palladium-catalyzed intermolecular heck: Topics by WorldWideScience.org

Efficient synthesis of unsymmetric diarylalkynes from decarboxylative coupling in a continuous flow reaction system

A general palladium-catalyzed carbonylative Sonogashira coupling of benzyl chlorides with terminal acetylenes has been established. Depending on the alkyne 1,4-diaryl-3-butyn-2-ones or substituted furanones are obtained in moderate to good yields. Best catalytic performance is achieved applying a mixed Pd(PPh(3))Cl(2)/P(OPh)(3) catalyst system. PMID:21968528

2011-10-01

British Library Electronic Table of Contents (United Kingdom)

Unsymmetric diaryl alkynes were synthesized from the palladium-catalyzed decarboxylative coupling of aryl halides and propiolic acid using a continuous flow reaction system. This flow chemistry system continuously gave the desired products in moderate to good yields, and produced less byproduct than was formed in the batch reaction.

2011-01-01

Palladium-catalyzed combustion of methane: Simulated gas turbine combustion at atmospheric pressure

Inelastic x-ray scattering of dense solid oxygen: Evidence for intermolecular bonding

Atmospheric pressure tests were performed in which a palladium catalyst ignites and stabilizes the homogeneous combustion of methane. Palladium exhibited a reversible deactivation at temperatures above 750 C, which acted to ``self-regulate`` its operating temperature. A properly treated palladium catalyst could be employed to preheat a methane/air mixture to temperatures required for ignition of gaseous combustion (ca. 800 C) without itself being exposed to the mixture adiabatic flame temperature. The operating temperature of the palladium was found to be relatively insensitive to the methane fuel concentration or catalyst inlet temperature over a wide range of conditions. Thus, palladium is well suited for application in the ignition and stabilization of methane combustion.

1995-04-01

UK PubMed Central (United Kingdom)

The detailing of the intermolecular interactions in dense solid oxygen is essential for an understanding of the rich polymorphism and remarkable properties of this element at high pressure. Synchrotron...Full Text Available

2008-08-19

On the homology of exotic Springer fibers

Vanishing integrals for Hall-Littlewood polynomials

We determine the structure of the total homology groups of exotic Springer fibers as affine Weyl group representations. As applications, we provide single top/socle property of standard modules in the exotic Deligne-Langlands correspondence (except for root of unity case), an analogue of Verma's theorem, the coincidence of analytic/geometric gradings in the $C ^{\\infty}$-realization of anti-spherical modules of graded Hecke algebras of type $\\mathsf{BC}$ with unequal parameters, among others.

2011-01-01

Symmetrizers and antisymmetrizers for the BMW algebra

It is well known that if one integrates a Schur function indexed by a partition $\\lambda$ over the symplectic (resp. orthogonal) group, the integral vanishes unless all parts of $\\lambda$ have even multiplicity (resp. all parts of $\\lambda$ are even). In a recent paper of Rains and Vazirani, Macdonald polynomial generalizations of these identities and several others were developed and proved using Hecke algebra techniques. However at $q=0$ (the Hall-Littlewood level), these approaches do not work, although one can obtain the results by taking the appropriate limit. In this paper, we develop a direct approach for dealing with this special case. This technique allows us to prove some identities that were not amenable to the Hecke algebra approach, as well as to explicitly control the nonzero values. Moreover, we are able to generalize some of the identities by introducing extra parameters. This leads us to a finite-dimensional analog of a ...

2010-01-01

Small angle X-ray scattering on concentrated hemoglobin solutions

Let $n\\in\\mathds{N}$ and $B_n(r,q)$ be the generic Birman-Murakami-Wenzl algebra with respect to indeterminants $r$ and $q$. It is known that $B_n(r,q)$ has two distinct linear representations generated by two central elements of $B_n(r,q)$ called the symmetrizer and antisymmetrizer of $B_n(r,q)$. These generate for $n\\geq 3$ the only one dimensional one sided ideals of $B_n(r,q)$ and generalize the corresponding notion for Hecke algebras of type $A$. In this paper the coefficients of these elements with respect to the graphical basis of $B_n(r,q)$ are determined explicitly.

2011-01-01

Interrelation between the spatial structure of unsaturated hydrocarbon molecules and heats of their adsorption

The small-angle X-ray scattering technique was used to determine the intermolecular structure and interaction potentials in oxi-and deoxi-hemoglobin solutions. The pair correlation function obtained by the ZERNICKE-PRINS equation characterizes the intermolecular structure of the hemoglobin molecules. The intermolecular structure is concentration dependent. The hemoglobin molecules have a 'short range order structure' with a range of about 4 molecule diameters at 324 g/l. The potential functions of the hemoglobin-hemoglobin interaction have been determined on the basis of fluid theories. Except for the deoxi-hemoglobin solution having the concentration 370 g/l, the pair interaction consists in a short repulsion and a weak short-range attraction against kT. The potential minimum is between 1.2 - 1.5 nm above the greatest hemoglobin diameter. (author).

British Library Electronic Table of Contents (United Kingdom)

The total area (s m) of Voronoi-Dirichlet polyhedron faces corresponding to all intermolecular contacts of one molecule in the structure of crystals and the total volume of pyramids (V m) built on such faces and containing the nuclei of atoms participating in intermolecular contacts in their vertices were determined for 19 unsaturated hydrocarbons. The differential molar heat of adsorption of the hydrocarbons on graphitized thermal carbon black was found to be linearly related to the s m or V m integral parameters of their Voronoi-Dirichlet polyhedra. Aromatic hydrocarbons on the one hand and saturated hydrocarbons, olefins, and acetylene on the other are characterized by different dependences because of the special shapes of their molecular Voronoi-Dirichlet polyhedra.

2008-01-01

Interrelation between the spatial structure of unsaturated hydrocarbon molecules and heats of their adsorption

Synthesis and antimicrobial activity of (E) stilbene derivatives

The total area ( s m) of Voronoi-Dirichlet polyhedron faces corresponding to all intermolecular contacts of one molecule in the structure of crystals and the total volume of pyramids ( V m) built on such faces and containing the nuclei of atoms participating in intermolecular contacts in their vertices were determined for 19 unsaturated hydrocarbons. The differential molar heat of adsorption of the hydrocarbons on graphitized thermal carbon black was found to be linearly related to the s m or V m integral parameters of their Voronoi-Dirichlet polyhedra. Aromatic hydrocarbons on the one hand and saturated hydrocarbons, olefins, and acetylene on the other are characterized by different dependences because of the special shapes of their molecular Voronoi-Dirichlet polyhedra.

2008-08-01

British Library Electronic Table of Contents (United Kingdom)

Plants use multiple defence mechanisms comprising both constitutive and inducible barriers to prevent entering of phytopathogenic micro-organisms. In many plant species one of the most efficient responses to combat attacking microbes is the rapid synthesis of antimicrobial low molecular weight phytoalexins, for example, resveratrol, 3,5,4prime-trihydroxystilbene (1). Resveratrol and its natural derivatives, however, display only moderate antimicrobial effects. Nevertheless, resveratrol may be a useful lead structure for the chemical synthesis of antimicrobials. In this study, several series of stilbenes have been synthesized, starting from the aldehydes using Wittig reactions to access the corresponding styrenes that were subjected to Mizoroki-Heck reactions to yield the stilbenes in good ...

2011-01-01

Density functional theory and topological analysis on the hydrogen bonding interactions in cysteine-thymine complexes

British Library Electronic Table of Contents (United Kingdom)

Abstract Hydrogen bonding interactions between amino acids and nucleic acid bases constitute the most important interactions responsible for the specificity of protein binding. In this study, complexes formed by hydrogen bonding interactions between cysteine and thymine have been studied by density functional theory. The relevant geometries, energies, and IR characteristics of hydrogen bonds (H-bonds) have been systematically investigated. The quantum theory of atoms in molecule and natural bond orbital analysis have also been applied to understand the nature of the hydrogen bonding interactions in complexes. More than 10 kinds of H-bonds including intra- and intermolecular H-bonds have been found in complexes. Most of intermolecular H-bonds involve O (or N) atom as H-acceptor, whereas the...

2011-01-01

Ultra-fast charge transfer in organic electronic materials and at hybrid interfaces studied using the core-hole clock technique

The influence of an intramolecular H-bond on the adsorption of sulfur-containing amino acids on graphitized thermal carbon black

Research highlights: {yields} The use of resonant photoemission in its 'core-hole clock' expression for the study of the dynamical charge transfer across hybrid organic-inorganic interfaces and for the intermolecular charge transfer in the bulk of organic thin films is reviewed. {yields} The electronic coupling to the substrate and the efficiency of charge transport across hybrid interfaces is different for individual electronic subsystems of the molecular adsorbate. {yields} The intermolecular charge transfer in the bulk of discotic liquid crystals occurs on the order of a few femtoseconds and is faster than expected from the macroscopic charge transport characteristics of the material. -- Abstract: The focus of this brief review is the use of resonant photoemission in its 'core-hole clock' expression for the study of two important problems relevant for the field of organic electronics: the dynamical charge ...

2011-01-15

British Library Electronic Table of Contents (United Kingdom)

The thermodynamic characteristics of adsorption of sulfur-containing amino acids and their derivatives on the surface of graphitized thermal carbon black were calculated by the molecular statistical method. The parameters of the atom-atom potential function of intermolecular interaction between the S atom in amino acids and the graphite C atom were determined. It was shown that an intramolecular H-bond influenced the adsorption of amino acids on the surface of graphitized thermal carbon black.

2009-01-01

The influence of an intramolecular H-bond on the adsorption of sulfur-containing amino acids on graphitized thermal carbon black

Parahydrogen clusters: Numerical estimates and physical effects

2009-04-01

Calculation of henry constants for the adsorption of isomeric phenylenediamines on graphitized thermal carbon black

We study by means of Quantum Monte Carlo simulations based on the Worm Algorithm the low temperature (down to T = 0.05 K) properties of parahydrogen clusters comprising up to 40 molecules. Three different intermolecular interactions are employed: the Silvera-Goldman, the Buck and the Lennard-Jones potential. Despite important discrepancies observed in the numerical estimates of energy and superfluid fraction, the mechanism by which clusters melt at low T is independent of the particular choice of the potential, whose only effect is to alter the temperature scale.

2009-02-01

British Library Electronic Table of Contents (United Kingdom)

Henry constants for the adsorption of o- and p-phenylenediamines on the surface of graphitized thermal carbon black within the temperature range 433?479 K were calculated by the molecular statistical method. The parameters of the atom-atom potential function of intermolecular interaction between the nitrogen atom in aniline and isomeric phenylenediamines and the carbon atom of the basal face of graphite were determined. It was shown that an intramolecular H bond influenced the geometry and adsorption properties of o-phenylenediamine.

2009-01-01

Calculation of henry constants for the adsorption of isomeric phenylenediamines on graphitized thermal carbon black

Effect of surface-perturbed intermolecular interaction on adsorption of simple gases on a graphitized carbon surface.

Henry constants for the adsorption of o- and p-phenylenediamines on the surface of graphitized thermal carbon black within the temperature range 433-479 K were calculated by the molecular statistical method. The parameters of the atom-atom potential function of intermolecular interaction between the nitrogen atom in aniline and isomeric phenylenediamines and the carbon atom of the basal face of graphite were determined. It was shown that an intramolecular H bond influenced the geometry and adsorption properties of o-phenylenediamine.

2009-12-01

Spontaneous and stimulated Raman studies of vibrational dephasing in condensed phases

In this paper, we investigate the effect of the solid surface on the fluid-fluid intermolecular potential energy. This modified fluid-fluid interaction energy due to the inducement of a solid surface is used in the grand canonical Monte Carlo (GCMC) simulation of various noble gases, nitrogen, and methane on graphitized thermal carbon black. This effect is such that the effective interaction potential energy between two particles close to surface is less than the potential energy if the solid substrate is not present. With this modification the GCMC simulation results agree extremely well with the experimental data over a wide range of pressures while the simulation results with the unmodified potential energy give rise to a shoulder near the neighborhood of monolayer coverage and the significant overprediction of the second and higher layer coverages. In particular the unmodified GCMC results exhibit very sharp change in those higher layers while the experimental ...

2004-08-31

1 2 3

An experimental and molecular-statistical study of the adsorption of the iodobenzene, 2-iodothiophene, and isomeric iodoadamantane molecules on the graphite basal face surface

Vibrational dephasing in condensed phases is studied from both a theoretical and experimental standpoint. A theory is presented which describes the dynamics of motional or exchange processes in weakly perturbed systems. This general formalism, which has been previously used to describe motional narrowing in magnetic resonance, is applied to vibrational spectroscopy. The model treats the case of a high frequency vibration anharmonically coupled to a low-frequency vibration. Intermolecular exchange of low frequency vibrational quanta results in a temperature dependent broadening and frequency shift of the high frequency vibration. Analysis of experimental data by this model yields both the exchange rates and the anharmonic couplings.

1980-05-01

British Library Electronic Table of Contents (United Kingdom)

The thermodynamic characteristics of adsorption of iodobenzene, 2-iodothiophene, and 1- and 2-iodoadamantanes on the surface of graphitized thermal carbon black were determined experimentally. The influence of the special features of the molecular structure of the adsorbates on the thermodynamic characteristics of adsorption was studied. The atom-atom approximation of the semiempirical molecular-statistical theory of adsorption was used to calculate the thermodynamic characteristics of adsorption of the adsorbates using the newly determined potential function parameters of pair intermolecular interaction (?(r)) of I with C atoms of the basal graphite face. For the example of isostructural monohalogenated benzenes, thiophenes, and adamantanes, a comparative analysis of the contributions of ...

2011-01-01

Uniform and Residue-specific {sup 15}N-labeling of Proteins on a Highly Deuterated Background

Study on the spatial structure of annomuricatin A, a cyclohexapeptide from the seeds of Annona muricata

A general method for stable-isotope labeling of large proteins is introduced and applied for studies of the E. coli GroE chaperone proteins by solution NMR. In addition to enabling the residue-specific {sup 15}N-labeling of proteins on a highly deuterated background, it is also an efficient approach for uniform labeling. The method meets the requirements of high-level deuteration, minimal cross-labeling and high protein yield, which are crucial for NMR studies of structures with sizes above 150 kDa. The results obtained with the new protocol are compared to other strategies for protein labeling, and evaluated with regard to the influence of external factors on the resulting isotope labeling patterns. Applications with the GroE system show that these strategies are efficient tools for studies of structure, dynamics and intermolecular interactions in large supramolecular complexes, when combined with TROSY- and CRINEPT-based experimental NMR schemes.

2004-07-15

British Library Electronic Table of Contents (United Kingdom)

A cyclic hexapeptide, annomuricatin A (the molecular formula: C27H38N6O7), was isolated from the seeds of Annona muricata. The types and sequence of the amino acids were confirmed by X-ray diffraction analysis. The stereochemistry of the title cyclopeptide was clarified by X-ray crystallographic study. The backbone contains two b-turns, one is type I b-turn and the other is type II, which are stabilized by two transannular 41 backbone hydrogen bonds between Ala and Phe. There are intermolecular hydrogen bonds between the cyclopeptide and the solvent molecules which maintained the steady spatial arrangement in crystal.

2007-01-01

SAXS studies on added-salt species dependence of conformation of fully-charged poly(L-glutamate) in aqueous solutions

Oxidation of polycaprolactone to induce compatibility with other degradable polyesters

The effect of counter-ion species on the local conformation of fully-charged poly(L-glutamate) in added-salt aqueous solutions were studied by small-angle X-ray scattering(SAXS). In the case of presence of monovalent counter-ion, the scattering behaviour could be explained by taking into consideration the excluded volume effect and intermolecular-interface interaction on the scattering function of wormlike chain. On the other hand, since SAXS profile of the solution in the presence of divalent counter-ion well fitted to the scattering function of dendrimer, it suggested that the conformation of polymer chain in such solution would be more compact conformation than that of presence of monovalent ion.

2010-10-01

British Library Electronic Table of Contents (United Kingdom)

Chemical modification of poly(?-caprolactone) PCL by oxidation with potassium permanganate in solution was investigated. According to the data obtained from Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance 1H NMR, after the oxidation reactions the PCL chains exhibited new functional groups (vinyl and hydroxyl) and possible intermolecular recombination, producing an oxidized-polycaprolactone (PCL-OX). Solution viscometry indicated that degradation also occurred during the oxidation reactions (30% drop in viscosity average molecular weight was detected). Differential scanning calorimetry (DSC) also indicated that PCL was chemically modified and degraded. The successive self-nucleation/annealing (SSA) treatment confirmed that a reduction (or interruption) in line...

2007-01-01

Novel miscible poly(ethylene sebacate)/poly(4-vinyl phenol) blends: Miscibility, melting behavior and crystallization study

British Library Electronic Table of Contents (United Kingdom)

High molecular weight samples of the novel biodegradable polyester poly(ethylene sebacate) (PESeb) were synthesized. Miscible poly(ethylene sebacate)/poly(4-vinyl phenol) semicrystalline/amorphous blends were prepared by applying the solvent casting method. Miscibility was proved by the single composition dependent glass transition temperature over the entire composition range observed in DSC traces of the quenched blend samples and also by the melting point depression. The Flory-Huggins interaction parameter was found to be x12 = -1.3. Also, FTIR spectra supported the hypothesis of intermolecular interactions due to hydrogen bonding. The crystallization of PESeb in blends was studied. As expected, isothermal crystallization rates decreased in the blends with increasing the PVPh content. T...

2011-01-01

Liquid crystal films on curved surfaces: An entropic sampling study

Evaluation of gels obtained from acetylation of chitosan in heterogeneous medium

The confining effect of a spherical substrate inducing anchoring (normal to the surface) of rod-like liquid crystal molecules contained in a thin film spread over it has been investigated with regard to possible changes in the nature of the isotropic-to-nematic phase transition as the sample is cooled. The focus of these Monte Carlo simulations is to study the competing effects of the homeotropic anchoring due to the surface inducing orientational ordering in the radial direction and the inherent uniaxial order promoted by the intermolecular interactions. By adopting entropic sampling procedure, we could investigate this transition with a high temperature precision, and we studied the effect of the surface anchoring strength on the phase diagram for a specifically chosen geometry. We find that there is a threshold anchoring strength of the surface below which uniaxial nematic phase results, and above which the isotropic fluid cools to a radially ordered nematic ...

2010-01-01

Effects of surface mediation on the adsorption isotherm and heat of adsorption of argon on graphitized thermal carbon black

Chitosan was acetylated during 2, 5 and 10 h and physical gels were obtained at different polymer concentrations in N,N-dimethylacetamide containing 5% of LiCl. Acetylation was confirmed by infrared spectroscopy and "1"3C NMR, and degrees of acetylation in the range of 0.82-0.91 were determined by NMR. The O-acetylation degree (0.12-0.15) was exclusively determined by a volumetric method. Rheological studies showed that the storage modulus values were smaller for the more acetylated samples and increased with the temperature and the polymer concentration. All the gels presented storage modulus superior to loss modulus, evidencing more elastic than viscous characteristics. The results obtained in this work suggest a gelation process based on a balance between O and N-acetylation and intermolecular bonds. (author)

British Library Electronic Table of Contents (United Kingdom)

In this paper, the effects of surface mediation on the adsorption isotherm and isosteric heat of adsorption on a graphite surface were investigated, as the surface mediation is known to affect the intermolecular interaction of adsorbed molecules close to the surface. Kim and Steele (Phys. Rev. B 45 (11) (1992) 6226-6233) and others have assumed that the surface mediation is confined only to the first layer. This will be tested in this paper with a combined experimental and Grand Canonical Monte Carlo (GCMC) simulation of adsorption of argon on graphitized thermal carbon black (GTCB) over a range of temperatures (77-95.25K). By matching the simulation results against the experimental data, we have found that the surface mediation is extended up to the fourth layer, rather than only the firs...

2010-01-01

Coherent spontaneous radiation of Frenkel excitons

Cluster approach to quantum-chemical calculations of chemisorption and heterogeneous catalytic systems

We have constructed a mathematical model that describes the coherent spontaneous radiation of a macroscopically filled exciton mode. We have demonstrated qualitatively ways in which a coherent subsystem of excitons can be formed. When this occurs under the influence of an external coherent source, exciton free induction occurs, while in the case of a spontaneous transition of the excitons to a coherent state through freezing of the reservoir of intermolecular interactions superradiance occurs. We have concluded that superradiance in the system of Frenkel excitons is possible under the influence of the non-Dicke mechanisms of self-induction of correlations, when the dipole transition moments of the individual atoms are coupled into a single macroscopic effective spin through their electrostatic interaction, this being analogous to the ordering of magnetic dipole moments in a ferromagnet.

1988-01-01

Chemical isomeric effects on propanol glassy structures

The increasing use of quantum-chemical methods in catalysis has underscored the importance of developing and improving semiempirical approximations oriented toward calculations of the total energy and geometry, offering a means for examining intermolecular interactions. In this article a general approach is proposed, using weighting factors for certain regions of distances, i.e., introducing different parametrization into the various regions. A scheme designated MINDO/3-HB is presented as an extension of the MINDO/3 scheme to the region of hydrogen bonds and ..pi..-complexes of olefins with Broensted acid centers (BACs). Examples of cluster calculations are given for the adsorption of ammonia, pyridine, ethylene, and ethanol on the BACs of zeolites. In the example of the process of zeolite synthesis, the possibilities of the cluster approach are discussed for calculations related to the formation of catalysts.

1987-07-01

Chemical isomeric effects on propanol glassy structures

We have studied the structure of both propanol isomers in their glassy and crystalline states by neutron diffraction. The glass-transition temperatures of 1- and 2-propanol are about 98 and 115 K, respectively and, surprisingly, even larger differences are observed for the melting temperatures of the stable crystals, which are 148 and 185 K, respectively. Their supercooled liquid phases show rather different relaxation spectra, 1-propanol manifesting strong deviations from Debye behavior, whereas 2-propanol shows a far weaker effect. We discuss the spectra obtained for the static structure factor and the static pair correlation function D(r). There is a noticeable difference in the position of the first sharp diffraction peak, which clearly indicates a density change, well correlated with the period of the intermolecular oscillations shown by D(r). (orig.)

2002-07-01

An experimental and molecular-statistical study of the adsorption of the iodobenzene, 2-iodothiophene, and isomeric iodoadamantane molecules on the graphite basal face surface

Surface activity at the planar interface in relation to the thermodynamics of intermolecular interactions in the ternary system: maltodextrin-small-molecule surfactant-legumin.

The thermodynamic characteristics of adsorption of iodobenzene, 2-iodothiophene, and 1- and 2-iodoadamantanes on the surface of graphitized thermal carbon black were determined experimentally. The influence of the special features of the molecular structure of the adsorbates on the thermodynamic characteristics of adsorption was studied. The atom-atom approximation of the semiempirical molecular-statistical theory of adsorption was used to calculate the thermodynamic characteristics of adsorption of the adsorbates using the newly determined potential function parameters of pair intermolecular interaction (?( r)) of I with C atoms of the basal graphite face. For the example of isostructural monohalogenated benzenes, thiophenes, and adamantanes, a comparative analysis of the contributions of the F, Cl, Br, and I atoms to the thermodynamic characteristics of adsorption was performed for the nonspecific adsorption of these compounds on a plane graphitized carbon black ...

2011-04-01

Solution processable fluorenyl hexa-peri-hexabenzocoronenes in organic field-effect transistors and solar cells

We report on the effect of potato maltodextrins with variable dextrose equivalent (Paselli SA-2, SA-6 and SA-10) on the surface behavior at the air-water interface of the mixture: legumin+small-molecule surfactant. Distinct in nature small-molecule surfactants (model: sodium salt of capric acid, Na-caprate; and commercially important: a citric acid ester of monoglyceride, CITREM) have been under our consideration. The role of the structure of both of the maltodextrins and the small-molecule surfactants in the effect studied has been elucidated by measurements in a bulk aqueous medium of the enthalpy of their interaction from mixing calorimetry, value of weight average molecular weight of the maltodextrins and the thermodynamics of the pair maltodextrin-solvent and maltodextrin-protein interactions from laser static light scattering. The combined data of mixing calorimetry and light scattering suggest some complex formation between the small-molecule surfactants and the maltodextrins. ...

2001-07-01

Effects of surface mediation on the adsorption isotherm and heat of adsorption of argon on graphitized thermal carbon black.

The organization of organic semiconductor molecules in the active layer of organic electronic devices has important consequences to overall device performance. This is due to the fact that molecular organization directly affects charge carrier mobility of the material. Organic field-effect transistor (OFET) performance is driven by high charge carrier mobility while bulk heterojunction (BHJ) solar cells require balanced hole and electron transport. By investigating the properties and device performance of three structural variations of the fluorenyl hexa-peri-hexabenzocoronene (FHBC) material, the importance of molecular organization to device performance was highlighted. It is clear from {sup 1}H NMR and 2D wide-angle X-ray scattering (2D WAXS) experiments that the sterically demanding 9,9-dioctylfluorene groups are preventing {pi}-{pi} intermolecular contact in the hexakis-substituted FHBC 4. For bis-substituted FHBC compounds 5 and 6, {pi}-{pi} ...

2010-03-24

Adsorption of carbon tetrachloride on graphitized thermal carbon black and in slit graphitic pores: five-site versus one-site potential models.

2009-11-14

Study of structural, thermodynamical and dynamical properties of molecular liquids confined in nano-porous materials

The performance of intermolecular potential models on the adsorption of carbon tetrachloride on graphitized thermal carbon black at various temperatures is investigated. This is made possible with the extensive experimental data of Machin and Ross(1), Avgul et al.,(2) and Pierce(3) that cover a wide range of temperatures. The description of all experimental data is only possible with the allowance for the surface mediation. If this were ignored, the grand canonical Monte Carlo (GCMC) simulation results would predict a two-dimensional (2D) transition even at high temperatures, while experimental data shows gradual change in adsorption density with pressure. In general, we find that the intermolecular interaction has to be reduced by 4% whenever particles are within the first layer close to the surface. We also find that this degree of surface mediation is independent of temperature. To understand the packing of carbon tetrachloride in slit ...

2006-05-18

Spattering and Crackle of Hot Cooking Oil with Water: A Classroom Demonstration and Discussion

When liquids are confined in nano-scopic dimensions, their properties differ from the corresponding bulk liquid, due to their reduced dimensionality and surface effects. Phase transition temperatures and pressures are often shifted from the bulk values and new phases can appear due to the strong interactions of the molecules with the confining walls. We have studied the structural and dynamical properties of aromatic liquids such as benzene, toluene, and ortho-terphenyl confined in nano-porous materials, MCM-41 and SBA-15, synthesized and characterized in our laboratory. A non-trivial dependence of the glass transition temperature, Tg, on the pore size and surface treatment of nano-porous materials is confirmed and interpreted as resulting from a competition between the fluid-wall and fluid-fluid intermolecular interactions. An increase of Tg is observed for small pore sizes and attractive surface while Tg decreases for non attractive surface, whatever the pore ...

2006-01-01

1 2 3

Some observations on amino acid racemization under pyrolytic temperatures and inorganic oxide-catalyzed intermolecular condensation.

Any student that has spent time in the kitchen knows that hot vegetable oil will pop and spatter violently after coming into contact with water such as that on the surface of foods (meat, fish, potatoes, etc.). This well-known effect can be used as an instructional resource to promote cooperative, active, and inquiry-based learning about central concepts of chemistry including boiling point, miscibility, and density of liquids. The starting point of the learning activity is a demonstration of (i) the effect of adding a drop of water to hot (as for cooking) vegetable oil and (ii) the effect of adding a drop of vegetable oil to hot water (near its boiling point). Intermolecular interactions, properties of vegetable oils, and a variety of other topics, such as the importance of other heat points (smoke, flash, and fire) for oils, the fundamental of the crackle test for checking the presence of water in oil, and why an oil fire (for example in a kitchen) never should ...

2009-11-01

SnPc on Ag(111) investigated by STM

The problem of homochirality is of crucial importance for the origins of Life. While most laboratory studies are focused on the search of physical and chemical sources of handedness in the Universe, they reflect only one aspect of the problem: the origin of homochiral biomolecules. At the same time, any space environments where biomolecules are expected to form and where they have to pass through before the first primitive forms of Life emerge, include strong irradiation or/and high temperatures. This automatically implies the possibility of losing the optical activity, i.e. racemization. The simulation experiments performed by our group deal with the following two aspects of amino acid abiotic chemistry: (1) amino acid pyrolysis associated with their extraterrestrial delivery; and (2) peptide formation from amino acids catalyzed by inorganic oxides. According to our observations, the racemization phenomena are very common in the systems considered, not only under pyrolytic ...

2001-01-01

Photophysical characteristics of 4,4'-bis(N-carbazolyl)tolan derivatives and their application in organic light emitting diodes

The investigation of interfaces between thin organic films and metal surfaces is a field of highest interest because it represents the basis for future applications of organic electronic devices. In this context, phtalocyanines are of particular interest since repulsive intermolecular interaction was found recently for this group of organic molecules. Tin(II)-phtalocyanine (SnPc) is non-planar and can adsorb in two different geometries: with the Sn atom pointing downwards (Sn down) or upwards (Sn up). In our group different Pc molecules have previously been studied using several experimental techniques like SPA-LEED or XSW. Here we present STM studies of SnPc on Ag(111), taken at different coverages and temperatures, and discuss the results in the context of our previous findings. At low coverages the formation of chains can be observed for Sn down molecules while Sn up molecules tend to stay separated. This originates from a strong interaction with the substrate ...

2010-07-01

Photochemistry on surfaces. 2. Intermolecular electron transfer on colloidal alumina-coated silica particles

4,4'-bis(N-carbazolyl)tolan (BCT) and 4,4'-bis[N-(3,6-di-t-butyl)carbazolyl]tolan (BCT-t-Bu) were synthesized as ?-expanded analogs of 4,4'-bis(N-carbazolyl)biphenyl. Their photophysical characteristics both in solution and films were thoroughly investigated. Interestingly, the phosphorescence spectrum of BCT was significantly medium-dependent, and the emission maximum was red-shifted by 131 nm from 489 nm in solution at 77 K to 620 nm in a deposited film at 5 K, suggesting the presence of strong intermolecular interactions in the film. BCT and BCT-t-Bu were found to be useful as host materials for fluorescence-based organic light emitting diodes (OLEDs). However, their low triplet energy levels in films negated their potential to act as hosts in phosphorescence-based OLEDs. - Research highlights: ? We synthesized N-carbazolyl-tolan derivatives (BCT) as ?-expanded analogues of CBP. ? We found that BCT derivatives are useful as host materials for fluorescence-based ...

2011-07-01

Palladium(II) and platinum(II) saccharinate complexes containing pyridine and 3-acetylpyridine: Synthesis, crystal structures, fluorescence and thermal properties

Reductive quenching of two photoexcited ruthenium(II) complexes by an anionic electron donor, 2,2{prime}-azinobis(3-ethyl-benzothiazoline-6-sulfonate) (ABTS{sup 2{minus}}), in aqueous solution was examined by laser flash photolysis before and after adding positively charged colloidal (250-{angstrom} diameter) alumina-coated silica particles. The kinetics and quantum yields of electron transfer with an anionic sensitizer, RuL{sub 3}{sup 4{minus}} (L = bathophenanthroline disulfonate), and a cationic one, Ru(bpy){sub 3}{sup 2+} (bpy = 2,2{prime}-bipyridine), were compared. Coadsorption of ABTS{sup 2{minus}} and RuL{sub 3}{sup 4{minus}} by the particles greatly enhanced the rate of quenching such that only the reaction occurring on the surfaces of the particles was observed. Electron transfer from ABTS{sup 2{minus}} to RuL{sub 3}{sup 4-*} occurred by a static (nondiffusional) process, and the quenching efficiency was maximal when there was close to monolayer coverage of the reactants on ...

1989-02-23

British Library Electronic Table of Contents (United Kingdom)

New palladium(II) and platinum(II) complexes of saccharinate (sac), trans-[Pd(py)"2(sac)"2] (1), cis-[Pt(py)"2(sac)"2] (2), trans-[Pd(3-acpy)"2(sac)"2] (3) and cis-[Pt(3-acpy)"2(sac)"2] (4) (py=pyridine and 3-acpy=3-acetylpyridine) have been synthesized. Elemental analysis, UV-Vis, IR, NMR and TG/DTA characterizations have been carried out. The structures of 1-4 were determined by X-ray diffraction. The palladium(II) and platinum(II) ions are coordinated by two N-bonded sac ligands, and two nitrogen atoms of py or 3-acpy, forming a distorted square-planar geometry. The palladium(II) complexes (1 and 3) are trans isomers, while the platinum(II) complexes (2 and 4) are cis isomers. The mononuclear species in the solid state are connected by weak intermolecular C-H...O hydrogen bonds, C-H...@...

2011-01-01

Novel high-throughput screening system for identifying STAT3-SH2 antagonists

Miscibility of Nylon 66 and Nylon 48 blend evaluated by crystallization dynamics

Constitutive activation of the oncogenic transcription factor STAT3 frequently occurs in various human malignancies. STAT3 activation involves dimerization via intermolecular pTyr-SH2 interaction. Thus, antagonizing this interaction is a feasible approach to inhibit STAT3 activation for cancer therapy. In order to identify selective STAT3 inhibitors, we developed a biochemical HTS system based on AlphaScreen technology, which measures the abilities of test compounds to antagonize pTyr-SH2 interactions. We screened our chemical libraries using this system and identified 5,15-diphenylporphyrin (5,15-DPP) as a selective STAT3-SH2 antagonist. Selective inhibition of STAT3 nuclear translocation and DNA biding activity was observed in cells treated with 5,15-DPP. IL-6-dependent dimerization of STAT3, c-myc promoter binding and c-myc protein expression were all suppressed by 5,15-DPP, whereas no decrement in either expression or phosphorylation level of STAT3 was ...

2009-03-13

Hydrogen isotope effects in hydride transfer reactions of formaldehyde and glyoxal

The crystallization dynamics of Nylon 66/Nylon 48 blends, the crystalline/crystalline polymer blend, was analyzed by differential scanning calorimetry (DSC) under isothermal conditions. The equilibrium melting temperature (T{sub m}{sup 0}), crystal growth rate (G) and the nucleation rate (N) depended on both the degree of supercooling ({delta}T) and the blend fraction (phi). The {delta}T/T{sub m}{sup 0} values obtained at the fixed G, which corresponded to the chemical potential different between molecules in the liquid and the crystal states, and the surface free energy parameters evaluated from G and N depended on phi for blends. The results suggested that Nylon 66/Nylon 48 blends are miscible in all blend fractions. The result agrees with the intermolecular interaction parameter ({chi}) obtained from T{sub m}{sup 0} depression. Infrared spectroscopic and X-ray diffraction data indicated that the hydrogen bond became weak and the crystalline structure became ...

2004-06-24

Deformed-coal structure and control to coal-gas outburst

In the presence of hydroxyl anion, both formaldehyde and glyoxal are known to undergo rearrangements involving intermolecular and intramolecular hydride transfer (the Cannizzaro and Benzilic acid rearrangements respectively). The authors report ab initio SCF-MO calculations of the transition state geometries, the activation barriers, and the hydrogen isotope effects for these two reactions. The structure of the transition state for the rection involving formaldehyde is usually basis set dependent, becoming more linear and symmetrical as the basis set size increases. In contrast, the analogous transition state for the glyoxal reaction involves a highly non-linear hydride transfer. They find the isotope effects to be quite low for the Cannizzaro reaction, and significantly larger for the non-linear benzilic acid rection, in apparent contradiction to Westheimer's suggestion the isotope effects reach a maximum for linear hydrogen transfers. Since this hypothesis does ...

1987-04-01

Bis(acetylacetonato)ruthenium Complexes of Noninnocent 1,2-Dioxolene Ligands: Qualitatively Different Bonding in Relation to Monoimino and Diimino Analogues

Based on techniques of organic solvent extraction and a thermal model experiments of coal-related hydrocarbon, the variation of coal structure and the character of deformed coal-related hydrocarbons were studied when the coal seam at Piagdingshan mine, China was modified by tectonic stress. The results show that the extraction ratio by n-hexane and benzene from the deformed coal approaches that form normal coal, but the extraction ratio by chloroform from the deformed coal is two times more than that from normal coal. The deformed coal has higher solvable low-molecular weight compounds than normal coal. The intermolecular force of deformed coal is relatively small. The deformed coal has low strength and high adsorption capacity, and these determine the outbreak of coal-gas outburst. The extraction yields by chloroform can be taken as an index of forecast risks of coal-gas outburst. The potentially of generating hydrocarbon from the deformed coal is relatively low. ...

2007-03-15

British Library Electronic Table of Contents (United Kingdom)

Abstract Coordination compounds [Ru(acac)2(Q)] (acac=acetylacetonate; Q=o-benzoquinone) were prepared as complexes 1 (Q=o-benzoquinone), 2 (Q=3-methoxy-o-benzoquinone), 3 (Q=4-methyl-o-benzoquinone), and 4 (Q=3,5-di-tert-butyl-o-benzoquinone). The structures of 1 and 2 were determined to reveal a RuIII/o-benzosemiquinone formulation, supported by analysis of experimental data (spectroscopy, magnetism of 1) and by DFT calculations. The S=1 ground state calculated for 1 stands in contrast to the spin-paired analogues with arylimino-o-benzosemiquinonato and diimino-o-benzoquinone ligands. The close contacts of about 5.3- possible between semiquinone O atoms of different molecules in the crystal allow for intermolecular spin-spin interactions and an overall complex magnetic behavior. One quasi...

2011-01-01

Spectroscopic studies on weak intermolecular interactions of fluoranthene derivatives with benzene or ethanol in cyclohexane

Tunable far infrared laser spectroscopy of Van der Waals molecules in a planar supersonic jet expansion

Complete text of publication follows. We have published on the spectroscopic study on the formation of a 1:1 molecular complex of fluoranthene (F) with benzene (B) in cyclohexane and estimated the equilibrium constant K(F-B) (0.147 dm3 mol-1 at 298 K), enthalpy change DH(F-B) (-5.9 kJ mol-1) and entropy change DS(F-B) (-36 JK-1mol-1 at 298 K) for this complex formation (S. Enomoto et al., Bull. Chem. Soc. Jpn., 75 (2002) 689-693). In this study, the electronic absorption spectra have been observed for the fluoranthene derivatives in cyclohexane-benzene and/or cyclohexane-ethanol mixed solvents to investigate the weak intermolecular interactions between fluoranthene derivatives and benzene or ethanol. The electronic absorption spectra of 3-aminofluoranthene (AF) in the mixed solvent mentioned above showed isosbestic points with varying B and ethanol (E) concentrations. These observations indicate that AF forms a 1:1 molecular complex with B or E, the K(AF-B) and ...

2009-09-03

Study of structural, thermodynamical and dynamical properties of molecular liquids confined in nano-porous materials; Etude des proprietes structurales, thermodynamiques et dynamiques de liquides moleculaires confines dans des materiaux nanoporeux modeles

The gas phase high resolution spectroscopic study of weakly bound clusters can provide the information necessary to develop an intermolecular potential energy surface. This surface can then be used to better understand condensed phases. In this work, a tunable far infrared laser spectrometer is used to study weakly bound dimers produced in the newly developed continuous planar supersonic jet expansion apparatus. The water dimer is an extensively studied hydrogen bonded dimer. It undergoes several tunneling motions which result in splittings and perturbations of the rovibrational energy levels. A review is presented of much of the experimental and theoretical work done on water dimer, including a description of the combined fit of all the high resolution spectroscopic results by Coudert and Hougen. Also included is a discussion of the measurement of the K = 1 lower {yields} K = 2 lower band performed using the tunable far infrared laser/planar jet apparatus. The ...

1990-12-01

Diffusion and adsorption of methane confined in nanoporous carbon aerogel: a combined quasi-elastic and small-angle neutron scattering study

When liquids are confined in nano-scopic dimensions, their properties differ from the corresponding bulk liquid, due to their reduced dimensionality and surface effects. Phase transition temperatures and pressures are often shifted from the bulk values and new phases can appear due to the strong interactions of the molecules with the confining walls. We have studied the structural and dynamical properties of aromatic liquids such as benzene, toluene, and ortho-terphenyl confined in nano-porous materials, MCM-41 and SBA-15, synthesized and characterized in our laboratory. A non-trivial dependence of the glass transition temperature, T{sub g}, on the pore size and surface treatment of nano-porous materials is confirmed and interpreted as resulting from a competition between the fluid-wall and fluid-fluid intermolecular interactions. An increase of T{sub g} is observed for small pore sizes and attractive surface while T{sub g} decreases for non attractive surface, ...

2006-11-15

Dependence of mobility on shallow localized gap states in single-crystal organic field-effect-transistors

The diffusion of methane confined in nano-porous carbon aerogel with the average pore size 48 {angstrom} and porosity 60% was investigated as a function of pressure at T = 298 K using quasi-elastic neutron scattering (QENS). The diffusivity of methane shows a clear effect of confinement: it is about two orders of magnitude lower than in bulk at the same thermodynamic conditions and is close to the diffusivity of liquid methane at 100 K (i.e. {approx} 90 K below the liquid-gas critical temperature T{sub C} {approx} 191 K). The diffusion coefficient (D) of methane initially increases with pressure by a factor of {approx}2.5 from 3.47 {+-} 0.41 x 10{sup -10} m{sup 2} s{sup -1} at 0.482 MPa to D = 8.55 {+-} 0.33 x 10{sup -10} m{sup 2} s{sup -1} at 2.75 MPa and starts to decrease at higher pressures. An explanation of the observed non-monotonic behavior of the diffusivity in the confined fluid is based on the results of small-angle neutron scattering experiments of the phase behavior of ...

2010-04-01

Adsorption of benzene on graphitized thermal carbon black: reduction of the quadrupole moment in the adsorbed phase.

In order to optimize the performance of molecular organic electronic devices it is important to study the intermolecular density of states and charge transport mechanisms in the environment of crystalline organic material. Using this approach in Field Effect Transistors (FETs) we show that material purification improves carrier mobility and decreases density of the deep localized electronic state. We also report a general exponential energy dependence of the density of localized states in a vicinity of the mobility edge (Fermi energies up to approx7 times higher than the thermal energy (kT)) in a variety of the extensively purified molecular organic crystal FETs. This observation and the low activation energy of the order of approxkT suggest that molecular structural misplacements of the sizes that are comparable with thermal molecular modes rather than impurity deep traps play a role in formation of these shallow states. We find that the charge carrier mobility in ...

2009-12-15