solvated-to-free water distribution. The solvated-to-free water ratios in NaCl, Na2SO4, and (NH4)2SO4 droplets are higher in the outer regions by about half a radius deep than at the center of the droplets.

Excited state intramolecular proton transfer reaction of 4'-N,N-diethylamino-3-hydroxyflavone and solvation dynamics in room temperature ionic liquids studied by optical Kerr gate fluorescence measurement.

PubMed

Kimura, Yoshifumi; Fukuda, Masanori; Suda, Kayo; Terazima, Masahide

2010-09-16

Fluorescence dynamics of 4'-N,N-diethylamino-3-hydroxyflavone (DEAHF) and its methoxy derivative (DEAMF) in various room temperature ionic liquids (RTILs) have been studied mainly by an optical Kerr gate method. DEAMF showed a single band fluorescence whose peak shifted with time by the solvation dynamics. The averaged solvation time determined by the fluorescence peak shift was proportional to the viscosity of the solvent except for tetradecyltrihexylphosphonium bis(trifluoromethanesulfonyl)amide. The solvation times were consistent with reported values determined with different probe molecules. DEAHF showed dual fluorescence due to the normal and tautomer forms produced by the excited state intramolecular proton transfer (ESIPT), and the relative intensities were dependent on the time and the solvent cation or anion species. By using the information of the fluorescence spectrum of DEAMF, the fluorescence spectrum of DEAHF at each delay time after the photoexcitation was decomposed into the normal and the tautomer fluorescence components, respectively. The normal component showed a very fast decay simulated by a biexponential function (2-3 and 20-30 ps) with an additional slower decay component. The tautomer component showed a rise with the time constants corresponding to the faster decay of the normal form with an additional instantaneous rise. The faster dynamics of the normal and tautomer population changes were assigned to the ESIPT process, while the slower decay of the fluorescence was attributed to the population decay from the excited state through the radiative and nonradiative processes. The average ESIPT time was much faster than the averaged solvation time of RTILs. Basically, the ESIPT kinetics in RTILs is similar to those in conventional liquid solvents like acetonitrile (Chou et al. J. Phys. Chem. A 2005, 109, 3777). The faster ESIPT is interpreted in terms of the activation barrierless process from the Franck-Condon state before the solvation of the normal state in the electronic excited state. With the advance of the solvation in the excited state, the normal form becomes relatively more stable than the tautomer form, which makes the ESIPT become an activation process.

Magnetic fields and chiral asymmetry in the early hot universe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sydorenko, Maksym; Shtanov, Yuri; Tomalak, Oleksandr, E-mail: maxsydorenko@gmail.com, E-mail: tomalak@uni-mainz.de, E-mail: shtanov@bitp.kiev.ua

In this paper, we study analytically the process of external generation and subsequent free evolution of the lepton chiral asymmetry and helical magnetic fields in the early hot universe. This process is known to be affected by the Abelian anomaly of the electroweak gauge interactions. As a consequence, chiral asymmetry in the fermion distribution generates magnetic fields of non-zero helicity, and vice versa. We take into account the presence of thermal bath, which serves as a seed for the development of instability in magnetic field in the presence of externally generated lepton chiral asymmetry. The developed helical magnetic field andmore » lepton chiral asymmetry support each other, considerably prolonging their mutual existence, in the process of 'inverse cascade' transferring magnetic-field power from small to large spatial scales. For cosmologically interesting initial conditions, the chiral asymmetry and the energy density of helical magnetic field are shown to evolve by scaling laws, effectively depending on a single combined variable. In this case, the late-time asymptotics of the conformal chiral chemical potential reproduces the universal scaling law previously found in the literature for the system under consideration. This regime is terminated at lower temperatures because of scattering of electrons with chirality change, which exponentially washes out chiral asymmetry. We derive an expression for the termination temperature as a function of the chiral asymmetry and energy density of helical magnetic field.« less

Laminar and Turbulent Dynamos in Chiral Magnetohydrodynamics. II. Simulations

NASA Astrophysics Data System (ADS)

Schober, Jennifer; Rogachevskii, Igor; Brandenburg, Axel; Boyarsky, Alexey; Fröhlich, Jürg; Ruchayskiy, Oleg; Kleeorin, Nathan

2018-05-01

Using direct numerical simulations (DNS), we study laminar and turbulent dynamos in chiral magnetohydrodynamics with an extended set of equations that accounts for an additional contribution to the electric current due to the chiral magnetic effect (CME). This quantum phenomenon originates from an asymmetry between left- and right-handed relativistic fermions in the presence of a magnetic field and gives rise to a chiral dynamo. We show that the magnetic field evolution proceeds in three stages: (1) a small-scale chiral dynamo instability, (2) production of chiral magnetically driven turbulence and excitation of a large-scale dynamo instability due to a new chiral effect (α μ effect), and (3) saturation of magnetic helicity and magnetic field growth controlled by a conservation law for the total chirality. The α μ effect becomes dominant at large fluid and magnetic Reynolds numbers and is not related to kinetic helicity. The growth rate of the large-scale magnetic field and its characteristic scale measured in the numerical simulations agree well with theoretical predictions based on mean-field theory. The previously discussed two-stage chiral magnetic scenario did not include stage (2), during which the characteristic scale of magnetic field variations can increase by many orders of magnitude. Based on the findings from numerical simulations, the relevance of the CME and the chiral effects revealed in the relativistic plasma of the early universe and of proto-neutron stars are discussed.

Magnetic fields and chiral asymmetry in the early hot universe

NASA Astrophysics Data System (ADS)

Sydorenko, Maksym; Tomalak, Oleksandr; Shtanov, Yuri

2016-10-01

In this paper, we study analytically the process of external generation and subsequent free evolution of the lepton chiral asymmetry and helical magnetic fields in the early hot universe. This process is known to be affected by the Abelian anomaly of the electroweak gauge interactions. As a consequence, chiral asymmetry in the fermion distribution generates magnetic fields of non-zero helicity, and vice versa. We take into account the presence of thermal bath, which serves as a seed for the development of instability in magnetic field in the presence of externally generated lepton chiral asymmetry. The developed helical magnetic field and lepton chiral asymmetry support each other, considerably prolonging their mutual existence, in the process of `inverse cascade' transferring magnetic-field power from small to large spatial scales. For cosmologically interesting initial conditions, the chiral asymmetry and the energy density of helical magnetic field are shown to evolve by scaling laws, effectively depending on a single combined variable. In this case, the late-time asymptotics of the conformal chiral chemical potential reproduces the universal scaling law previously found in the literature for the system under consideration. This regime is terminated at lower temperatures because of scattering of electrons with chirality change, which exponentially washes out chiral asymmetry. We derive an expression for the termination temperature as a function of the chiral asymmetry and energy density of helical magnetic field.

Chirality in distorted square planar Pd(O,N)2 compounds.

PubMed

Brunner, Henri; Bodensteiner, Michael; Tsuno, Takashi

2013-10-01

Salicylidenimine palladium(II) complexes trans-Pd(O,N)2 adopt step and bowl arrangements. A stereochemical analysis subdivides 52 compounds into 41 step and 11 bowl types. Step complexes with chiral N-substituents and all the bowl complexes induce chiral distortions in the square planar system, resulting in Δ/Λ configuration of the Pd(O,N)2 unit. In complexes with enantiomerically pure N-substituents ligand chirality entails a specific square chirality and only one diastereomer assembles in the lattice. Dimeric Pd(O,N)2 complexes with bridging N-substituents in trans-arrangement are inherently chiral. For dimers different chirality patterns for the Pd(O,N)2 square are observed. The crystals contain racemates of enantiomers. In complex two independent molecules form a tight pair. The (RC) configuration of the ligand induces the same Δ chirality in the Pd(O,N)2 units of both molecules with varying square chirality due to the different crystallographic location of the independent molecules. In complexes and atrop isomerism induces specific configurations in the Pd(O,N)2 bowl systems. The square chirality is largest for complex [(Diop)Rh(PPh3 )Cl)], a catalyst for enantioselective hydrogenation. In the lattice of two diastereomers with the same (RC ,RC) configuration in the ligand Diop but opposite Δ and Λ square configurations co-crystallize, a rare phenomenon in stereochemistry. © 2013 Wiley Periodicals, Inc.

Characterization of an Indole-3-Acetamide Hydrolase from Alcaligenes faecalis subsp. parafaecalis and Its Application in Efficient Preparation of Both Enantiomers of Chiral Building Block 2,3-Dihydro-1,4-Benzodioxin-2-Carboxylic Acid.

PubMed

Mishra, Pradeep; Kaur, Suneet; Sharma, Amar Nath; Jolly, Ravinder S

2016-01-01

Both the enantiomers of 2,3-dihydro-1,4-benzodioxin-2-carboxylic acid are valuable chiral synthons for enantiospecific synthesis of therapeutic agents such as (S)-doxazosin mesylate, WB 4101, MKC 242, 2,3-dihydro-2-hydroxymethyl-1,4-benzodioxin, and N-[2,4-oxo-1,3-thiazolidin-3-yl]-2,3-dihydro-1,4-benzodioxin-2-carboxamide. Pharmaceutical applications require these enantiomers in optically pure form. However, currently available methods suffer from one drawback or other, such as low efficiency, uncommon and not so easily accessible chiral resolving agent and less than optimal enantiomeric purity. Our interest in finding a biocatalyst for efficient production of enantiomerically pure 2,3-dihydro-1,4-benzodioxin-2-carboxylic acid lead us to discover an amidase activity from Alcaligenes faecalis subsp. parafaecalis, which was able to kinetically resolve 2,3-dihydro-1,4-benzodioxin-2-carboxyamide with E value of >200. Thus, at about 50% conversion, (R)-2,3-dihydro-1,4-benzodioxin-2-carboxylic acid was produced in >99% e.e. The remaining amide had (S)-configuration and 99% e.e. The amide and acid were easily separated by aqueous (alkaline)-organic two phase extraction method. The same amidase was able to catalyse, albeit at much lower rate the hydrolysis of (S)-amide to (S)-acid without loss of e.e. The amidase activity was identified as indole-3-acetamide hydrolase (IaaH). IaaH is known to catalyse conversion of indole-3-acetamide (IAM) to indole-3-acetic acid (IAA), which is phytohormone of auxin class and is widespread among plants and bacteria that inhabit plant rhizosphere. IaaH exhibited high activity for 2,3-dihydro-1,4-benzodioxin-2-carboxamide, which was about 65% compared to its natural substrate, indole-3-acetamide. The natural substrate for IaaH indole-3-acetamide shared, at least in part a similar bicyclic structure with 2,3-dihydro-1,4-benzodioxin-2-carboxamide, which may account for high activity of enzyme towards this un-natural substrate. To the best of our knowledge this is the first application of IaaH in production of industrially important molecules.

The chiral magnetic effect and chiral symmetry breaking in SU(3) quenched lattice gauge theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Braguta, V. V., E-mail: braguta@mail.ru; Buividovich, P. V., E-mail: buividovich@itep.ru; Kalaydzhyan, T., E-mail: tigran.kalaydzhyan@desy.de

2012-04-15

We study some properties of the non-Abelian vacuum induced by strong external magnetic field. We perform calculations in the quenched SU(3) lattice gauge theory with tadpole-improved Luescher-Weisz action and chirally invariant lattice Dirac operator. The following results are obtained: The chiral symmetry breaking is enhanced by the magnetic field. The chiral condensate depends on the strength of the applied field as a power function with exponent {nu} = 1.6 {+-} 0.2. There is a paramagnetic polarization of the vacuum. The corresponding susceptibility and other magnetic properties are calculated and compared with the theoretical estimations. There are nonzero local fluctuations ofmore » the chirality and electromagnetic current, which grow with the magnetic field strength. These fluctuations can be a manifestation of the Chiral Magnetic Effect.« less

Spin-Wave Chirality and Its Manifestations in Antiferromagnets

NASA Astrophysics Data System (ADS)

Proskurin, Igor; Stamps, Robert L.; Ovchinnikov, Alexander S.; Kishine, Jun-ichiro

2017-10-01

As first demonstrated by Tang and Cohen in chiral optics, the asymmetry in the rate of electromagnetic energy absorption between left and right enantiomers is determined by an optical chirality density. Here, we demonstrate that this effect can exist in magnetic spin systems. By constructing a formal analogy with electrodynamics, we show that in antiferromagnets with broken chiral symmetry, the asymmetry in local spin-wave energy absorption is proportional to a spin-wave chirality density, which is a direct counterpart of optical zilch. We propose that injection of a pure spin current into an antiferromagnet may serve as a chiral symmetry breaking mechanism, since its effect in the spin-wave approximation can be expressed in terms of additional Lifshitz invariants. We use linear response theory to show that the spin current induces a nonequilibrium spin-wave chirality density.

Stoichiometry-Controlled Inversion of Supramolecular Chirality in Nanostructures Co-assembled with Bipyridines.

PubMed

Wang, Fang; Feng, Chuan-Liang

2018-02-01

To control supramolecular chirality of the co-assembled nanostructures, one of the remaining issues is how stoichiometry of the different molecules involved in co-assembly influence chiral transformation. Through co-assembly of achiral 1,4-bis(pyrid-4-yl)benzene and chiral phenylalanine-glycine derivative hydrogelators, stoichiometry is found to be an effective tool for controlling supramolecular chirality inversion processes. This inversion is mainly mediated by a delicate balance between intermolecular hydrogen bonding interactions and π-π stacking of the two components, which may subtly change the stacking of the molecules, in turn, the self-assembled nanostructures. This study exemplifies a simplistic way to invert the handedness of chiral nanostructures and provide fundamental understanding of the inherent principles of supramolecular chirality. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral Responsive Liquid Quantum Dots.

PubMed

Zhang, Jin; Ma, Junkai; Shi, Fangdan; Tian, Demei; Li, Haibing

2017-08-01

How to convert the weak chiral-interaction into the macroscopic properties of materials remains a huge challenge. Here, this study develops highly fluorescent, selectively chiral-responsive liquid quantum dots (liquid QDs) based on the hydrophobic interaction between the chiral chains and the oleic acid-stabilized QDs, which have been designated as (S)-1810-QDs. The fluorescence spectrum and liquidity of thermal control demonstrate the fluorescence properties and the fluidic behavior of (S)-1810-QDs in the solvent-free state. Especially, (S)-1810-QDs exhibit a highly chiral-selective response toward (1R, 2S)-2-amino-1,2-diphenyl ethanol. It is anticipated that this study will facilitate the construction of smart chiral fluidic sensors. More importantly, (S)-1810-QDs can become an attractive material for chiral separation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of Δ- and λ-isomerism of octahedral metal complexes for inducing chiral nematic phases.

PubMed

Sato, Hisako; Yamagishi, Akihiko

2009-11-20

The Delta- and Lambda-isomerism of octahedral metal complexes is employed as a source of chirality for inducing chiral nematic phases. By applying a wide range of chiral metal complexes as a dopant, it has been found that tris(beta-diketonato)metal(III) complexes exhibit an extremely high value of helical twisting power. The mechanism of induction of the chiral nematic phase is postulated on the basis of a surface chirality model. The strategy for designing an efficient dopant is described, together with the results using a number of examples of Co(III), Cr(III) and Ru(III) complexes with C(2) symmetry. The development of photo-responsive dopants to achieve the photo-induced structural change of liquid crystal by use of photo-isomerization of chiral metal complexes is also described.

Application of Δ- and Λ-Isomerism of Octahedral Metal Complexes for Inducing Chiral Nematic Phases

PubMed Central

Sato, Hisako; Yamagishi, Akihiko

2009-01-01

The Δ- and Λ-isomerism of octahedral metal complexes is employed as a source of chirality for inducing chiral nematic phases. By applying a wide range of chiral metal complexes as a dopant, it has been found that tris(β-diketonato)metal(III) complexes exhibit an extremely high value of helical twisting power. The mechanism of induction of the chiral nematic phase is postulated on the basis of a surface chirality model. The strategy for designing an efficient dopant is described, together with the results using a number of examples of Co(III), Cr(III) and Ru(III) complexes with C2 symmetry. The development of photo-responsive dopants to achieve the photo-induced structural change of liquid crystal by use of photo-isomerization of chiral metal complexes is also described. PMID:20057959

Chirality controlled responsive self-assembled nanotubes in water† †Electronic supplementary information (ESI) available: Detailed experimental procedures and analyses, UV-vis absorption and CD spectroscopy, cryo-TEM and widefield microscopy. See DOI: 10.1039/c6sc02935c Click here for additional data file.

PubMed Central

van Dijken, D. J.; Štacko, P.; Stuart, M. C. A.; Browne, W. R.

2017-01-01

The concept of using chirality to dictate dimensions and to store chiral information in self-assembled nanotubes in a fully controlled manner is presented. We report a photoresponsive amphiphile that co-assembles with its chiral counterpart to form nanotubes and demonstrate how chirality can be used to effect the formation of either micrometer long, achiral nanotubes or shorter (∼300 nm) chiral nanotubes that are bundled. The nature of these assemblies is studied using a variety of spectroscopic and microscopic techniques and it is shown that the tubes can be disassembled with light, thereby allowing the chiral information to be erased. PMID:28451300

Asymmetric synthesis using chiral-encoded metal

NASA Astrophysics Data System (ADS)

Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

2016-08-01

The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity.

Residue length and solvation model dependency of elastinlike polypeptides

NASA Astrophysics Data System (ADS)

Bilsel, Mustafa; Arkin, Handan

2010-05-01

We have performed exhaustive multicanonical Monte Carlo simulations of elastinlike polypeptides with a chain including amino acids (valine-proline-glycine-valine-glycine)n or in short (VPGVG)n , where n changes from 1 to 4, in order to investigate the thermodynamic and structural properties. To predict the characteristic secondary structure motifs of the molecules, Ramachandran plots were prepared and analyzed as well. In these studies, we utilized a realistic model where the interactions between all types of atoms were taken into account. Effects of solvation were also simulated by using an implicit-solvent model with two commonly used solvation parameter sets and compared with the vacuum case.

Quantum chemical approach for condensed-phase thermochemistry (IV): Solubility of gaseous molecules

NASA Astrophysics Data System (ADS)

Ishikawa, Atsushi; Kamata, Masahiro; Nakai, Hiromi

2016-07-01

The harmonic solvation model (HSM) was applied to the solvation of gaseous molecules and compared to a procedure based on the ideal gas model (IGM). Examination of 25 molecules showed that (i) the accuracy of ΔGsolv was similar for both methods, but the HSM shows advantages for calculating ΔHsolv and TΔSsolv; (ii) TΔSsolv contributes more than ΔHsolv to ΔGsolv in the HSM, i.e. the solvation of gaseous molecules is entropy-driven, which agrees well with experimental understanding (the IGM does not show this); (iii) the temperature dependence of Henry's law coefficient was correctly reproduced with the HSM.

Preferential Solvation of Silver (I) Bromate in Methanol-Dimethylsulfoxide Mixtures

NASA Astrophysics Data System (ADS)

Janardhanan, S.; Kalidas, C.

1984-06-01

The solubiltiy of silver bromate, the Gibbs transfer energy of Ag+ and BrO3- and the solvent transport number in methanol-dimethyl sulfoxide mixtures are reported. The solubility of silver bromate increases with addition of DMSO. The Gibbs energy of transfer of the silver ion (based on the ferrocene reference method) decreases, while that of the bromate ion becomes slightly negative with the addition of DMSO. The solvent transport number A passes through a maximum (⊿ = 1.0 at XDMSO = 0.65. From these results, it is concluded that the silver ion is preferentially solvated by DMSO whereas the bromate ion shows no preferential solvation.

Physical transformation of niclosamide solvates in pharmaceutical suspensions determined by DSC and TG analysis.

PubMed

de Villiers, M M; Mahlatji, M D; Malan, S F; van Tonder, E C; Liebenberg, W

2004-07-01

This study reports the preparation of four niclosamide solvates and the determination of the stability of the crystal forms in different suspension vehicles by DSC and TG analysis. Thermal analysis showed that the niclosamide solvates were extremely unstable in a PVP-vehicle and rapidly changed to monohydrated crystals. A suspension in propylene glycol was more stable and TG analysis showed that crystal transformation was less rapid. In this vehicle, the crystals transformed to the anhydrate, rather than the monohydrate, since the vehicle was non-aqueous. The TEG-hemisolvate was the most stable in suspension and offered the best possibility of commercial exploitation.

Synthesis and Monkey-PET Study of (R)- and (S)-18F-Labeled 2-Arylbenzoheterocyclic Derivatives as Amyloid Probes with Distinctive in Vivo Kinetics.

PubMed

Yang, Yanping; Wang, Xuedan; Yang, Hui; Fu, Hualong; Zhang, Jinming; Zhang, Xiaojun; Dai, Jiapei; Zhang, Zhiyong; Lin, Chunping; Guo, Yuzhi; Cui, Mengchao

2016-11-07

This study describes an effective strategy to improve pharmacokinetics of Aβ imaging agents, offering a novel class of (R)- and (S)- 18 F-labeled 2-arylbenzoheterocyclic derivatives which bear an additional chiral hydroxyl group on the side chain. These ligands displayed binding abilities toward Aβ aggregates with K i values ranging from 3.2 to 195.6 nM. Chirality-related discrepancy was observed in biodistribution, and (S)-2-phenylbenzoxazole enantiomers exhibited vastly improved brain clearance with washout ratios higher than 20. Notably, (S)-[ 18 F]28 possessed high binding potency (K i = 7.6 nM) and exceptional brain kinetics (9.46% ID/g at 2 min, brain 2min /brain 60min = 27.8) that is superior to well-established [ 18 F]AV45. The excellent pharmacokinetics and low nonspecific binding of (S)-[ 18 F]28 were testified by dynamic PET/CT scans in monkey brains. In addition, (S)-[ 18 F]28 clearly labeled Aβ plaques both in vitro and ex vivo. These results might qualify (S)-[ 18 F]28 to detect Aβ plaques with high signal-to-noise ratio.

Chiral determination of cinchonine using an electrochemiluminescent sensor with molecularly imprinted membrane on the surfaces of magnetic particles.

PubMed

Yuan, Xingyi; Tan, Yanji; Wei, Xiaoping; Li, Jianping

2017-11-01

A novel molecular imprinting electrochemiluminescence sensor for detecting chiral cinchonine molecules was developed with a molecularly imprinted polymer membrane on the surfaces of magnetic microspheres. Fe 3 O 4 @Au nanoparticles modified with 6-mercapto-beta-cyclodextrin were used as a carrier, cinchonine as a template molecule, methacrylic acid as a functional monomer and N,N'-methylenebisacrylamide as a cross-linking agent. Cinchonine was specifically recognized by the 6-mercapto-beta-cyclodextrin functional molecularly imprinted polymer and detected based on enhancement of the electrochemiluminescence intensity caused by the reaction of tertiary amino structures of cinchonine molecules with Ru(bpy) 3 2+ . Cinchonine concentrations of 1 × 10 -10 to 4 × 10 -7  mol/L showed a good linear relationship with changes of the electrochemiluminescence intensity, and the detection limit of the sensor was 3.13 × 10 -11  mol/L. The sensor has high sensitivity and selectivity, and is easy to renew. It was designed for detecting serum samples, with recovery rates of 98.2% to 107.6%. Copyright © 2017 John Wiley & Sons, Ltd.

Chiral electroweak currents in nuclei

DOE PAGES

Riska, D. O.; Schiavilla, R.

2017-01-10

Here, the development of the chiral dynamics based description of nuclear electroweak currents is reviewed. Gerald E. (Gerry) Brown’s role in basing theoretical nuclear physics on chiral Lagrangians is emphasized. Illustrative examples of the successful description of electroweak observables of light nuclei obtained from chiral effective field theory are presented.

Chiral pesticides: identification, description, and environmental implications.

PubMed

Ulrich, Elin M; Morrison, Candice N; Goldsmith, Michael R; Foreman, William T

2012-01-01

Of the 1,693 pesticides considered in this review, 1,594 are organic chemicals, 47 are inorganic chemicals, 53 are of biological origin (largely non chemical; insect,fungus, bacteria, virus, etc.), and 2 have an undetermined structure. Considering that the EPA's Office of Pesticide Programs found 1,252 pesticide active ingredients(EPA Pesticides Customer Service 2011), we consider this dataset to be comprehensive; however, no direct comparison of the compound lists was undertaken. Of all pesticides reviewed, 482 (28%) are chiral; 30% are chiral when considering only the organic chemical pesticides. A graph of this distribution is shown in Fig. 7a. Each pesticide is classified with up to three pesticidal utilities (e.g., fungicide, plant growth regulator, rodenticide, etc.), taken first from the Pesticide Manual as a primary source, and the Compendium of Common Pesticide Names website as a secondary source. Of the chiral pesticides, 195 (34%) are insecticides (including attractants, pheromones, and repellents), 150 (27%) are herbicides (including plant growth regulators and herbicide safeners), 104 (18%) are fungicides, and 55 (10%)are acaricides. The distribution of chiral pesticides by utility is shown in Fig. 7b,including categories of pesticides that make up 3%t or less of the usage categories.Figure 7c shows a similar distribution of non chiral pesticide usage categories. Of the chiral pesticides, 270 (56%) have one chiral feature, 105 (22%) have two chiral features, 30 (6.2%) have three chiral features, and 29 (6.0%) have ten or more chiral features.Chiral chemicals pose many difficulties in stereospecific synthesis, characterization, and analysis. When these compounds are purposely put into the environment,even more interesting complications arise in tracking, monitoring, and predicting their fate and risks. More than 475 pesticides are chiral, as are other chiral contaminants such as pharmaceuticals, polychlorinated biphenyls, brominated flame retardants, synthetic musks, and their degradates (Kallenborn and Hiihnerfuss 2001;Heeb et al. 2007; Hihnerfuss and Shah 2009). The stereoisomers of pesticides can have widely different efficacy, toxicity to nontarget organisms, and metabolic rates in biota. For these reasons, it is important to first be aware of likely fate and effect differences, to incorporate molecular asymmetry insights into research projects, and to study the individual stereoisomers of the applied pesticide material.With the advent of enantioselective chromatography techniques, the chirality of pesticides has been increasingly studied. While the ChirBase (Advanced ChemistryDevelopment 1997-2010) database does not include all published chiral analytical separations, it does contain more than 3,500 records for 146 of the 482 chiral pesticides (30%). The majority of the records are found in the liquid chromatography database (2,677 or 76%), followed by the gas chromatography database (652 or 18%),and the capillary electrophoresis database (203 or 6%). The finding that only 30% of the chiral pesticides covered in this review have entries in ChirBase highlights the need for expanded efforts to develop additional enantioselective chromatographic methods. Other techniques (e.g., nuclear magnetic resonance and other spectroscopy)are available for investigation of chiral compounds, but often are not utilized because of cost, complexity, or simply not recognizing that a pesticide is chiral.In this review, we have listed and have briefly described the general nature of chiral fungicides, herbicides, insecticides, and other miscellaneous classes. A data-set generated for this review contains 1,693 pesticides, the number of enantioselective separation records in ChirBase, pesticide usage class, SMILES structure string and counts of stereogenic centers. This dataset is publically available for download at the following website: http://www.epa.gov/heasd/products/products.html. With the information herein coupled to the publically accessible dataset, we can begin to develop the tools to handle molecular asymmetry as it applies to agrochemicals.Additional structure-based resources would allow further analysis of key parameters (e.g., exposure, toxicity, environmental fate, degradation, and risks) for individual stereoisomers of chiral compounds.

Predicting solvation free energies and thermodynamics in polar solvents and mixtures using a solvation-layer interface condition

PubMed Central

Goossens, Spencer; Mehdizadeh Rahimi, Ali

2017-01-01

We demonstrate that with two small modifications, the popular dielectric continuum model is capable of predicting, with high accuracy, ion solvation thermodynamics (Gibbs free energies, entropies, and heat capacities) in numerous polar solvents. We are also able to predict ion solvation free energies in water–co-solvent mixtures over available concentration series. The first modification to the classical dielectric Poisson model is a perturbation of the macroscopic dielectric-flux interface condition at the solute–solvent interface: we add a nonlinear function of the local electric field, giving what we have called a solvation-layer interface condition (SLIC). The second modification is including the microscopic interface potential (static potential) in our model. We show that the resulting model exhibits high accuracy without the need for fitting solute atom radii in a state-dependent fashion. Compared to experimental results in nine water–co-solvent mixtures, SLIC predicts transfer free energies to within 2.5 kJ/mol. The co-solvents include both protic and aprotic species, as well as biologically relevant denaturants such as urea and dimethylformamide. Furthermore, our results indicate that the interface potential is essential to reproduce entropies and heat capacities. These and previous tests of the SLIC model indicate that it is a promising dielectric continuum model for accurate predictions in a wide range of conditions.

Nonlinear functional for solvation in Density Functional Theory

NASA Astrophysics Data System (ADS)

Gunceler, Deniz; Sundararaman, Ravishankar; Schwarz, Kathleen; Letchworth-Weaver, Kendra; Arias, T. A.

2013-03-01

Density functional calculations of molecules and surfaces in a liquid can accelerate the development of many technologies ranging from solar energy harvesting to lithium batteries. Such studies require the development of robust functionals describing the liquid. Polarizable continuum models (PCM's) have been applied to some solvated systems; but they do not sufficiently capture solvation effects to describe highly polar systems like surfaces of ionic solids. In this work, we present a nonlinear fluid functional within the framework of Joint Density Functional Theory. The fluid is treated not as a linear dielectric, but as a distribution of dipoles that responds to the solute, which we describe starting from the exact free energy functional for point dipoles. We also show PCM's can be recovered as the linear limit of our functional. Our description is of similar computational cost to PCM's, and captures complex solvation effects like dielectric saturation without requiring new fit parameters. For polar and nonpolar molecules, it achieves millihartree level agreement with experimental solvation energies. Furthermore, our functional now makes it possible to investigate chemistry on the surface of lithium battery materials, which PCM's predict to be unstable. Supported as part of the Energy Materials Center at Cornell, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001086

Applications of the solvation parameter model in reversed-phase liquid chromatography.

PubMed

Poole, Colin F; Lenca, Nicole

2017-02-24

The solvation parameter model is widely used to provide insight into the retention mechanism in reversed-phase liquid chromatography, for column characterization, and in the development of surrogate chromatographic models for biopartitioning processes. The properties of the separation system are described by five system constants representing all possible intermolecular interactions for neutral molecules. The general model can be extended to include ions and enantiomers by adding new descriptors to encode the specific properties of these compounds. System maps provide a comprehensive overview of the separation system as a function of mobile phase composition and/or temperature for method development. The solvation parameter model has been applied to gradient elution separations but here theory and practice suggest a cautious approach since the interpretation of system and compound properties derived from its use are approximate. A growing application of the solvation parameter model in reversed-phase liquid chromatography is the screening of surrogate chromatographic systems for estimating biopartitioning properties. Throughout the discussion of the above topics success as well as known and likely deficiencies of the solvation parameter model are described with an emphasis on the role of the heterogeneous properties of the interphase region on the interpretation and understanding of the general retention mechanism in reversed-phase liquid chromatography for porous chemically bonded sorbents. Copyright © 2016 Elsevier B.V. All rights reserved.

Predicting solvation free energies and thermodynamics in polar solvents and mixtures using a solvation-layer interface condition

NASA Astrophysics Data System (ADS)

Molavi Tabrizi, Amirhossein; Goossens, Spencer; Mehdizadeh Rahimi, Ali; Knepley, Matthew; Bardhan, Jaydeep P.

2017-03-01

We demonstrate that with two small modifications, the popular dielectric continuum model is capable of predicting, with high accuracy, ion solvation thermodynamics (Gibbs free energies, entropies, and heat capacities) in numerous polar solvents. We are also able to predict ion solvation free energies in water-co-solvent mixtures over available concentration series. The first modification to the classical dielectric Poisson model is a perturbation of the macroscopic dielectric-flux interface condition at the solute-solvent interface: we add a nonlinear function of the local electric field, giving what we have called a solvation-layer interface condition (SLIC). The second modification is including the microscopic interface potential (static potential) in our model. We show that the resulting model exhibits high accuracy without the need for fitting solute atom radii in a state-dependent fashion. Compared to experimental results in nine water-co-solvent mixtures, SLIC predicts transfer free energies to within 2.5 kJ/mol. The co-solvents include both protic and aprotic species, as well as biologically relevant denaturants such as urea and dimethylformamide. Furthermore, our results indicate that the interface potential is essential to reproduce entropies and heat capacities. These and previous tests of the SLIC model indicate that it is a promising dielectric continuum model for accurate predictions in a wide range of conditions.

Unraveling Complexity in the Solid Form Screening of a Pharmaceutical Salt: Why so Many Forms? Why so Few?

PubMed Central

2017-01-01

The solid form landscape of 5-HT2a antagonist 3-(4-(benzo[d]isoxazole-3-yl)piperazin-1-yl)-2,2-dimethylpropanoic acid hydrochloride (B5HCl) proved difficult to establish. Many crystalline materials were produced by solid form screening, but few forms readily grew high quality crystals to afford a clear picture or understanding of the solid form landscape. Careful control of crystallization conditions, a range of experimental methods, computational modeling of solvate structures, and crystal structure prediction were required to see potential arrangements of the salt in its crystal forms. Structural diversity in the solid form landscape of B5HCl was apparent in the layer structures for the anhydrate polymorphs (Forms I and II), dihydrate and a family of solvates with alcohols. The alcohol solvates, which provided a distinct packing from the neat forms and the dihydrate, form layers with conserved hydrogen bonding between B5HCl and the solvent, as well as stacking of the aromatic rings. The ability of the alcohol hydrocarbon moieties to efficiently pack between the layers accounted for the difficulty in growing some solvate crystals and the inability of other solvates to crystallize altogether. Through a combination of experiment and computation, the crystallization problems, form stability, and desolvation pathways of B5HCl have been rationalized at a molecular level. PMID:29018305

Ab initio molecular dynamics of solvation effects on reactivity at electrified interfaces

DOE PAGES

Herron, Jeffrey A.; Morikawa, Yoshitada; Mavrikakis, Manos

2016-08-08

Using ab initio molecular dynamics (as implemented in periodic, self-consistent (GGA-PBE) density functional theory (DFT) we investigated the mechanism of methanol electro-oxidation on Pt(111). We investigated the role of solvation and electrode potential on the energetics of the first proton transfer step, methanol electro-oxidation to methoxy (CH 3O) or hydroxymethyl (CH 2OH). The results show that solvation weakens the adsorption of methoxy to uncharged Pt(111), while the binding energy of methanol and hydroxymethyl are not significantly affected. The free energies of activation for breaking the C-H and O-H bonds in methanol were calculated through a Blue Moon Ensemble using constrainedmore » ab initio molecular dynamics. Calculated barriers for these elementary steps on unsolvated, uncharged Pt(111) are similar to results for climbing-image nudged elastic band calculations from the literature. Solvation reduces the barrier for both C-H and O-H bond activation steps with respect to their vapor phase values, though the effect is more pronounced for C-H bond activation due to less disruption of the hydrogen-bond network. The calculated activation energy barriers show that breaking the C-H bond of methanol is more facile than the O-H bond on solvated negatively biased, or uncharged Pt(111). Furthermore, with positive bias, O-H bond activation is enhanced, becoming slightly more facile than C-H bond activation.« less

A novel aggregation-induced emission enhancement triggered by the assembly of a chiral gelator: from non-emissive nanofibers to emissive micro-loops.

PubMed

Chen, Wenrui; Qing, Guangyan; Sun, Taolei

2016-12-22

In this study, a novel aggregation-induced emission (AIE) enhancement triggered by the self-assembly of chiral gelator is described. Tuning of molecular chirality in situ triggers different assemblies of superstructures exhibiting fluorescence. This novel AIE material can constitute an emerging library of chiral supramolecules for turn-on fluorescent sensors. It will also help in better understanding the effects of chiral factors on the photophysical process.

Construction of axial chirality by rhodium-catalyzed asymmetric dehydrogenative Heck coupling of biaryl compounds with alkenes.

PubMed

Zheng, Jun; You, Shu-Li

2014-11-24

Enantioselective construction of axially chiral biaryls by direct C-H bond functionalization reactions has been realized. Novel axially chiral biaryls were synthesized by the direct C-H bond olefination of biaryl compounds, using a chiral [Cp*Rh(III)] catalyst, in good to excellent yields and enantioselectivities. The obtained axially chiral biaryls were found as suitable ligands for rhodium-catalyzed asymmetric conjugate additions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterizing optical chirality

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bliokh, Konstantin Y.; Advanced Science Institute, RIKEN, Wako-shi, Saitama 351-0198; Nori, Franco

We examine the recently introduced measure of chirality of a monochromatic optical field [Y. Tang and A. E. Cohen, Phys. Rev. Lett. 104, 163901 (2010)] using the momentum (plane-wave) representation and helicity basis. Our analysis clarifies the physical meaning of the measure of chirality and unveils its close relation to the polarization helicity, spin angular momentum, energy density, and Poynting energy flow. We derive the operators of the optical chirality and of the corresponding chiral momentum, which acquire remarkably simple forms in the helicity representation.

Search for evidence of life in space: analysis of enantiomeric organic molecules by N,N-dimethylformamide dimethylacetal derivative dependant Gas Chromatography-Mass Spectrometry.

PubMed

Freissinet, C; Buch, A; Sternberg, R; Szopa, C; Geffroy-Rodier, C; Jelinek, C; Stambouli, M

2010-01-29

Within the context of the future space missions to Mars (MSL 2011 and Exomars 2016), which aim at searching for traces of life at the surface, the detection and quantitation of enantiomeric organic molecules is of major importance. In this work, we have developed and optimized a method to derivatize and analyze chiral organic molecules suitable for space experiments, using N,N-dimethylformamide dimethylacetal (DMF-DMA) as the derivatization agent. The temperature, duration of the derivatization reaction, and chromatographic separation parameters have been optimized to meet instrument design constraints imposed upon space experiment devices. This work demonstrates that, in addition to its intrinsic qualities, such as production of light-weight derivatives and a great resistance to drastic operating conditions, DMF-DMA facilitates simple and fast derivatization of organic compounds (three minutes at 140 degrees C in a single-step) that is suitable for an in situ analysis in space. By using DMF-DMA as the derivatization agent, we have successfully identified 19 of the 20 proteinic amino acids and been able to enantiomerically separate ten of the potential 19 (glycine being non-chiral). Additionally, we have minimized the percentage of racemized amino acid compounds produced by optimizing the conditions of the derivatization reaction itself. Quantitative linearity studies and the determination of the limit of detection show that the proposed method is also suitable for the quantitative determination of both enantiomeric forms of most of the tested amino acids, as limits of detection obtained are lower than the ppb level of organic molecules already detected in Martian meteorites. Copyright (c) 2009 Elsevier B.V. All rights reserved.

Theory of magnetoelastic resonance in a monoaxial chiral helimagnet

NASA Astrophysics Data System (ADS)

Tereshchenko, A. A.; Ovchinnikov, A. S.; Proskurin, Igor; Sinitsyn, E. V.; Kishine, Jun-ichiro

2018-05-01

We study magnetoelastic resonance phenomena in a monoaxial chiral helimagnet belonging to the hexagonal crystal class. By computing the spectrum of a coupled elastic wave and spin wave, it is demonstrated how hybridization occurs depending on their chirality. Specific features of the magnetoelastic resonance are discussed for the conical phase and the soliton lattice phase stabilized in the monoaxial chiral helimagnet. The former phase exhibits appreciable nonreciprocity of the spectrum, and the latter is characterized by a multiresonance behavior. We propose that the nonreciprocal spin wave around the forced-ferromagnetic state has potential capability to convert the linearly polarized elastic wave to a circularly polarized one with the chirality opposite to the spin-wave chirality.

Asymmetric Michael Addition Mediated by Chiral Ionic Liquids

PubMed Central

Suzuki, Yumiko

2018-01-01

Chiral ionic liquids with a focus on their applications in asymmetric Michael additions and related reactions were reviewed. The examples were classified on the basis of the mode of asymmetric induction (e.g., external induction/non-covalent interaction or internal induction/covalent bond formation), the roles in reactions (as a solvent or catalyst), and their structural features (e.g., imidazolium-based chiral cations, other chiral oniums; proline derivatives). Most of the reactions with high chiral induction are Michael addition of ketones or aldehydes to chalcones or nitrostyrenes where proline-derived chiral ionic liquids catalyze the reaction through enamine/ iminium formation. Many reports demonstrate the recyclability of ionic liquid-tagged pyrrolidines. PMID:29861702

A complex-polarization-propagator protocol for magneto-chiral axial dichroism and birefringence dispersion.

PubMed

Cukras, Janusz; Kauczor, Joanna; Norman, Patrick; Rizzo, Antonio; Rikken, Geert L J A; Coriani, Sonia

2016-05-21

A computational protocol for magneto-chiral dichroism and magneto-chiral birefringence dispersion is presented within the framework of damped response theory, also known as complex polarization propagator theory, at the level of time-dependent Hartree-Fock and time-dependent density functional theory. Magneto-chiral dichroism and magneto-chiral birefringence spectra in the (resonant) frequency region below the first ionization threshold of R-methyloxirane and l-alanine are presented and compared with the corresponding results obtained for both the electronic circular dichroism and the magnetic circular dichroism. The additional information content yielded by the magneto-chiral phenomena, as well as their potential experimental detectability for the selected species, is discussed.