The pKa theoretical estimation of C―H,N―H,O―H and S―H acids in dimethylsulfoxide solution

A scheme for the pK_a estimation of organic acids in dimethylsulfoxide (DMSO) solution based on quantum chemical calculations is proposed. The procedure of pK_a calculation requires several steps. The first is the calculation of the gas phase acidity of the compound. The G3MP2B3, G4MP2 as well as CBS‐QB3 composite methods made it possible to estimate values of gas phase acidities of an extensive set of structures with a high confidence level (standard deviations equal to 1.15, 1.13 and 1.29 kcal mol^?1, respectively; the test set included 91 compounds). The second step is the computation of the solvation correction with the integral equation formalism version of polarizable continuum model (IEF‐PCM)–B3LYP/6‐311+G(d,p) approximation. Within the bounds of our approach, the medium properties were covered only by the PCM model, i.e. the proposed procedure neglects specific interactions between DMSO and the solute. It was determined that the approach to pK_a estimation mentioned above is the most balanced in terms of accuracy, resource intensity and computation time cost. In the third step, the error of the pK_a calculation was decreased by correlation allowances. Correlation allowances were determined for each acid class (62 С―Н, 55 N―Н, 24 O―Н and 5 S―Н acids) in the range of 50 units in terms of logarithmic scale using the test set including 146 compounds. Seven O―H acids showing the ability to form cyclic dimers were separated into a discrete group. The proposed methodology was applied to the estimation of pK_a for trans‐ and cis‐dimethyl‐4,5‐dihydro‐3H‐pyrazol‐3,5‐dicarboxylates as well as for 5‐fluorouracil subject to competitive dissociation, the latter by N1―H or N3―H bonds. Copyright © 2014 John Wiley & Sons, Ltd.     

High-resolution infrared spectrum of CHD279Br: ro-vibrational analysis of the ν5 and ν9 fundamentals

ABSTRACT

The high-resolution infrared spectrum of CHD₂⁷⁹Br has been investigated by Fourier transform spectroscopy in the range 700–900?cm^?1 at an unapodized resolution of 0.0035?cm^?1. This spectral region is characterised by the absorptions of the ν₅ (814.5185?cm^?1) and ν₉ (716.9649?cm^?1) fundamental bands, corresponding to H–C–Br deformation and CD₂ rocking modes, respectively. The ν₅ vibration of symmetry species A^′ gives rise to an a-/c-hybrid band with a predominant a-type component, while the ν₉ mode of A^′′ symmetry produces a b-type envelope. The spectral analysis resulted in the identification of 5290 (J^′?≤?63 and K_a^′?≤?13) and 1657 (J^′?≤?53 and K_a^′?≤?12) transitions for ν₅ and ν₉ bands, respectively. The assigned data were fitted using the Watson’s S-reduced Hamiltonian in the I^r representation and the v₅?=?1 and v₉?=?1 state parameters up to the quartic centrifugal distortion terms have been obtained. From spectral simulations the dipole moment ratio |Δμ_a/Δμ_c| of the ν₅ band has been determined to be 1.4?±?0.1 while the intensity ratio between ν₅ and ν₉ fundamentals has been estimated to have a value of 4.3?±?0.5.     

Experimental and computational determination of Brønsted coefficients for equilibrium transfer of the O,O‐dimethyl phosphorothioyl group between oxyanion nucleophiles

An experimental determination of the β^Eq value for equilibrium transfer of the O,O‐dimethyl phosphorothioyl group between oxyanion nucleophiles in water and methanol at 25 °C is presented. The respective β^Eq values in the two solvents are experimentally the same at ?1.45 ± 0.08 and ?1.39 ± 0.12. Based on the observation that the Brønsted correlation for the nucleophilic reaction of phenoxides in water with substrate 1d (dimethyl 4‐nitrophenyl phosphorothioate, pK_a^HOAr of 7.14) is linear over the entire range of phenoxides employed (5.53 ≤ pK_a^Nu ≤ 12.38), the reaction for phenoxide nucleophiles displacing phenoxide leaving groups is probably concerted. The obtained data allow one to calculate, for a symmetrical transition state involving 2,4,5‐trichlorophenoxide as a nucleophile and leaving group, an approximately 60% P–OAr cleavage and about 40% P–Nuc bond formation. A computational method is presented for the rapid prediction of the β^Eq values for such processes in water and methanol, and the results are compared with known values from the literature. Copyright © 2011 John Wiley & Sons, Ltd.     

Investigation of ionization equilibria of L-aspartic and L-glutamic acids in water at a microscopic level by DFT method

The pK_a values of different dissociable groups of L-Aspartic and L-Glutamic acids in vacuo and in aqueous medium over a wide pH range have been estimated by DFT/B3LYP/6-31G(d) and 6-31G++(d,p) methods. For both the amino acids discrete water molecules (n?=?0, 3 and 6) have been used to get the first hydration sphere. Starting from a low pH, all possible tautomers resulting from each dissociation step are assumed to exist in a cyclic equilibrium. The structures of the species involved in the dissociation and tautomerization processes have been optimized in vacuo and also in aqueous medium considering H-bonded water molecules under the PCM formalism. For obtaining pK_a in aqueous medium the difference in Gibbs energy of the clusters H₃O⁺.mH₂O and (H₂O) _m+1 (m?=?an integer) is necessary and has been evaluated from computed literature data. Calculations reveal that in vacuo the neutral or less charged species predominate but in aqueous medium the zwitterionic or more chargeable forms contribute appreciably. The Gibbs energy changes for the microscopic cyclic equilibria have been estimated theoretically. These lead to overall (macroscopic) pK_a values for the ionization steps which are in good agreement with available experimental data for both the amino acids.     

Computational study of the proton affinity and basicity of structurally diverse α1‐adrenoceptor ligands

The α₁‐adrenoceptor is a target for the treatment of several conditions from hypertension to benign prostatic hyperplasia. In this paper, we describe a new analysis approach to explore the conformational space of several ligands of the α₁‐adrenoceptor and we also present the calculation of their proton affinity and basicity. For each compound a conformational search followed by a semi‐empirical optimisation was performed and a selection of conformations for each ligand was subjected to further optimisation using density functional theory methods. Different positions were explored to determine the favoured site of protonation, and then, the proton affinity (in the gas phase) and basicity (using the polarisable continuum model for the aqueous solution) were calculated for each of them. In addition, an alternative method using one explicit water molecule in combination with the polarisable continuum model for aqueous solvent was explored. Moreover, the acid dissociation constant (pK_a) in water of these 26 compounds was calculated because this is an important parameter for a ligand when binding to its receptor. The experimental pK_a values of six of these ligands and those of two compounds with a very low and a very large pK_a were used to validate the theoretical methodology. Copyright © 2011 John Wiley & Sons, Ltd.     

High-resolution FTIR spectroscopy of CHD279Br: ro-vibrational analysis of the v4 fundamental and determination of the ground state constants

The first high-resolution infrared spectrum of CHD₂⁷⁹Br has been investigated by Fourier transform spectroscopy in the range 940–1100 cm^?1 at an unapodised resolution of 0.0025 cm^?1. This spectral region is characterised by the v₄ (1036.8389 cm^?1) fundamental band, corresponding to the CD₂ wagging mode. The rotational structure of the a- and c-type components of the hybrid band has been extensively assigned for transitions involving values of J and K_a up to 65 and 15, respectively. The ground state constants up to the quartic centrifugal distortion terms have been obtained for the first time by ground state combination differences from 5251 assigned transitions and subsequently employed for the evaluation of the band origin and the excited state parameters of v₄. Watson’s S-reduced Hamiltonian in the I^r representation has been used in the ro-vibrational analysis. The dipole moment ratio |Δμ_a/Δμ_c| of the band has been estimated to be 1.3?±?0.1 from spectral simulations.     

Kinetic investigation on carbamate formation from the reaction of carbon dioxide with amino acids in homogeneous aqueous solution

The kinetics of carbamate formation from the reaction of carbon dioxide with α‐amino acids in D₂O was first investigated by means of nuclear magnetic resonance spectroscopy. Potassium carbonate was used as the CO₂ source. For each amino acid, the maximum carbamate yield, the apparent rate constant for the carbamate formation k_app, and the rate constants for the formation k₁ and the breakdown k_?1 of the carbamate were estimated. Plots of log k₁ or log k_?1 versus pK_a of amino acids indicated that the formation rate k₁ increased with the basicity (pK_a) of amino acid, while the decomposition rate k_?1 decreased. A Br?nsted β value of 0.39 was obtained from the former plot, being in good agreement with the previously reported ones (0.26–0.43). The observed negative pK_a dependence of log k_?1 (Br?nsted α = 0.34) is reasonable, because the carbamate decomposition is acid‐catalyzed and the steady‐state concentration of H⁺ should be higher for weaker basic amines. The charge (σ) and the lone‐pair energy (E_N) at the nitrogen atom of the amino group were calculated. Although log k₁ correlated with σ and E_N, log k_?1 was unrelated with both of these parameters. Considering that the carbamate formation (k₁) is not only base‐catalyzed but should also be promoted by the nucleophilicity of the amino nitrogen, its correlation with σ and E_N in addition to pK_a is rational. The irrelevance of log k_?1 to σ and E_N is not surprising, because σ and E_N are not a direct measure of [H⁺] of the solution. Copyright © 2011 John Wiley & Sons, Ltd.     

On kaonic hydrogen. Phenomenological quantum field theoretic model revisited

We argue that due to isospin and U-spin invariance of strong low-energy interactions the S-wave scattering lengths a ⁰ ₀ and a ¹ ₀ of ˉN scattering with isospin I = 0 and I = 1 satisfy the low-energy theorem a ⁰ ₀ +3a ¹ ₀ = 0 valid to leading order in chiral expansion. In the model of strong low-energy ˉN interactions at threshold (Eur. Phys. J. A 21, 11 (2004)) we revisit the contribution of the Σ(1750) resonance, which does not saturate the low-energy theorem a ⁰ ₀ +3a ¹ ₀ = 0, and replace it by the baryon background with properties of an SU(3) octet. We calculate the S-wave scattering amplitudes of K^-N and K^-d scattering at threshold. We calculate the energy level displacements of the ground states of kaonic hydrogen and deuterium. The result obtained for kaonic hydrogen agrees well with recent experimental data by the DEAR Collaboration. We analyse the cross-sections for elastic and inelastic K^-p scattering for laboratory momenta 70MeV/c < p _K < 150MeV/c of the incident K^--meson. The theoretical results agree with the available experimental data within two standard deviations.     

A new study of the ν 2(A 1) infrared band of phosphorus trifluoride

The high-resolution Fourier transform infrared spectrum of phosphorus trifluoride (PF₃) has been reinvestigated in the v_2?=?1 vibrational excited state near 487?cm^?1 (at a resolution of 3?×?10^–3?cm^–1). Thanks to our new accurate rotational ground-state C ₀ value, 0.159970436(69)?cm^–1, and to recent pure rotational measurements, 318 new infrared transitions of the ν ₂ fundamental band have been assigned, extending the rotational quantum number values up to K _max?=?71 and J _max?=?72. A merge, for the first time, of 135 reported microwave data (K _max?=?42 and J _max?=?49) within the v_2?=?1 excited level and 2860 rovibrational transitions yielded improved constants of ν ₂. Parameters of this band have been obtained, up to sextic centrifugal distortion constants, by least-squares fits, σ _IR?=?3.60?×?10^–4?cm^–1 and σ _MW?=?5.53?×?10^–6?cm^–1 (166?kHz). Comparison of these constants with those measured previously by infrared spectroscopy reveals orders of magnitude higher accuracy of these new values.     

Kinetics and mechanism of the anilinolysis of aryl 4‐nitrophenyl thionocarbonates in aqueous ethanol

The reactions of bis(4‐nitrophenyl), 3‐chlorophenyl 4‐nitrophenyl, and 3‐methoxyphenyl 4‐nitrophenyl thionocarbonates ( 1 , 2 , and 3 , respectively) with a series of anilines are subjected to a kinetic investigation in 44 wt.% ethanol–water, at 25.0 °C and an ionic strength of 0.2 M. Under aniline excess, pseudo‐first‐order rate coefficients (k_obs) are found. Plots of k_obs versus aniline concentration are linear, with the slopes (k_N) pH independent, k_N being the rate coefficient for the anilinolysis of the thionocarbonates. The Brønsted plot (log k_N vs. pK_a of anilinium ions) for thionocarbonate 1 is linear, with slope (β) 0.62, which is consistent with a concerted mechanism. The Brønsted plots for thionocarbonates 2 and 3 are curved, with slopes 0.1 at high pK_a for both reaction series and slopes 0.84 and 0.79 at low pK_a for the reactions of 2 and 3 , respectively. The latter plots are in accordance to stepwise mechanisms, through a zwitterionic tetrahedral intermediate (T^±) and its anionic analogue (T^?), the latter being formed by deprotonation of T^± by the basic form of the buffer (HPO). The Brønsted curves are explained by a change in the rate‐limiting step, from deprotonation of T^± at low pK_a, to its formation at high pK_a. The influence of the amine nature and the non‐leaving and electrophilic groups of the substrate on the kinetics and mechanism is also discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Positron annihilation in polycrystalline metals

The empirical relation θ _p ⁶ /I _p=aK (where θ _p is the limiting angle of the parabolic component in the angular distributions of annihilation photons in metals, I _p is the integrated contribution of this component, K=1, 2, 3, ... is an integer, and a is a constant independent of the type of metal) observed earlier has been tested on magnesium, aluminum, copper, zinc, lead, and bismuth samples. The validity of this relation has been substantiated. The value of the dimensionless constant a has been determined and was found to coincide within experimental error with the result obtained in previous measurements. It is shown that the value of K for the same metal but for different samples may be different. It is conjectured that this may be due to different defect concentrations in samples. Fiz. Tverd. Tela (St. Petersburg) 40, 600–602 (April 1998)     

Relationship between experimental pKa values in aqueous solution and a gas phase bond length in bicyclo[2.2.2]octane and cubane carboxylic acids

Linear correlations were established between the calculated bond lengths and the pK_a or σ_I values for a series of 4‐substituted bicyclo[2.2.2]octane‐1‐carboxylic acid and 4‐cubane‐1‐carboxylic acid derivatives. The bond lengths have been calculated at a modest computational level, HF/6‐31G(d), both in the gas phase and with the continuum solvation model, polarisable continuum model (PCM). In general, the best correlations are obtained when the PCM model is taken into account, especially when neutral and charged molecules are considered together. The best models in each case show square correlation coefficients (R²) larger than 0.9 and indicate that they can be used as predictive tools. These results expand previous results that indicate the possibility of a relationship between gas phase bond length and pK_a values in aqueous solution and indicate that such relationships are more general than hitherto expected. Copyright © 2013 John Wiley & Sons, Ltd.     

Stability of One-Electron Molecules in the Brown–Ravenhall Model

In appropriate units, the Brown-Ravenhall Hamiltonian for a system of 1 electron relativistic molecules with K fixed nuclei having charge and position Zk, R_k, k=1,2, ?,Kk=1,2, \ldots,K, is of the form \bB_1,K = L₊ ( D₀ + aV_c) L₊ \bB_{1,K}= \Lambda_+ \bigl( D_0 + \alpha V_c\bigr) \Lambda_+ , where v₊ is the projection onto the positive spectral subspace of the free Dirac operator D₀ and V_c = - ?_k=1^K \fracaZ_k\lmod \bx-R_k \rmod + ?_{k < l,  k,l=1}^K \fracaZ_k Z_l\lmod R_k-R_l \rmod V_c= - \sum_{k=1}^K \frac{\alpha Z_k}{\lmod \bx-R_k \rmod} + \sum_{kZ_k ￡ aZ_c = \frac2p/2 + 2/ p\alpha Z_k \leq \alpha Z_c = \frac{2}{\pi /2 + 2/ \pi}, k=1,2, ?,Kk=1,2, \ldots,K, and a ￡ \frac2 p(p²+4)(2+?{1+ p/2})\alpha \leq \frac{2 \pi}{(\pi^2+4)(2+\sqrt{1+ \pi /2})}, \ \bB_1,K 3 \operatornameconst \cdotp K\bB_{1,K} \geq \operatorname{const} \cdotp K.     

NMR studies on hydrogen bonding and proton transfer in Mannich bases

A review of studies on the ortho Mannich bases containing various substituents in the phenyl ring on the basis of¹H,¹³C and¹⁵N nuclear magnetic resonance (NMR) spectra in various solvents over the temperature range 110–298 K is presented. Some new results are also included. The data gathered so far show that there is some critical (inversion) range of ΔpK _a (= pK _a(NH⁺) − pK _a(OH)) in which the proton transfer equilibrium appears. This inversion range is well reflected in the behaviour of secondary deuterium isotope effect in¹³C NMR spectra. A strong temperature effect on the strength of hydrogen bonding should be emphasized. The¹H chemical shift for trichloroderivative increases from 13.5 at room temperature up to 17 ppm at 130 K when the proton is equally shared between the bridging atoms (¹ J(¹H,¹⁵N) = 30–40 Hz). The potential for the proton motion in such bridges is discussed taking into account the behaviour in the ultraviolet and infrared spectra. The role of dimerization in proton transfer equilibria is shown. In addition the rotation of OH groups involved in hydrogen bond formation and nitrogen pyramidal inversion was studied by the¹H dynamical NMR spectra.     

The kappa in J/Ψ↦K<Superscript>+</Superscript>π

BES II data for J/Ψ↦K ^*(890)Kπ reveal a strong κ peak in the Kπ S-wave near threshold. Both magnitude and phase are determined in slices of Kπ mass by interferences with strong K ₀(1430), K ₁(1270) and K ₁(1400) signals. The phase variation with mass agrees within errors with LASS data for Kπ elastic scattering. A combined fit is presented to both BES and LASS data. The fit uses a Breit-Wigner amplitude with an s-dependent width containing an Adler zero. The κ pole is at (760±20(stat)±40(syst)) - i(420±45(stat)±60(syst)) MeV. The S-wave I = 0 scattering length a ₀ = 0.23±0.04 m _π ^-1 is close to the prediction 0.19±0.02 m _π ^-1 of Chiral Perturbation Theory at O(p ⁴). An erratum to this article can be found at .     

In-situ X-ray diffraction study on β-CrOOH at high pressure and high-temperature

ABSTRACT

High pressure hydrous phases with distorted rutile-type structure have attracted much interest as potential water reservoirs in the Earth’s mantle. An in-situ X-ray diffraction study of β-CrOOH was performed at high pressures of up to 6.2?GPa and high-temperatures of up to 700?K in order to clarify the temperature effect on compression behaviors of β-CrOOH. The P-V-T data fitted to a Birch–Murnaghan equation of state yielded the following results: isothermal bulk modulus K_T0?=?191(4)?GPa, temperature derivative (?K_T/?T)_P?=??0.04(2)?GPa?K^?1, and volumetric thermal expansion coefficient α?=?3.3(2)?×?10^?5?K^?1. In this study, at 300?K, the a-axis became less compressible at pressures above 1–2?GPa. We found that the pressure where the slopes of a/b and a/c ratios turned positive increased with temperature. This is the first experimental study indicating the temperature dependence of the change in the axial compressibility in distorted rutile-type M³⁺OOH.     

Relationship between Hansen Solubility Parameters and Lewis Acid–Base Parameters of Polymers

Hansen solubility parameters and Lewis acid–base parameters are two groups of parameters that are used to characterize solvents, polymers, and the interactions between polymer matrix and additives. Although their definitions are very different, they can well explain the interactions in polymer composites. Therefore, some relations should exist between them. In this paper, the Lewis acid–base parameters of three polymers (PET, PS, and PVA) were measured by IGC technique. Including five other polymers (PE, PMMA, PC, PVC, and PVDF), the relationship between total Lewis acid–base intensity (K _a+K _b) and total polar intensity (δ² _p+δ² _h) of the eight kinds of polymers are discussed, where δ_p and δ_h are the polar components of the Hansen parameters. It is found that these polymers are all Lewis base polymers according to the values of K _b/K _a. Generally, a polymer with a larger (K _a+K _b) value possesses a higher (δ² _p+δ² _h) value.     

Theoretical estimation of the aqueous pKas of thiols

The ionisation state of a compound is a key parameter influencing the compound's activity as a drug, metabolite, pollutant, or other active chemical agent. Sulfhydrol compounds (thiols) tend to be considerably more acidic than their hydroxyl (alcohol) analogues. In this report, quantum chemical approaches previously used for the estimation of the aqueous pK_as of alcohols are applied to the estimation of the acidities of thiols. Acidity estimates obtained from the general-purpose SPARC calculational programme (S.H. Hilal, S.W. Karickhoff, and L.A. Carreira, Quant. Struct.-Act. Relat. 14, 348 (1995)) and the ACD/Labs PhysChem Suite v12 programme package are employed as benchmarks. Quantum chemical calculations were performed using both the semiempirical RM1 method and the density functional theory B3LYP/6-31+G^* method. The effectiveness of the SM5.4 and SM8 solvent models in estimating the aqueous-phase acidities was also evaluated. All of the approaches examined demonstrated strong correlations with the experimental acidity values.     

High-resolution FTIR spectra of CH2 = CClF in the 930-1050 cm−1 region

The gas-phase infrared spectra of natural CH₂ = CClF have been measured in the v ₆ and 2v ₁₂ band regions (930–1050 cm^?1) by high-resolution Fourier transform spectroscopy at room temperature. 1-Chloro-1-fluoroethylene is a planar asymmetric rotor (κ = ?0.54) belonging to the symmetry point group C_s and the vibrations investigated of symmetry species A′ give rise to a/b-hybrid bands with contributions of comparable intensity from both the components.

The rovibrational analysis of the fine structure led to the identification of 1894 (J ? 73, K_a ? 20) and 718 (J ? 53, K_a ? 8) transitions for the v ₆ and 2v ₁₂ bands of the ³⁵Cl isotopic species, respectively. Using the Watson's A-reduction Hamiltonian in the I^r representation a set of accurate spectroscopic parameters for both the excited states u ₆ = 1 and u12 = 2 of ³⁵Cl has been obtained for the first time. Transitions of ³⁷Cl isotopomer could also be assigned in the Q branch region of the 2v ₁₂ overtone; the determined band origin shift of 0.782 cm^?1 towards the lower wavenumbers led to describing the v ₁₂ fundamental as a vibration mainly involving the CFCl bending motion.