Buffers for the physiological pH range: Thermodynamic constants of substituted aminopropanesulfonic acids from 5 to 55°C

ThepK ₂ values for 3-[(l,l-Dimethyl-2-hydroxymethyl)amino]-2-hydroxypropanesulfonic acid (AMPSO), and 3-[N,N-Bis(-hydroxyethyl)amino]-2-hydroxypropanesulfonic acid (DIPSO) have been determined at 12 temperatures over the range 5 to 55‡C by measurements of the emf of cells without liquid junction containing hydrogen and silver-silver chloride electrodes. The values of pK ₂ for AMPSO and DIPSO were found to be 9.138 and 7.576, respectively, at 25‡C. The thermodynamic quantities, δG‡, δH‡, δS‡, and δC _p ^‡ were calculated from the change of the equilibrium constants with temperature. These buffer substances are useful as secondary pH standards in the physiological region of pH 7 to 9. Camille and Henry Dreyfus Fellow, 1994–1996.     

Thermodynamic Properties of Alanylpeptide Buffer Systems and Their Potential as Standards in Biological Applications

The second dissociation constants pK ₂of the NH₃ ⁺charge center of the alanylpeptides, alanylglutamine (Ala–Gln), alanylleucine (Ala–Leu), alanylglycine (Ala–Gly), and DL-alanyl–DL-methionine (DL-Ala–DL-Met) were determined at ten temperatures in the range, 5–50°C. These pK ₂values were calculated from the emf of cells containing buffer solutions of these dipeptides. A cell of the type described by Harned and Ehlers,⁽¹⁾utilizing hydrogen and silver–silver bromide electrodes was used. The thermodynamic quantities, H^o, S^o, and C_p ^owere derived from the temperature coefficients of the dissociation constants. The pK ₂values at 25°C, 8.2105 ( Ala–Gln), 8.2668 ( Ala–Leu), 8.2940 ( Ala–Gly), and 8.3054 ( DL-Ala–DL-Met). These values show that different substituent groups on the -carbon atom (which include polar and nonpolar groups), have a small effect on the dissociation of the NH₃ ⁺charge center. These compounds were also found to be suitable as buffers in the pH range(7–9). The thermodynamics of the solute–solvent interaction is interpreted in terms of the mixture model.⁽²⁾     

Calculation of reference pH values for standard solutions from the corresponding acid dissociation constants

Making the simplest possible assumption about the activity coefficient of the charged species, pH values of standard buffer solutions have been evaluated from the thermodynamic acidity constants, K, of the weak acids involved. A general equation is given for a triprotic acid, H₃A, as it can be simplified to derive the equations for other systems. A computer program for the solution of the equation was written giving m_H values, species distribution coefficients, α, buffer capacities, β, species activity coefficients, γ, and ionic strength, I. Iteration was continued until agreement between successive values to within 1 ± 10^?6 was reached.The activity coefficients of singly charged ions were taken as equal to γ_Cl, where log γ_Cl=?AI^1/2 (1 + 1.5I^1/2), which is the Bates-Guggenheim convention, and those of doubly and triply charged ions were given by the valence relations of the Debye-Hückel theory as γ⁴_Cl and γ⁹_Cl, respectively.     

Mass distribution, polydispersity, and focusing properties of carrier ampholytes for IEF. Part V: pH 9-11 interval

As a last part of an investigation on all 2-pH-unit intervals of carrier ampholytes (CAs) for IEF (see Electrophoresis 2006, 27, 3919-3934; 2006, 27, 4849-4858; 2007, 28, 715-723) two different lots of Servalyt CAs, in the pH 9-11 range, have been analyzed by a 2-D technique based on preparative Rotofor fractionation followed by capillary electrophoresis mass-spectrometry of 10 out of 20 fractions harvested, in the second dimension. The findings: the two lots contain 65 and 69 different M(r) compounds, in the M(r) interval of 232-667 Da, for a total of 341-387 isoforms, respectively. Since this is a chaotic organic synthesis, the high reproducibility (here demonstrated for the first time during the 40 years of existence of CAs) of the synthetic process (for two batches produced at 6 years of distance) is remarkable, considering that a 94% agreement for the individual chemicals and 88% agreement for the total number of isoforms for the two lots is found. It is additionally demonstrated that the lower pI species are accompanied by considerably more isoforms than the high pI forms and that in all cases such isoforms consist of family of compounds clustered around the pI of the parental form, with a pI spread of ca. 0.1-0.2 pH units.     

酸碱滴定：滴定剂液滴尺寸与滴定突跃

存在滴定突跃是滴定分析可以进行的先决条件。国内教科书讨论突跃范围的概念时均利用了滴定分数100±0.1%的条件,即按照滴定分数99.9%和100.1%来计算突跃范围。实际上,滴定过程中滴定剂是以液滴为单位加入到被测溶液中的,指示剂滴定法中也是以一滴或半滴标准溶液加入后被测溶液颜色发生改变来确定终点的,因此,按照化学计量点前后欠缺或过量半滴标准溶液来计算突跃范围更具科学性和实用价值。本文将计量点附近单滴滴定剂加入被测溶液引起的p H变化定义为突跃范围。对强碱滴定一元强酸体系的突跃范围进行了数学计算。结果表明,突跃范围与被测溶液的体积和浓度、滴定剂的浓度和液滴尺寸、被测溶液和滴定剂的浓度比等因素都有密切相关性,给出了不同于教科书的某些重要结论,这些新结论与实际滴定情形相符,对指导滴定分析具有重要参考价值。     

Buffers for the Physiological pH Range: Studies of 4-(N-Morpholino)butanesulfonic Acid (MOBS) from 5 to 55 °C

In this study, we report the pH values of two buffer solutions without chloride ion and eight buffer solutions with NaCl with an ionic strength I=0.16 mol?kg^?1. Electromotive force (emf) techniques have been used to get the cell potentials at 12 temperatures from 5 to 55?°C, including 37?°C. An extended form of the Bates-Guggenheim convention is used in the entire ionic strength range, 0.04 to 0.16?mol?kg^?1. The residual liquid junction potentials (??E _j ) of the buffer solutions of MOBS have been estimated from previous measurements with a flowing junction cell. These values of ??E _j have been used for correction in order to ascertain the operational pH values of four buffer solutions of MOBS at 25 and 37?°C. These solutions are recommended as pH standards for physiological application in the pH range 7.4 to 7.7.     

高效热管传热工质的热力学研究

用精密绝热量热法测量了高效热管传热工质在78～320 K温区内的热容.结果表明，在78.41～245.19 K， Cp/(J•K－1•g－1)=0.5369T＋0.07279.在274.08～318.51 K， Cp/(J•K－1•g－1)=3.403±0.020.在245～274 K， 高效热管传热工质发生固液相变.其相变温度、相变焓和相变熵分别是271.21 K、353.6 J•g－1，和1.304 J•K－1•g－1.根据热容与温度的定量关系和热力学函数之间的关系，得到了以标准温度298.15 K为基准的高效热管传热工质的热力学函数.     

Ionization Constants of o-Phthalic Acid and Standard pH Values of Potassium Hydrogen Phthalate Buffer Solutions in Glycerol + Water Solvent Mixtures at Normal and Subzero Temperatures

Determination of primary standards for pH measurements in glycerol + water solventmixtures has been carried out based on reversible emf measurements of the cellPt|H₂|KHPh (m _PS) + KCl (m _Cl)|AgCl|Ag|Ptwhere KHPh denotes the potassium hydrogen phthalate buffer solution of molalitym _PS = 0.05 mol-kg^–1, at glycerol mass fractions w _G = 0.2 and 0.4, within thetemperature range –10 to 40°C. A multilinear regression procedure as a functionof electrolyte molality, glycerol mass fraction w _G, and temperature T has beenapplied for the data processing leading to the values of primary standards pH_PS.These can be represented by the following regression equationpH_PS = (4.007037±0.001113) + (3.55844±0.01776)x _G+(0.39622±0.01410)z + (4.3084±0.3377)z ²– (50.66±10.53)x _G z ² + (457.10±78.48)x _G ² z ²where z = (T – 298.15)/298.15. Parallel values of the first ionization constantof o-phthalic acid (H₂Ph; benzene-1,2-dicarboxylic acid, the parent acid of KHPh),which are essential for the above calculations, have been determined fromreversible emf measurements of the cellPt|H₂|H₂Ph (m ₁) + KHPh (m ₂) + KCl (m ₃)|AgCl|Ag|Ptover the range of solvent composition and temperatures mentioned above.     

Isoelectric buffers, part 3: determination of pKa and pI values of diamino sulfate carrier ampholytes by indirect UV-detection capillary electrophoresis

Ampholytes with close pK(a) values (i.e., good carrier ampholytes (CAs)) are needed as buffers in pH-biased isoelectric trapping (IET) separations. The syntheses of two families of such good CAs were reported recently. Members of the family of diamino sulfate ampholytes (first series) had pI values in the 5.7 < pI < 9.0 range. Members of the family of quaternary ammonium dicarboxylic acid ampholytes (second series) had pI values in the pI < 4.3 range. To further characterize the diamino sulfate ampholytes, their effective mobilities were measured by indirect UV-absorbance detection capillary electrophoresis in a series of background electrolytes (BGEs) with different pH values. The pK(a) and limiting ionic mobility values of the CAs were obtained by fitting these mobility values, as a function of the pH and the ionic strength of the BGEs, to the theoretical mobility expression. These diamino sulfates complete the list of CAs suitable for IET separations.     

Mass distribution, polydispersity and focusing properties of carrier ampholytes for IEF. III: pH 2.5-4 intervals

To study the molecular mass distribution and number of species in narrow-range (2-pH-unit wide, in the nominal pI 2-4 or 3-5 interval) carrier ampholytes from four commercial sources (Bio-Lyte, Servalyt, Ampholine and Pharmalyte), a 2-D technique was adopted, consisting of a preparative focusing step in a Rotofor instrument, followed by analysis of every other collected fraction (10 out of 20) by CE-MS. It was found that Ampholine pH 3.5-5 contains 105 different molecular mass (M(r)) compounds, in the M(r) interval 205-965 Da, for a total of 446 isoforms. Bio-Lyte pH 3-5 consists of 84 different M(r) species, in the M(r) range 216-965 Da, for a total of 383 isoforms. Servalyt pH 2-4 is made of 227 different M(r) compounds, in the M(r) interval 204-929 Da, for a total of 1201 isoforms. Pharmalyte pH 2.5-5 comprises 245 amphoteres, in the M(r) range 203-857 Da, for a total of 857 isoforms. Pharmalyte appears to be the best brand, with the vast majority of species focusing sharply at their pI position and almost no 'poor' species, distributed along the entire pH gradient, denoting an extremely shallow pH/mobility curve across the pI value. Due to some overlap with the adjacent acidic pH 4-6 interval, the species in common have been evaluated: the most extended overlaps are found in Ampholine (55% of the species appearing in the two neighbouring intervals) and in Servalyt (47% coincidence). The lowest overlaps are found in Pharmalyte (23%) and in Bio-Lyte (20%).     

Reassessment of pH reference values with improved methodology for the evaluation of ionic strength

The conflict between pH as empirical number in routine control and the pH value regarded as conveying some information concerning the effective concentration or activity of hydrogen ions, a_H, has caused much confusion.There are, however, reasons to conclude that the overwhelming amount of thermodynamic data is not sufficiently accurate—either due to ignorance of metrological concepts or due to insufficiently specified measurement processes of fundamental chemical quantities pH.The commonly used seven reference buffer solutions to which primary pH values have been conventional assigned, represent a selection out of a more extensive list, recommended by NBS (now NIST) in 1962. From then onwards conventions concerning the Debye-Hückel model of electrolyte solutions and ionic strength have been revised and the pH(S) values reassessed in conformity but only for these seven reference buffer solutions. The others have, so far remained unchanged, locking harmonisation of the conventionally assigned pH(S) values.In this work, ionic strength is calculated through complete equations derived from the acidity constants. Concentrations of the various species involved in the conventional assignment of pH and their corresponding activity coefficients are therefore, more rigorously known. The process proves particularly useful for poliprotic acids with overlapping acidity constants, where the ratio is less than 10³.As a consequence, conventionally assigned pH values of reference buffer solutions are recalculated and corrections are introduced as appropriate.     

Addressing the Structural Complexity of Fluorinated Glucose Analogues: Insight into Lipophilicities and Solvation Effects

In this work, we synthesized all mono-, di-, and trifluorinated glucopyranose analogues at positions C-2, C-3, C-4, and C-6. This systematic investigation allowed us to perform direct comparison of ¹⁹F resonances of fluorinated glucose analogues and also to determine their lipophilicities. Compounds with a fluorine atom at C-6 are usually the most hydrophilic, whereas those with vicinal polyfluorinated motifs are the most lipophilic. Finally, the solvation energies of fluorinated glucose analogues were assessed for the first time by using density functional theory. This method allowed the log P prediction of fluoroglucose analogues, which was comparable to the C log P values obtained from various web-based programs.     

PSYCHE CPMG–HSQMBC: An NMR Spectroscopic Method for Precise and Simple Measurement of Long‐Range Heteronuclear Coupling Constants

Among the NMR spectroscopic parameters, long‐range heteronuclear coupling constants convey invaluable information on torsion angles relevant to glycosidic linkages of carbohydrates. A broadband homonuclear decoupled PSYCHE CPMG–HSQMBC method for the precise and direct measurement of multiple‐bond heteronuclear couplings is presented. The PSYCHE scheme built into the pulse sequence efficiently eliminates unwanted proton–proton splittings from the heteronuclear multiplets so that the desired heteronuclear couplings can be determined simply by measuring frequency differences between peak maxima of pure antiphase doublets. Moreover, PSYCHE CPMG–HSQMBC can provide significant improvement in sensitivity as compared to an earlier Zangger–Sterk‐based method. Applications of the proposed pulse sequence are demonstrated for the extraction of ⁿJ(¹H,⁷⁷Se) and ⁿJ(¹H,¹³C) values, respectively, in carbohydrates; further extensions can be envisioned in any J‐based structural and conformational studies.     

Fe/Fe3C Nanoparticles Encapsulated in N-Doped Hollow Carbon Spheres as Efficient Electrocatalysts for the Oxygen Reduction Reaction over a Wide pH Range

Nonprecious-metal-based electrocatalysts with low cost, high activity, and stability are considered as one of the most promising alternatives to Pt-based catalysts for the oxygen reduction reaction (ORR). Herein, an economical and easy-to-fabricate catalyst is developed, that is, Fe/Fe₃C embedded in N-doped hollow carbon spheres (Fe/Fe₃C/NHCS), which gave the half-wave potential of 0.84 V in 0.1 m KOH, similar to the commercial Pt/C catalyst. Surprisingly, the favorable ORR performance of the as-prepared catalyst was obtained in both acidic and neutral conditions with almost a four-electron pathway and low H₂O₂ yield, which desirable the development of the proton exchange membrane (PEM) and microbial electrolysis cell (MEC) technology. Additionally, the obtained catalyst demonstrated better long-term stability and high methanol tolerance over a wide range of pH. These features could be mainly attributed to the synergistic effect between Fe/Fe₃C and Fe-N_x sites, the hollow structure with mesopores, and the well-dispersed Fe/Fe₃C nanoparticles owing to the existence of the abundant hydrophilic groups within the HCS precursor. As such, designing an efficient and cheap ORR catalyst that can operate at alkaline, acidic, and neutral solutions is highly desirable, yet challenging.     

α‐FeOOH−MoO3 Nanorod for Effective Photo‐Fenton Degradation of Dyes and Antibiotics at a Wide Range of pH

It's highly significant to develop a novel catalyst, which can be active at a wide range of pH, for an effective photo‐Fenton reaction. In this work, α‐FeOOH?MoO₃ nanorod was prepared by a one‐step hydrothermal method and applied in photo‐Fenton degradation of organic pollutants. Benefit from the electron migration mechanism of Z‐scheme and excellent photoelectric performance, the catalyst exhibited superior photo‐Fenton activity in degradation of organic pollutants. In addition, the catalyst holds good stability after 5 recycles. These results demonstrated that this catalyst has wide application prospect in organic wastewater treatment.     

Computational Prediction of 1H and 13C NMR Chemical Shifts for Protonated Alkylpyrroles: Electron Correlation and Not Solvation is the Salvation

Prediction of chemical shifts in organic cations is known to be a challenge. In this article we meet this challenge for α-protonated alkylpyrroles, a class of compounds not yet studied in this context, and present a combined experimental and theoretical study of the ¹³C and ¹H chemical shifts in three selected pyrroles. We have investigated the importance of the solvation model, basis set, and quantum chemical method with the goal of developing a simple computational protocol, which allows prediction of ¹³C and ¹H chemical shifts with sufficient accuracy for identifying such compounds in mixtures. We find that density functional theory with the B3LYP functional is not sufficient for reproducing all ¹³C chemical shifts, whereas already the simplest correlated wave function model, Møller–Plesset perturbation theory (MP2), leads to almost perfect agreement with the experimental data. Treatment of solvent effects generally improves the agreement with experiment to some extent and can in most cases be accomplished by a simple polarizable continuum model. The only exception is the NH proton, which requires inclusion of explicit solvent molecules in the calculation.     

Calculation of Spectroscopic Constants for the Ground Electronic States of KRb and RbCs Molecules

The vibrational, rotational, and centrifugal constants have been calculated for the ground electronic states of KRb and RbCs molecules. The calculation is performed using the semiempirical potential curves constructed in a wide range of internuclear distances. The estimated spectroscopic constants are compared with experimental data.     

Statistical and Mathematical Investigations for Determining the Binding Constants of Micelle with Reactants Molecules from Kinetic Data

Binding constants between reactants molecules with micelles are considered to be important parameters particularly in micellar catalysis area. Recently, we developed a statistical method based on multiple linear regression for determining those parameters from kinetic data (Phys. Chem. Liq. 2008, 46, 34–46). In the present work, we derived further two statistical equations from the same original equation using also multiple linear regression method. A substantial difference has been found between the results of those equations and with that of the recently published one. This strongly indicates that the statistical procedures are not valid for such a purpose, that is, the available statistical and graphical methods in the literature are also not suitable for such treatment. A mathematical procedure using iterative method for evaluating the binding constants is introduced. An equation for such treatment has also been derived from the same original equation, and a computer program for this purpose has been written. Application of the developed method to the kinetic data has been found to be quite successful. It has been concluded that the presented mathematical method is simple, reliable, and accurate.     

Rational design of FLP catalysts for reversible H2 activation: A DFT study of the geometric and electronic effects

The thermodynamics of reversible H₂ activation could be controlled by adjusting substituents of LA group and using different polar solvents, which forges a guide to design potential FLPs catalysts for reversible H₂ activation.