Their Application (their + application)

Distribution by Scientific Domains
Distribution within Chemistry

Selected Abstracts

Grammatical Inference Techniques and Their Application in Ground Investigation

Ian Morrey
The data obtained from trial pits can be coded into a form that can be used as sample observations for input to a grammatical inference machine. A grammatical inference machine is a black box, which when presented with a sample of observations of some unknown source language, produces a grammar which is compatible with the sample. This article presents a heuristic model for a grammatical inference machine, which takes as data sentences and non-sentences identified as such, and is capable of inferring grammars in the class of context-free grammars expressed in Chomsky Normal Form. An algorithm and its corresponding software implementation have been developed based on this model. The software takes, as input, coded representations of ground investigation data, and produces as output a grammar which describes and classifies the geotechnical data observed in the area, and also promises the possibility of being able to predict the likely configuration of strata across the site. [source]

Microporous Silica Hollow Microspheres and Hollow Worm-Like Materials: A Simple Method for Their Synthesis and Their Application in Controlled Release

Mingwei Zhao
Abstract Hollow silica microspheres and hollow worm-like materials were synthesized by using a simple method with the aid of 1-dodecyl-3-methylimidazolium bromide (C12mimBr). Hollow silica microspheres were initially produced by utilizing the combination of evaporation and an emulsion template. At a longer mixing time, the microspheres fused to form hollow worm-like silica materials due to the fusion of the emulsion templates. The resultant silica materials were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and nitrogen adsorption/desorption. Both the hollow silica microspheres and the hollow worm-like materials are microporous. On the basis of experimental observations and the resulting products, a plausible formation mechanism is proposed. Preliminary tests demonstrate that the hollow silica microspheres and worm-like materials are capable of being loaded with Rhodamine B and releasing it, thus showing a great potential in controlled delivery applications. [source]

Mono(aryloxido)Titanium(IV) Complexes and Their Application in the Selective Dimerization of Ethylene

Jean-Benoit Cazaux
Abstract We report on the synthesis of mono(aryloxido)titanium(IV) complexes of general formula {Ti[O(o -R)Ar]X3}, with X = OiPr, ArO = 2- tert -butyl-4-methylphenoxy and R = CMe3 (2a), CMe2Ph (2b) and CH2NMe2 (2c). Attempts to reach pure mono(aryloxido) complexes when R = CH2NMe(CH2Ph) (2d) or CH2N(CH2Ph)2 (2e) were unsuccessful. When R = CH2OMe, the analogous mononuclear complex was not obtained, and instead, a dinuclear complex [(2- tert -butyl-4-methyl-6-methoxymethylphenoxy) TiCl(OiPr)(,2 -OiPr)2TiCl(OiPr)2] (3) was formed. Complexes 2b and 3 were characterized by single-crystal X-ray diffraction. The former contains a tetrahedrally coordinated TiIV centre, whereas in the latter the aryloxido ligand behaves as a chelating,bridging ligand between the two, chemically very different metal centres that form two face-sharing octahedra. Different synthetic approaches starting from [Ti(OiPr)4] or [TiCl(OiPr)3] were evaluated and are discussed. The hemilabile behaviour of the aryloxido ligand resulting from reversible coordination of its side arm was studied by variable-temperature 1H NMR spectroscopy for 2c (R = CH2NMe2). Complexes 2a,d were contacted with ethylene and AlEt3 as cocatalyst. When activated with AlEt3 (3 equiv.) at 20 bar and 60 °C, complex 2c exhibits interesting activity (2100 g/gTi/h) for the selective dimerization of ethylene to 1-butene (92,% C4=; 99+% C4=1). Noticeable differences in catalyst activity were observed when the R group was modified. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

[Bis(guanidine)]zinc Complexes and Their Application in Lactide Polymerisation

Janna Börner
Abstract The bis(guanidine)-stabilised zinc complexes [N1,N2 -bis(1,3-dimethylimidazolidin-2-ylidene)ethane-1,2-diamine]dichloridozinc(II), [Zn(DMEG2e)Cl2] (C1), diacetato[N1,N2 -bis(1,3-dimethylimidazolidin-2-ylidene)ethane-1,2-diamine]zinc(II),[Zn(DMEG2e)(CH3COO)2] (C2), and bis[N1,N2 -bis(1,3-dimethylimidazolidin-2-ylidene)ethane-1,2-diamine]zinc(II) bis(trifluoromethanesulfonate), [Zn(DMEG2e)2](CF3SO3)2 (C3), have been synthesised and completely characterised by means of X-ray structure analysis, NMR spectroscopy and mass spectrometry. These [bis(guanidine)]zinc complexes were investigated regarding their activity in the bulk polymerisation of D,L -lactide. It could be shown that these compounds are able to act as initiators for lactide polymerisation, and polylactides with molecular weights (Mw) of around 18000,59000 g/mol could be obtained. Variation of the reaction temperature revealed that the molecular weights decrease with increasing temperature. Additionally, the correlation of the intrinsic viscosity with the molecular weight demonstrates that the obtained polymers are linear and structurally homogeneous.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

Synthesis of Binaphthyl Sulfonimides and Their Application in the Enantioselective Michael Addition of Ketones to Nitroalkenes

Shurong Ban
Abstract Novel types of L -proline-based binaphthyl sulfonimides and sulfonamides were found to be efficient organocatalysts for the asymmetric Michael addition of ketones to nitroalkenes to provide optically active ,-nitroketone derivatives of synthetic and biological importance. After the fine optimization of solvents, temperature, and additive, good to excellent enantioselectivities and diastereoselectivities (71,96,%,ee, up to >99:1,dr) can be achieved. [source]

Synthesis of an Inherently Chiral Calix[4]arene Amino Acid and Its Derivatives: Their Application to Asymmetric Reactions as Organocatalysts

Seiji Shirakawa
Abstract The synthesis of an inherently chiral calix[4]arene amino acid as a chiral building block has been achieved in order for subsequent transformation to various types of inherently chiral calix[4]arenes. The optically pure, inherently chiral calix[4]arene amino acids were prepared by the separation of a diastereomeric mixture of calix[4]arene amino acid derivatives bearing a (R)-BINOL moiety. The separated optically pure calix[4]arene amino acid derivatives with a (R)-BINOL moiety were easily transformed to novel inherently chiral calix[4]arenes containing an amino alcohol structure or a quaternary ammonium moiety. These optically pure chiral calix[4]arenes were applied to asymmetric reactions as organocatalysts.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Preparation of Chiral Homoannularly Bridged N,P-Ferrocenyl Ligands by Intramolecular Coupling of 1,5-Dilithioferrocenes and Their Application in Asymmetric Allylic Substitution Reactions,

Shin-ichi Fukuzawa
Abstract Homoannularly bridged ferrocene 6b was prepared by intramolecular coupling of 1,5-dilithioferrocene 5b mediated by Fe(acac)3. Dilithioferrocene 5b was prepared by lithium,halogen exchange of the corresponding diiodide, which was prepared by 1,5-dilithiation of the o -TMS-blocked ferrocene and followed by trapping with iodine and removal of the TMS group. Alternatively, 5b could be readily prepared by the reaction of o -bromophenylferrocene 8 with nBuLi (>2 equiv.). The benzene ring of 6b underwent ortho lithiation with tBuLi, and the resulting lithiated species was trapped with Ph2PCl to produce corresponding aminophosphane 7d. Aminophosphane 13, which has the phosphanyl group on the cyclopentadienyl ring, was prepared by intramolecular coupling of 1,5-dilithiated PhPPFA 11 mediated by Fe(acac)3. New N,P ligands 7d and 13 were used in the palladium-catalyzed allylic alkylation and amination of 1,3-diphenyl-2-propenyl acetate (14), and ligand 7d was found to give good yields with enantioselectivities as high as 96,% ee. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]

A Modular Approach to a New Class of Monodentate Chiral Phosphorus Ligands and Their Application in Enantioselective Copper-Catalysed Conjugate Additions of Diethylzinc to Cyclohexenone

Chiara Monti
Abstract A new family of chiral phosphorus ligands (5) for use in enantioselective catalysis have been synthesised. The ligands contain the electron-poor bis(sulfonyl)diazaphospholidine moiety and possess a highly modular structure which is well suited to the synthesis of a library. A small library (23 members) of ligands 5 was prepared and tested in the enantioselective copper-catalysed conjugate addition of diethylzinc to cyclohexenone. Complete conversions were obtained with enantiomeric excesses (ee) of up to 75%. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]

Biotemplated Synthesis of Gold Nanoparticle,Bacteria Cellulose Nanofiber Nanocomposites and Their Application in Biosensing

Taiji Zhang
Abstract Bacteria cellulose (BC) nanofibers are used as robust biotemplates for the facile fabrication of novel gold nanoparticle (NP),bacteria cellulose nanofiber (Au,BC) nanocomposites via a one-step method. The BC nanofibers are uniformly coated with Au NPs in aqueous suspension using poly(ethyleneimine) (PEI) as the reducing and linking agent. With the addition of different halides, Au,BC nanocomposites with different Au shell thicknesses are formed, and a possible formation mechanism is proposed by taking into account the special role played by PEI. A novel H2O2 biosensor is constructed using the obtained Au,BC nanocomposites as excellent support for horseradish peroxidase (HRP) immobilization, which allows the detection of H2O2 with a detection limit lower than 1,µM. The Au,BC nanocomposites could be further used for the immobilization of many other enzymes, and thus, may find potential applications in bioelectroanalysis and bioelectrocatalysis. [source]

[Ru(0)]@SiO2 and [RuO2]@SiO2 Hybrid Nanomaterials: From Their Synthesis to Their Application as Catalytic Filters for Gas Sensors

Victor Matsura
Abstract [Ru(0)]@SiO2 and [RuO2]@SiO2 hybrid nanomaterials are produced following a facile method consisting of the synthesis of size-controlled ruthenium nanoparticles as elemental bricks. This route takes advantage of the organometallic approach and the use of a bifunctional ligand for the synthesis of ruthenium nanoparticles from [Ru(COD)(COT)](COD,=,1,3-cyclooctadiene, COT,=,1,3,5-cyclooctatriene) as metal precursor and (PhCH2)2N(CH2)11O(CH2)3Si(OEt)3 (benzenemethanamine) as stabilizer. Hydrolysis and polycondensation steps via a sol,gel approach lead to the formation of the silica materials containing the metal nanoparticles. A final calcination step in air at 400,°C yields the [RuO2]@SiO2 nanocomposites. Such hybrid nanomaterials display a good dispersion of the nanoparticles inside the silica matrix and interesting porosity properties making them attractive materials for catalytic applications. This is shown by using [RuO2]@SiO2 hybrid nanomaterials as catalytic filters for gas sensors. [source]

Large-Scale Synthesis of Long Crystalline Cu2-xSe Nanowire Bundles by Water-Evaporation-Induced Self-Assembly and Their Application in Gas Sensing

Jun Xu
Abstract By a facile water evaporation process without adding any directing agent, Cu2-xSe nanowire bundles with diameters of 100,300,nm and lengths up to hundreds of micrometers, which comprise crystalline nanowires with diameters of 5,8,nm, are obtained. Experiments reveal the initial formation/stacking of CuSe nanoplates and the subsequent transformation to the Cu2-xSe nanowire bundles. A water-evaporation-induced self-assembly (WEISA) mechanism is proposed, which highlights the driving force of evaporation in promoting the nanoplate stacking, CuSe-to-Cu2-xSe transformation and the growth/bundling of the Cu2-xSe nanowires. The simplicity, benignancy, scalability, and high-yield of the synthesis of this important nanowire material herald its numerous applications. As one example, the use of the Cu2-xSe nanowire bundles as a photoluminescence-type sensor of humidity is demonstrated, which shows good sensitivity, ideal linearity, quick response/recovery and long lifetime in a very wide humidity range at room temperature. [source]

Reactive Template Method to Synthesize Gold Nanoparticles with Controllable Size and Morphology Supported on Shells of Polymer Hollow Microspheres and Their Application for Aerobic Alcohol Oxidation in Water

Jie Han
Abstract A novel method has been developed to synthesize gold nanoparticles with tunable size and morphology supported on both inner and outer surfaces of poly(o -phenylenediamine) (PoPD) hollow microspheres, which act as both reductant and template/stabilizer. The size of gold nanoparticles supported on shells of PoPD hollow microspheres can be tuned from 3 to 15,nm by changing the concentration of the gold source, HAuCl4. Gold nanorods supported on shells of PoPD hollow microspheres can also be fabricated by introducing a well-known seed-growth strategy. In addition, silver nanoparticles supported on shells of PoPD hollow microspheres can also be successfully fabricated using the same strategy, which indicates the diversity of this proposed method for polymer hollow microspheres supporting noble metal nanoparticles. The products are characterized by X-ray diffraction and contact angle analysis. Furthermore, the catalytic activity of the obtained PoPD-microsphere-supported gold nanoparticles for aerobic alcohol oxidation is investigated. The results demonstrate that such polymer-supported gold nanoparticles can be used as reusable catalysts with high catalytic activity for aerobic alcohol oxidation in water. [source]

Luminescence Properties of Aminobenzanthrones and Their Application as Host Emitters in Organic Light-Emitting Devices,

M.-X. Yu
Abstract A series of aminobenzanthrone derivatives, possessing a keto and an amino group on the aromatic ring, are synthesized and their photoluminescence (PL) and electroluminescence (EL) properties are studied in detail. These compounds emit strongly in solution and in the solid state, with the emission maxima in the range of 528,668,nm resulting from charge-transfer transitions from the amino group to the keto moiety. The emission wavelength depends greatly on the polarity of the solvent. A red shift of nearly 100,nm is observed from n -hexane to dichloromethane for each of these compounds. The PL quantum yields of these molecules also depend tremendously on the solvent. The values are between 88 and 70,% in n- hexane and decrease as the polarity of the solvent increases. The single-crystal X-ray diffraction data reveal that the aminobenzanthrone planes of these molecules stack in the crystals in an antiparallel head-to-tail fashion. This strong dipole,dipole interaction accounts for the observed red-shifted emissions of the aminobenzanthrone molecules in powders and in films relative to those in nonpolar solvents. Electroluminescent devices using aminobenzanthrone derivatives as the host emitters or dopants emit orange to red light in the range 590,645,nm. High brightness, current efficiency, and power efficiency are observed for some of these devices. For example, the device using N -(4- t -butylphenyl)- N -biphenyl-3-benzanthronylamine as the emitter gives saturated red light with a current efficiency of 1.82,cd,A,1, brightness of 11,253,cd,m,2, and Commission Internationale de l'Éclairage (CIE) coordinates of (0.64,0.36); the device using N -(2-naphthyl)- N -phenyl-3-benzanthronylamine as the emitter gives orange,red light with a current efficiency of 3.52,cd,A,1, brightness of 25,000,cd,m,2, and CIE coordinates of (0.61,0.38). [source]

Synthesis of Indium and Indium Oxide Nanoparticles from Indium Cyclopentadienyl Precursor and Their Application for Gas Sensing,

K. Soulantica
Abstract Decomposition of the organometallic precursor [In(,5 -C5H5)] in toluene in the presence of methanol (8 vol.-%) at room temperature leads to the immediate formation of aggregates of indium nanoparticles of 15,±,2 nm mean diameter. The aggregates are roughly spherical with a mean size of 400,±,40 nm. The particles were characterized by means of transmission electron and high-resolution transmission electron microscopies (TEM and HRTEM), and X-ray diffraction (XRD) studies indicate that the powder consists of the tetragonal phase of indium. The thermal oxidation in air of these nanoparticles yields well-crystallized nanoparticles of In2O3 with unchanged morphology (aggregates of nanoparticles of 16.6,±,2 nm mean diameter with aggregate mean size of 400,±,40 nm) and without any sign of coalescence. XRD pattern shows that the powder consists of the cubic phase of In2O3. The electrical conductivity measurements demonstrate that this material is highly sensitive to an oxidizing gas such as nitrogen dioxide and barely sensitive to a reducing gas such as carbon monoxide. Its association with SnO2 -based sensors allows the selective detection of carbon monoxide (30 ppm) and sub-ppm amounts of nitrogen dioxide (400 ppb) in a mixture at 21,°C and at a relative humidity of 60,%. [source]

Preparation of Metallic Films on Elastomeric Stamps and Their Application for Contact Processing and Contact Printing,

H. Schmid
Abstract The formation of permanent or reversible metallic patterns on a substrate has applications in microfabrication and analytical techniques. Here, we investigate how to metallize an elastomeric stamp, either for processing of a substrate mediated by the proximity between the metal on the stamp and an active layer on the substrate, or for contact printing of the metal from a stamp to a substrate. The stamps were made from poly(dimethylsiloxane) (PDMS) and were modified before metallizing them with Au by adding to or removing from their bulk mobile silicone residues, by oxidizing their surface with an O2 -plasma, by surface-fluorination via silanization, or by priming them with a Ti layer. The interplay between the adhesion of the different layers defines two categories of application: contact processing and contact printing. Contact processing corresponds to keeping the metal on the stamp after contacting a substrate; it is reversible and nondestructive, and useful to define transient electrical contacts or quench fluorescence on a surface, for example. Contact printing occurs when the metal on the stamp adheres to the printed surface. Contact printing can transfer a metal, layers of metals, or an oxide onto a substrate with submicrometer lateral resolution. The transfer can be total or localized to the regions of contact, depending on the morphology of the metal on the stamp and/or the surface chemistry of the substrate. [source]

Coaxial Metal Nano-/Microcables with Isolating Sheath: Synthetic Methodology and Their Application as Interconnects

Min-Rui Gao
Abstract Synthesis of coaxial nano-/microcables has been an intensive research subject due to their heterogeneous structures, tuneable properties, and important applications in nano-/micrometer-scale electronic and optoelectronic devices. Research on the fabrication of nanocables via solution strategies has made great progress in the past few years. In this Research News article, rapidly emerging new solution strategies such as hydrothermal carbonization (HTC) and synergistic soft,hard templates (SSHTs) are highlighted. Unique and flexible coaxial nano-/microcables synthesized by those methods have obvious advantages such as long-term stability and their electrical transport properties, compared with bare counterparts, suggesting that they are potential candidates as interconnects in the future. [source]

Electrocatalysts: Facile Construction of Pt,Co/CNx Nanotube Electrocatalysts and Their Application to the Oxygen Reduction Reaction (Adv. Mater.

Pt,Co alloyed nanoparticles can be facilely immobilized onto CNx nanotubes due to the incorporated nitrogen, report Yanwen Ma, Zheng Hu, and co-workers on p. 4953. The as-prepared electrocatalysts exhibit good performance for oxygen reduction reactions in acidic media arising from the high dispersion and alloying effect of Pt,Co nanoparticles, as well as the intrinsic catalytic capacity of CNx nanotubes, which is significant for the development of fuel cells. [source]

Facile Construction of Pt,Co/CNx Nanotube Electrocatalysts and Their Application to the Oxygen Reduction Reaction

Shujuan Jiang
A straight forward method for immobilizing Pt,Co alloyed nanoparticles onto nitrogen-doped CNx nanotubes is presented (see image). The as-prepared electrocatalysts exhibit good performance for oxygen reduction reaction in acidic medium arising from the high-dispersion and alloying effect of the Pt,Co nanoparticles and the intrinsic catalytic capacity of the CNx nanotubes. [source]

Characterization of Quantum Dot/Conducting Polymer Hybrid Films and Their Application to Light-Emitting Diodes

Jeonghun Kwak
Quantum dot/conducting polymer hybrid films are used to prepare light-emitting diodes (LEDs). The hybrid films (CdSe@ZnS quantum dots excellently dispersed in a conducting polymer matrix, see figure) are readily prepared by various solution-based processes and are also easily micropatterned. The LEDs exhibit a turn-on voltage of 4,V, an external quantum efficiency greater than 1.5%, and almost pure-green quantum-dot electroluminescence. [source]

Thermally Activated Delayed Fluorescence from Sn4+,Porphyrin Complexes and Their Application to Organic Light Emitting Diodes , A Novel Mechanism for Electroluminescence

Ayataka Endo
Electroluminescence based on TADF, that is, thermally activated delayed fluorescence, is demonstrated in Sn4+,porphyrin complexes. On excitation by a short electrical pulse, prompt and delayed electroluminescence components were clearly observed. The delayed component was composed of both TADF and phosphorescence (see figure), and the TADF component significantly increased with increasing temperature. [source]

Micrometer- and Nanometer-Sized, Single-Crystalline Ribbons of a Cyclic Triphenylamine Dimer and Their Application in Organic Transistors

Rongjin Li
A cyclic triphenylamine dimer with high crystallinity is demonstrated. Micrometer- and nanometer-sized single-crystalline ribbons are easily produced by a physical vapor transport technique. Field-effect transistors of the ribbons exhibit mobilities up to 0.05,cm2 V,1 s,1. The mobility of the devices depends greatly on the size of the ribbons: the smaller the ribbons, the higher the mobility. [source]

Controlled Preparation of MnO2 Hierarchical Hollow Nanostructures and Their Application in Water Treatment,

B. Fei
Hierarchical hollow manganese dioxide nanosheets with intricate and well-controlled 3D morphologies are synthesized by combining the Kirkendall effect with a sacrificial crystalline template. The as-prepared MnO2 nanomaterials (see figure) exhibit a good absorbing ability, useful in the removal of organic pollutants from waste water. [source]

Fabrication of Highly Conductive Poly(3,4-ethylenedioxythiophene) Films by Vapor Phase Polymerization and Their Application in Efficient Organic Light-Emitting Diodes,

A. Levermore
Flexible polymer light-emitting diodes (see photo) are fabricated using highly conductive vapor-phase polymerized poly(3,4-ethylenedioxythiophene) (VPP,PEDOT) as an anode material. The influence of the VPP,PEDOT film thickness and the effects of thermal annealing and oxygen-plasma treatment on conductivity, work function, and optical transmission are explored and used to optimize device performance, resulting ultimately in devices that have efficiencies comparable to those with indium tin oxide anodes. [source]

Silicone Nanofilaments and Their Application as Superhydrophobic Coatings,


Silicone nanofilaments (see figure) are grown by a simple chemical vapor deposition method on different substrate materials. The filaments are flexible, and have lengths of up to several micrometers and diameters of up to 150,nm. The dense and entangled arrangement of these filaments yields a superhydrophobic coating that is also optically transparent and antireflective. [source]

Macroscopic Fibers of Oriented Vanadium Oxide Ribbons and Their Application as Highly Sensitive Alcohol Microsensors,

L. Biette
Vanadium oxide macroscopic fibers (see Figure) are obtained by an extrusion process. The fibers consist of nanoscopic ribbons with a preferential orientation and a longitudinal Young's modulus of around 15,GPa. As well as showing high sensitivity, the fibers reversibly cycle between insulating and semiconducting upon exposure to alcohol vapor sources, with signature responses to different alcohols. [source]

Formation of Europium Chelate Complexes by Vacuum Co-Deposition and Their Application in Organic Light-Emitting Diodes,

T. Oyamada
A unique method of material synthesis based on vacuum co-deposition is reported. A Eu complex was formed by co-deposition of bis(dipivaloymethanato)europium (Eu(DPM)3) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), which both showed excellent volatility during vacuum deposition. Photoexcitation of the BCP led to intense emission from the Eu3+ ions, verifying efficient exciton energy transfer and therefore complex formation. [source]

Fabrication of Reversely Tapered Three-Dimensional Structures and Their Application to Organic Light-Emitting Diodes

J. Rhee
Cathode separators typically used for patterning metal cathodes of organic light-emitting diodes (OLEDs),see Figure,can be fabricated using a lithography-based technique that allows the construction of reversely tapered 3D structures in one single molding step. The physics involved in making the fabrication of such 3D structures possible is outlined and the efficacy of the separator thus fabricated is demonstrated with an OLED. [source]

Development of Diphenylamine-Linked Bis(imidazoline) Ligands and Their Application in Asymmetric Friedel,Crafts Alkylation of Indole Derivatives with Nitroalkenes

Han Liu
Abstract The new diphenylamine-linked bis(imidazoline) ligands were prepared through Kelly-You's imidazoline formation procedure mediated by Hendrickson's reagent in good yields. The novel ligands were tested in the asymmetric Friedel,Crafts alkylation of indole derivatives with nitroalkenes. In most cases, good yields (up to 97%) and excellent enantioselectivities (up to 98%) can be achieved. The optimized bis(imidazoline) ligand with trans -diphenyl substitution on the imidazoline ring gave better enantioselectivity than the corresponding bis(oxazoline) ligand. [source]

Synthesis of Diastereomeric 1,4-Diphosphine Ligands Bearing Imidazolidin-2-one Backbone and Their Application in Rh(I)-Catalyzed Asymmetric Hydrogenation of Functionalized Olefins

Jian Zhang
Abstract The diastereomeric 1,4-diphosphine ligands, (S,S,S,S)- 1a, (R,S,S,R)- 1b and (R,S,S,S)- 1c, with the imidazolidin-2-one backbone were synthesized, and utilized for an investigation of the effects of backbone chirality on the enantioselectivity in the Rh(I)-catalyzed hydrogenation of various functionalized olefinic substrates. It was found that the catalytic efficiencies are largely dependent on the configurations of the ,-carbons to phosphine. Thus, the Rh complex of the pseudo- C2 -symmetrical diphosphine, (R,S,S,S)- 1c, showed excellent enantioselectivities (93.0,98.6% ees) in the hydrogenations of a broad spectrum of substrates, and especially in the hydrogenations of methyl ,-(N -acetyamino)-,-arylacrylates (95.3,97.0% ees). However, the enantioselectivities obtained with the C2 -symmetrical (R,S,S,R)- 1b were largely dependent on the substrate (19.8,97.3% ees). The Rh complex of ligand 1a having the (S,S,S,S)-configuration showed the lowest catalytic efficiency for all of the substrates examined (0,84.8% ees). [source]

Photophysics of Aminoxanthone Derivatives and Their Application as Binding Probes for DNA,

Tamara C. S. Pace
ABSTRACT Xanthones with amino substituents were synthesized to diminish the photoreactivity of the xanthone chromophore with DNA, with the objective of using these molecules to study their binding dynamics with DNA. The aminoxanthones showed a strong solvatochromic effect on their singlet and triplet excited-state photophysics, where polar solvents led to a decrease of the energies for the excited states. Quenching of the triplet excited states by nitrite anions was used to determine the binding dynamics, and a residence time in the microsecond time domain was estimated for the bound 2-aminoxanthone with DNA. The quenching experiments performed showed that this methodology will not be applicable to study the binding dynamics of a wide variety of guests with DNA. [source]