A study of solute-solute interactions of amides dissolved in N-methylformamide by enthalpic interaction coefficients

Enthalpies of dilution of formamide, acetamide, propionamide, butyramide and hexanamide, dissolved in N-methylformamide have been measured calorimetrically at 25°C. From the results McMillan-Mayer coefficient related enthalpic pair and triplet interaction coefficients have been calculated. Except for those of formamide, all pair coefficients are negative, whereas the triplet terms are positive. The values in the protic solvent N-methylformamide presented in this paper together with those published before are compared with results for corresponding solutes dissolved in the aprotic solvent N,N-dimethylformamide. A discussion of the dependence of the interaction coefficients on the applied concentration scale is given and conversion factors are presented. The influence of hydrogen bonding, of substituent effects on this hydrogen bonding, and of polarophobic interaction is discussed. The latter is comparable in N,N-dimethyl-and N-methylformamide. The enthalpic pair interaction coefficients have been correlated with the Excess Group Additivity approach.To whom correspondence should be addressed.     

Enthalpies of dilution of N,N-dialkylformamides dissolved in formamide,N-methylformamide,and N-methylacetamide

The enthalpies of dilution of N,N-dimethylformamide, N,N-diethylformamide, N,N-dipropylformamide, N,N-dibutylformamide, and N,N-dipent-ylformamide dissolved in formamide, N-methylformamide, and N-methylacetamide have been measured calorimetrically. From these, enthalpic interaction coefficients have been calculated, which were interpreted also in terms of an additivity model.     

Enthalpic Interaction Coefficients of Formamide in Aqueous Methanol and Ethanol Solutions at 298.15 K

The dilution enthalpies of formamide in aqueous methanol and ethanol solutions have been determined using a CSC-4400 isothermal calorimeter at 298.15 K. The homogeneous solution enthalpic interaction coefficients have been calculated over a range of alcohol concentrations according to the excess enthalpy concept. The results show that the enthalpic pair interaction coefficients h ₂ of formamide are negative in aqueous alcohol solutions and pass through a minimum in mixed solvents, whereas the h ₂ coefficients of formamide in aqueous ethanol solutions are more negative than those in aqueous methanol solutions. The results are discussed in terms of solute-solute and solute-solvent interactions.     

Chiral recognition between enantiomeric α-aminoacids. A calorimetric study at 25°C

Homotactic and heterotactic enthalpic pair interaction coefficients were determined at 25°C from the enthalpies of dilution of binary and ternary aqueous solutions containing the L and D forms of -aminoacids bearing alkyl chains of increasing length (alanine, -aminobutyric acid, valine, norvaline, leucine, isoleucine and norleucine). Significant differences were found between the values of the homotactic (h _DD or h _LL ) and heterotactic (h _DL ) pairwise coefficients, for the enantiomers of leucine and its isomers. The role of the zwitterionic interactions is discussed to explain the nature of the chiral recognition.     

甲酰胺在乙二醇-水混合溶剂中的稀释焓

酰胺是肽的基本结构单元, 而且在蛋白质的二级结构中与酰胺联系的氢键对蛋白质的稳定起着十分重要的作用. 作为蛋白质模型化合物热力学性质研究的一部分, 报道了甲酰胺在乙二醇水溶液中的稀释焓.      

Solute-solute interactions in non-aqueous solvents. Enthalpic interaction coefficients of substituted acetamides dissolved in N,N-dimethylformamide

Enthalpies of dilution of acetamide, N-methylacetamide, N-ethylacetamide, N-propylacetamide, N-butylacetamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide and N,N-dibutylacetamide dissolved in N,N-dimethylformamide as solvent have been measured calorimetrically at 25°C. The results are interpreted in terms of the McMillan-Mayer theory. The enthalpic interaction parameters are obtained for pairs, triplets and some quadruplets of solute molecules. All enthalpic pair interaction coefficients but one in this non-aqueous solvent are negative, whereas the triplet coefficients are positive. The concept of ‘solvophobic interaction’ can be used to explain these results in connection with the assumption of the formation of solute-solvent associates. The enthalpic pair interaction coefficients can be described by the additivity approach of Savage and Wood.     

The enthalpies of solution of L-α-alanyl-L-α-alanine in water-organic solvent mixtures at 298.15 K

The integral enthalpies of solution (T = 298.15 K) of L-α-alanyl-L-α-alanine in aqueous-organic solvents (acetonitrile, 1,4-dioxane, acetone, formamide, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, and N,N-dimethylsulfoxide) were measured at organic component concentrations x ₂ = 0–0.3 mole fractions. The standard enthalpies of solution (Δ_sol H ^o) and transfer (Δ_tr H ^o) of the peptide from water into mixed solvents were calculated. The influence of the structure and properties of solutes and mixture composition on solute thermochemical characteristics is considered. The enthalpy pair interaction coefficients h _xy between L-α-alanyl-L-α-alanine and organic solvent molecules were calculated. The linear Kamlet-Taft four-parameter equation was used to reveal correlation between the h _xy values and the properties of organic solvents.     

On the role of the functional group in determining the strength of hydrophobic interactions in aqueous solutions of α-amino acid derivatives

Calorimetric measurements were carried out at 25°C on binary aqueous solutions containing N-acetyl derivatives of the following -amino acids: glycine, alanine, valine, leucine, norleucine, aspartic acid, glutamic acid, phenylalanine, methionine, asparagine, glutamine, cysteine, histidine, serine. The N-acetyl derivative of the -amino acid proline was also studied. The results obtained have been used to calculate the pairwise enthalpic interaction coefficients and these are compared with results reported in the literature concerning free -amino acids, and their acetylamide derivatives. The coefficients largely increase passing from free amino acids to N-acetyl derivatives. The derivatives of -amino acids bearing unsubstituted alkyl chains present an increased cooperativity of hydrophobic interactions.     

Solvation of amides of carboxylic acids in aqueous solutions of ethylene glycol

Enthalpies of solution of amides of formic, acetic, and propionic acids with different degrees of N-substitution in aqueous solutions of ethylene glycol were measured at 298.15 K. The concentration of ethylene glycol did not exceed 4 mol kg^–1. The reasons for increasing endothermic values of the enthalpies characterizing the amide transfer from water to a mixed aqueous-organic solvent on going from primary to tertiary amides and from formamides to the corresponding acetamides are discussed. The enthalpic coefficients of pair interactions between amides and ethylene glycol in water were calculated. The endothermicity of the interaction of the alkyl groups of the amide molecules with ethylene glycol results in positive values of the coefficients. The coefficient values increase with the enhancement of the hydrophobic properties of hydrophilic non-electrolytes (urea, formamide, ethylene glycol) due to an increase in the contribution of the hydrophobic component and a decrease in the contribution from the interaction of the polar groups of amides to the total interaction.     

The agonistic binding site at the histamine H2 receptor. II. Theoretical investigations of histamine binding to receptor models of the seven α-helical transmembrane domain

Summary In the first part (pp. 461–478 in this issue) of this study regarding the histamine H₂ receptor agonistic binding site, the best possible interactions of histamine with an -helical oligopeptide, mimicking a part of the fifth transmembrane -helical domain (TM5) of the histamine H₂ receptor, were considered. It was established that histamine can only bind via two H-bonds with a pure -helical TM5, when the binding site consists of Tyr¹⁸²/Asp¹⁸⁶ and not of the Asp¹⁸⁶/Thr¹⁹⁰ couple. In this second part, two particular three-dimensional models of G-protein-coupled receptors previously reported in the literature are compared in relation to agonist binding at the histamine H₂ receptor. The differences between these two receptor models are discussed in relation to the general benefits and limitations of such receptor models. Also the pros and cons of simplifying receptor models to a relatively easy-to-deal-with oligopeptide for mimicking agonistic binding to an agonistic binding site are addressed. Within complete receptor models, the simultaneous interaction of histamine with both TM3 and TM5 can be analysed. The earlier suggested three-point interaction of histamine with the histamine H₂ receptor can be explored. Our results demonstrate that a three-point interaction cannot be established for the Asp⁹⁸/Asp¹⁸⁶/Thr¹⁹⁰ binding site in either of the investigated receptor models, whereas histamine can form three H-bonds in case the agonistic binding site is constituted by the Asp⁹⁸/Tyr¹⁸²/Asp¹⁸⁶ triplet. Furthermore this latter triplet is seen to be able to accommodate a series of substituted histamine analogues with known histamine H₂ agonistic activity as well.     

Chiral recognition in aqueous solutions: On the role of urea in hydrophilic and hydrophobic interactions of unsubstituted α-amino acids

Calorimetric and nuclear relaxation time measurements were carried out at 25°C on concentrated aqueous solutions of urea containing the L and D forms of the following -aminoacids: alanine, -aminobutyric acid, norvaline, and norleucine. Glycine was also studied under the same experimental conditions. The enthalpic interaction coefficients were rationalized according to the preferential configuration model. The trends of the homochiral coefficients at increasing concentration of urea underline an interaction mechanism not different from that occurring in water. Chiral recognition is the quantity more affected by the nature of the solvent. Among the amino acids studied, only norleucine presents this effect, which vanishes at the highest concentrations of urea because the attenuated electrostatic interactions cannot impose preferential configurations.     

Excess enthalpies of aqueous solutions of small peptides at 25°C

Heats of dilution of aqueous solutions of the following di-and tripeptides were determined at 25°C over a wide concentration range: -alanyl-glycine, -alanyl--alanine, DL--alanyl-glycine, glycyl-DL--alanine, L--alanyl-L-alanine, DL--alanyl-DL--alanine, DL--alanyl-DL-valine, DL--alanyl--alanine, glycyl--aminobutyric acid, glycyl-L-leucine and DL--alanyl-glycylglycine. The excess enthalpies H^ex and partial molar relative enthalpies L₂ were calculated and enthalpy coefficients of intermolecular interaction were analysed using the additivity principle of Savage and Wood. The concentration dependence of the enthalpic characteristics of peptide-peptide interactions is discussed based on of their hydrophobicity and hydrophilicity. The three-stage model of peptide association is described using enthalpic coefficients of intermolecular interactions.     

Enthalpic interaction coefficients of amides dissolved in N,N-dimethylformamide

Enthalpies of dilution of propionamide, butyramide, pentanamide, hexanamide, N-pentylacetamide, N,N-dipentylacetamide, N-ethylhexanamide and N,N-diethylhexanamide dissolved in N,N-dimethylformamide as solvent have been measured calorimetrically at 25°C. The results are interpreted in terms of the McMillan-Mayer theory. Enthalpic interaction parameters are obtained for pairs, triplets and some quadruplets of solute molecules. All enthalpic pair interaction coefficients are negative, whereas those for triplets are positive. For unsubstituted amides the change of the enthalpic coefficients with the number of C-atoms differs considerably from that of the substituted compounds. The concept of polarophobic interaction is used for the interpretation of the results in connection with the assumption of formation of solute-solvent associates. For solutes with longer alkyl chains the results cannot be described satisfactorily in terms of the additivity approach of Savage and Wood. Probably the pair interactions of these compounds are not the result of interaction in a random way. Also the linear dependence of the pair interaction coefficients of the larger molecules with the number of C-atoms and the results for the unsubstituted amides support the occurrence of preferential orientations for these compounds.     

Enthalpic pair interaction coefficients in DMF solution

Dissolution enthalpies of NaI in mixtures of N,N-dimethylformamide with urea, formamide, acetamide and N,N-dimethylacetamide were measured. The results were compared with data measured earlier for other DMF — non-electrolyte mixtures. The enthalpic pair interaction coefficients,h _xy (Na⁺I^? — non-electrolyte) in DMF were calculated and analysed together with the appropriate data concerning other Na⁺I^? — non-electrolyte pairs in DMF. The group interaction coefficients illustrating the interactions of Na⁺I^? with the CH₂, OH, O, CO, ‘Pep’ and ‘iPep’ groups were determined and discussed.     

Enthalpy parameters for interaction of small peptides with 18-crown-6 and aza-18-crown-6 in water at 25°C

Enthalpies of dilution have been determined for binary aqueous solutions of 1-aza-18-crown-6 as well as for ternary aqueous solutions containing glycine, glycylglycine, glycyl-L--alanine, L--alanyl-glycine, L--alanyl-L--alanine, DL--alanyl-DL--alanine, trialanine and 18-crown-6 and/or 1-aza-18-crown-6 and or 1,10-diaza-18-crown-6 at 25°C. The results have been treated by the McMillan-Mayer approach in order to obtain enthalpic virial coefficients for homotactic and heterotactic interactions. A significant exo-effect is demonstrated by the enthalpically favorable interaction between peptides and the 18-crown-6. The additivity of the positive alanyl group contribution toh _xy has been confirmed on the basis of oligomeric data. The influence on the enthalpy of the 18-crown-6-peptide interaction of the methyl group position, in relation to the ammonium group in peptides, has been found to result in the exo-effect decreasing with a decrease of this distance. Some decrease in enthalpy of L--alanyl-L--alanine and DL--alanyl-DL--alanine by 18-crown-6 has been observed as well.Deceased.     

The effect of carbon chain length of the diphosphine ligand on the aurophilic interaction. Synthesis and X-ray structural study for a series of Au(I) compounds with Ph2P-R-PPh2 and S-(CH2)n-py ligands

The effect of the carbon chain-length for Ph₂P-R-PPh₂ (R = -CHCH-, -CH₂-CH₂-, -CH₂-CH₂-CH₂-, and -CH₂-CH₂-CH₂- CH₂-) and S-(CH₂)_n-pyridine ligand (n = 0 to 2) on the aurophilic interaction has been explored systematically. The effect of the N position in x-mercaptopyridine (x = 2 or 4) toward Au(I) center and/or the SR group was also investigated. X-ray structural study was made for 12 new derivatives. The Au-Au distances are below 3.0 Å for 2-S-pyridine derivatives with Ph₂P-CHCH-PPh₂ (t-dpen) and Ph₂P-CH₂-CH₂-PPh₂ (dppe) ligand and the pyridine N atoms come in close contact with the H atoms of these diphosphine carbon chains. A local coplanar conformation is formed between 2-S-pyridine and Au-P-CH groups for these derivatives. The carbon chain lengths are not too consequential on the induction of aurophilicity. Various infinite and/or dimer structures have been revealed from single crystal X-ray analysis for the present series of compounds.     

Chiral recognition in aqueous solutions between enantiomeric α-amino acids bearing substituted alkyl chains at 25°C: The peferential configuration model

Calorimetric, densimetric, and nuclear relaxation time measurements were carried out at 25°C on binary and ternary aqueous solutions containing L and D forms of the following amino acids bearing substituted alkyl chains: lysine, glutamine, arginine, asparagine, serine, and homoserine. For three of them (lysine, glutamine, and arginine), very high differences were found between the values of the homochiral and heterochiral pairwise enthalpic interaction coefficients. Volume and spectroscopic data showed that it is possible to detect chiral recognition by techniques other than calorimetric. The role of the zwitterionic interaction and of the substituted side chain is discussed to explain the enhanced chiral recognition of these -aminoacids in respect to those bearing unsubstituted alkyl chains (alanine, -aminobutyric acid, valines and leucines).     

Calorimetric and Volumetric Studies of the Interactions of Propionamide in Aqueous Alkan-1-ol Solutions at 298.15 K

Enthalpies of solution and apparent molar volumes have been determined for propionamide in aqueous methanol, ethanol and propanol solutions at 298.15 K using a C-80 microcalorimeter and a DMA60/602 vibrating-tube digital densimeter. The enthalpic and volumetric interaction coefficients have been calculated. Using the present results along with results from previous studies for formamide, the pair-interaction coefficients are discussed from the perspective of dipole-dipole and structural interactions. In addition, the triplet interaction coefficients are interpreted by using the solvent-separated association mechanism.     

X-Ray Diffraction Study of Aluminum Monoxycarbide

The structural characteristics of aluminum monoxycarbide Al₂OC are refined and systematized. Based on our X-ray diffraction data, three modifications of Al₂OC: -Al₂OC, '-Al₂OC, and '-Al₂OC have been revealed. Structural models are suggested for them.     

Zur Reaktion von Carbonsäureanhydriden mit Formamid und N-Methylformamid

Zusammenfassung Das Erhitzen von (in der Mehrzahl) aromatischen intramolekularen Dicarbonsäureanhydriden mit einem Überschuß an Formamid bzw. N-Methylformamid stellt eine sehr einfache und allgemein anwendbare Darstellungsweise für die entsprechenden Imide bzw. N-Methylimide dar. Es zeigt sich, daß die für die Umsetzung nötigen Temperaturen für Anhydrid- und Carboxylgruppen vom Formamid über N-Methylformamid zum Dimethylformamid ansteigen. Durch Reaktion von Trimellithsäureanhydrid entsteht mit N-Methylformamid das Trimellithsäure-N-methylimid. Die Umsetzung von Terephthalsäure mit N-Methylformamid in Gegenwart von P₄O₁₀ führt in guter Ausbeute zum Terephthalsäure-N,N-bis(methylamid).

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Reaction of carboxylic anhydrides with formamide and N-methylformamide

The reaction of (mostly) aromatic carboxylic anhydrides with an excess of formamide or N-methylformamide at elevated temperatures is a very simple and useful synthesis for the appropiate imides or N-methylimides. The reaction temperature increases from formamide to N-methylformamide to dimethylformamide. Trimellitic anhydride yields with N-methylformamide trimellitic acid-N-methylimide. Excellent yields of terephthal-N,N-bis(methylamide) are obtained by the reaction of terephthalic acid with N-methylformamide in the presence of P₄O₁₀.