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Determination of partial molar volumes from free energy perturbation theory

28-Feb-2015 | Jonah Z. Vilseck; Julian Tirado-Rives; William L. Jorgensen, Physical Chemistry Chemical Physics, 2015

Partial molar volume is an important thermodynamic property that gives insights into molecular size and intermolecular interactions in solution. Theoretical frameworks for determining the partial molar volume (V°) of a solvated molecule generally apply Scaled Particle Theory or Kirkwood–Buff ...

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Monitoring ultrafast intramolecular proton transfer processes in an unsymmetric [small beta]-diketone

27-Feb-2015 | Pramod Kumar Verma; Andreas Steinbacher; Federico Koch; Patrick Nuernberger; Tobias Brixner, Physical Chemistry Chemical Physics, 2015

We report the experimental determination of the intramolecular enol–enol tautomerization rate of an unsymmetric β-diketone, benzoylacetone, with femtosecond transient absorption in the ultraviolet. Initially, there is an equilibrium of two possible enolic structures in solution, which is ...

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113Cd NMR Experiments Reveal an Unusual Metal Cluster in the Solution Structure of the Yeast Splicing Protein Bud31p

20-Feb-2015 | Anne‐Marie M. van Roon, Ji‐Chun Yang, Daniel Mathieu, Wolfgang Bermel, Kiyoshi Nagai, David Neuhaus, Angewandte Chemie International Edition, 2015

Abstract Establishing the binding topology of structural zinc ions in proteins is an essential part of their structure determination by NMR spectroscopy. Using 113Cd NMR experiments with 113Cd‐substituted samples is a useful approach but has previously been limited mainly to very small protein ...

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Electrospray ionization for determination of non‐polar polyaromatic hydrocarbons and polyaromatic heterocycles in heavy crude oil asphaltenes

18-Feb-2015 | Lilla Molnárné Guricza, Wolfgang Schrader, Journal of Mass Spectrometry, 2015

Electrospray ionization (ESI) is the most common ionization method in atmospheric pressure ionization mass spectrometry because of its easy use and handling and because a diverse range of components can be effectively ionized from high to medium polarity. Usually, ESI is not employed for the ...

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Using Nonequilibrium Capillary Electrophoresis of Equilibrium Mixtures (NECEEM) for Simultaneous Determination of Concentration and Equilibrium Constant

18-Feb-2015 | Mirzo Kanoatov; Victor A. Galievsky; Svetlana M. Krylova; Leonid T. Cherney; Hanna K. Jankowski; Sergey N. Krylov, Analytical Chemistry, 2015

Nonequilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) is a versatile tool for studying affinity binding. Here we describe a NECEEM-based approach for simultaneous determination of both the equilibrium constant, Kd, and the unknown concentration of a binder that we call a ...

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Detection of Bromine by ICP-oa-ToF-MS Following Photochemical Vapor Generation

17-Feb-2015 | Ralph E. Sturgeon, Analytical Chemistry, 2015

A unique flow-through photochemical reactor is utilized for the generation of volatile methyl bromide from aqueous solutions of bromide and bromate ions in a medium of 2% acetic acid containing 3000 μg/mL NH4Cl. The volatile product is transported to a thin-film gas–liquid phase separator and ...

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Sensing Remote Chirality: Stereochemical Determination of β‐, γ‐, and δ‐Chiral Carboxylic Acids

12-Feb-2015 | Marina Tanasova, Mercy Anyika, Babak Borhan, Angewandte Chemie International Edition, 2015

Abstract Determining the absolute stereochemisty of small molecules bearing remote nonfunctionalizable stereocenters is a challenging task. Presented is a solution in which appropriately substituted bis(porphyrin) tweezers are used. Complexation of a suitably derivatized β‐, γ‐, or δ‐chiral ...

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Exploring Molecular Insights into Aggregation of Hydrotrope Sodium Cumene Sulfonate in Aqueous Solution: A Molecular Dynamics Simulation Study

10-Feb-2015 | Shubhadip Das; Sandip Paul, Journal of Physical Chemistry B, 2015

Hydrotropes are an important class of molecules that enhance the solubility of an otherwise insoluble or sparingly soluble solute in water. Besides this, hydrotropes are also known to self-assemble in aqueous solution and form aggregates. It is the hydrotrope aggregate that helps in solubilizing ...

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A fragmentation and reassembly method for ab initio phasing

09-Feb-2015 | Rojan Shrestha, Kam Y. J. Zhang, Acta Crystallographica Section D, 2015

Ab initio phasing with de novo models has become a viable approach for structural solution from protein crystallographic diffraction data. This approach takes advantage of the known protein sequence information, predicts de novo models and uses them for structure determination by molecular ...

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Multinuclear Diffusion NMR Spectroscopy and DFT Modeling: A Powerful Combination for Unraveling the Mechanism of Phosphoester Bond Hydrolysis Catalyzed by Metal‐Substituted Polyoxometalates

04-Feb-2015 | Thi Kim Nga Luong, Pavletta Shestakova , Tzvetan T. Mihaylov, Gregory Absillis, Kristine Pierloot, Tatjana N. Parac‐Vogt, Chemistry - A European Journal, 2015

Abstract A detailed reaction mechanism is proposed for the hydrolysis of the phosphoester bonds in the DNA model substrate bis(4‐nitrophenyl) phosphate (BNPP) in the presence of the ZrIV‐substituted Keggin type polyoxometalate (Et2NH2)8[{α‐PW11O39Zr(μ‐OH) (H2O)}2]⋅7 H2O (ZrK 2:2) at pD 6.4. ...

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