Parahydrogen hyperpolarized NMR detection of underivatized short oligopeptides.

Parahydrogen hyperpolarization has evolved into a versatile tool in NMR, allowing substantial sensitivity enhancements in analysis of biological samples. Herein we show how its application scope can be extended from small metabolites to underivatized oligopeptides in solution. Based on a homologous series of alanine oligomers, we report on an experimental and DFT study on the structure of the oligopeptide and hyperpolarization catalyst complexes formed in the process.

Solution- and gas-phase study of binding of ammonium and bisammonium hydrocarbons to oxacalix[4]arene carboxylate.

Oxacalixarenes represent a distinctive class of macrocyclic compounds, which are closely related to the parent calixarene family, offering binding motifs characteristic of calixarenes and crown ethers. Nevertheless, they still lack extensive characterization in terms of molecular recognition properties and the subsequent practical applicability. We present here the results of binding studies of an oxacalix[4]arene carboxylate macrocycle toward a variety of organic ammonium cationic species.

On-off-on Control of Molecular Inversion Symmetry via Multi-stage Protonation: Elucidating Vibronic Laporte Rule.

The Laporte rule dictates that one- and two-photon absorption spectra of inversion-symmetric molecules should display alternatively forbidden electronic transitions; however, for organic fluorophores, drawing clear distinction between the symmetric- and non-inversion symmetric two-photon spectra is often obscured due to prevalent vibronic interactions. We take advantage of consecutive single- and double-protonation to break and then reconstitute inversion symmetry in a nominally symmetric diketopyrrolopyrrole, causing large changes in two-photon absorption. By performing detailed one- and two-photon titration experiments, with supporting quantum-chemical model calculations, we explain how certain low-frequency vibrational modes may lead to apparent deviations from the strict Laporte rule.

Novel Lipophilic Fluorophores with Highly Acidity-Dependent Two-Photon Response.

Lipophilic fluorophores are widely implemented in nonlinear microscopy; however, few existing membrane-specific probes combine the high brightness of two-photon excited fluorescence (2PEF) with pH sensitivity. Herein we describe four novel two-photon excited fluorophores, based on a coumarin 151 core structure, where lipophilicity is induced by a covalently attached phosphazene moiety. Changing the environmental acidity using trifluoromethanesulfonic (triflic) acid leads to profound changes in the linear fluorescence and 2PEF characteristics, due to chromophores' switching between neutral- and protonated forms.

Experimental and Computational Study of Aminoacridines as MALDI(-)-MS Matrix Materials for the Analysis of Complex Samples.

Monoaminoacridines (1-, 2-, 3-, 4-, and 9-aminoacridine) were studied for suitability as matrices in the negative ion mode matrix-assisted laser desorption/ionization mass spectrometry (MALDI(-)-MS) analysis of various samples. This is the first study to examine 1-, 2-, and 4-aminoacridine as potential matrix material candidates for MALDI(-)-MS. In addition, spectral (UV-Vis absorption and fluorescence), proton transfer-related (basicity and autoprotolysis), and crystallization properties of these compounds were characterized experimentally and/or computationally.

Validation and extension of the gas-phase superacidity scale.

Rationale: In recent years it has become increasingly evident that the previously reported experimental gas-phase acidity (GA) values of several strong acids differ markedly from the corresponding high-level computational values. In this work, the superacidic part of the current gas-phase acidity scale was validated and extended.

Methods: For that, the strongly acidic section of the gas-phase acidity scale was remeasured using the equilibrium Fourier transform ion cyclotron resonance (FTICR-MS) method, adding new compounds and introducing methodological changes.

Spontaneous Symmetry Breaking Facilitates Metal-to-Ligand Charge Transfer: A Quantitative Two-Photon Absorption Study of Ferrocene-phenyleneethynylene Oligomers.

Change of the permanent molecular electric dipole moment, Δμ, in a series of nominally centrosymmetric and noncentrosymmteric ferrocene-phenyleneethynylene oligomers was estimated by measuring the two-photon absorption cross-section spectra of the lower energy metal-to-ligand charge-transfer transitions using femtosecond nonlinear transmission method and was found to vary in the range up to 12 D, with the highest value corresponding to the most nonsymmetric system. Calculations of the Δμ performed by the TD-DFT method show quantitative agreement with the experimental values and reveal that facile rotation of the ferrocene moieties relative to the organic ligand breaks the ground-state inversion symmetry in the nominally symmetric structures.

TD-DFT calculations of one- and two-photon absorption in Coumarin C153 and Prodan: attuning theory to experiment.

We use TD-DFT to calculate the one-photon absorption (1PA) and two-photon absorption (2PA) properties of C153 and Prodan in toluene and DMSO, and benchmark different methods relative to accurate experimental data available from the literature on these particular systems. As the first step, we modify the range-separated TD-DFT to provide the best prediction for the peak 1PA wavelength, and then apply the optimized functionals to achieve quantitative predictions of the corresponding two-photon absorption cross section, σ, with an accuracy ∼10-20% in C153 and ∼20-30% in Prodan. To elucidate the origin of residual discrepancies between the theory and experimental observations, we invoked the two essential states model for σ, which allows us to verify not only the transition wavelength and the σ value, but also to quantitatively benchmark the calculation of key molecular parameters such as the transition dipole moment and the change of the permanent dipole moment.

Hydrogen-Bond Donicity in DMSO and Gas Phase and Its Dependence on Brønsted Acidity.

The hydrogen-bond (HB) donicity of various HB donors, expressed as standard Gibbs free energy of HB formation with chloride ion, was studied experimentally in dimethyl sulfoxide (DMSO) and computationally in DMSO and the gas phase. Acidity and HB donicity data in the gas phase and DMSO have been obtained for 77 HB donors from different compound families. Applicability of two computational methods (SMD and COSMO-RS) for calculation of solvation contribution to reaction free energy in DMSO was evaluated and discussed.

Acidity of Strong Acids in Water and Dimethyl Sulfoxide.

Careful analysis and comparison of the available acidity data of HCl, HBr, HI, HClO4, and CF3SO3H in water, dimethyl sulfoxide (DMSO), and gas-phase has been carried out. The data include experimental and computational pKa and gas-phase acidity data from the literature, as well as high-level computations using different approaches (including the W1 theory) carried out in this work. As a result of the analysis, for every acid in every medium, a recommended acidity value is presented.

Two-photon voltmeter for measuring a molecular electric field.

We present a new approach for determining the strength of the dipolar solute-induced reaction field, along with the ground- and excited-state electrostatic dipole moments and polarizability of a solvated chromophore, using exclusively one-photon and two-photon absorption measurements. We verify the approach on two benchmark chromophores N,N-dimethyl-6-propionyl-2-naphthylamine (prodan) and coumarin 153 (C153) in a series of toluene/dimethyl sulfoxide (DMSO) mixtures and find that the experimental values show good quantitative agreement with literature and our quantum-chemical calculations. Our results indicate that the reaction field varies in a surprisingly broad range, 0-10(7)  V cm(-1) , and that at close proximity, on the order of the chromophore radius, the effective dielectric constant of the solute-solvent system displays a unique functional dependence on the bulk dielectric constant, offering new insight into the close-range molecular interaction.

Calculations of pKa of superacids in 1,2-dichloroethane.

Acidity calculations for some CH and NH superacids in 1,2-dichloroethane (DCE) were carried out using SMD and COSMO-RS continuum solvation models. After comparing the results of calculations with respective experimental pK(a) values it was found that the performance of SMD/M05-2X/6-31G* method is characterized by the mean unsigned error (MUE) of 0.5 pK(a) units and the slope of regression line of 0.

IEF-PCM calculations of absolute pKa for substituted phenols in dimethyl sulfoxide and acetonitrile solutions.

Absolute (nonrelative) pKa calculations for substituted phenols were carried out in nonaqueous media, demonstrating the predictive power of the integral equation formalism PCM method with a mean unsigned error of 0.6 pKa units for DMSO and 0.7 pKa units for MeCN at the B3LYP/6-31+G** level of theory combined with the scaled B3LYP/6-311+G** gas-phase data.