Dimers of the higher-energy conformer of formic acid: experimental observation

We report on the first experimental observation of formic acid dimers composed of two molecules of the higher-energy cis conformer. The cis-cis formic acid dimers are prepared in an argon matrix by selective vibrational excitation of the ground state trans conformer (deuterated form HCOOD) combined with thermal annealing of the matrix at about 30 K. Five cis-cis formic acid dimers are predicted by ab initio calculations (interaction energies from -16.9 to -27.2 kJ mol(-1)), and these structures are used for the assignment of the experimental spectra. Selective vibrational excitation of the obtained cis-cis dimers leads to the formation of several trans-cis dimers, which supports the proposed assignments.     

Experimental and computational study of crystalline formic acid composed of the higher-energy conformer

Crystalline formic acid (FA) is studied experimentally and by first-principles simulations in order to identify a bulk solid structure composed of the higher-energy (cis) conformer. In the experiments, deuterated FA (HCOOD) was deposited in a Ne matrix and transformed to the cis conformer by vibrational excitation of the ground state (trans) form. Evaporation of the Ne host above 13 K prepared FA in a bulk solid state mainly composed of cis-FA. Infrared absorption spectroscopy at 4.3 K shows that the obtained solid differs from that composed of trans-FA molecules and that the state persists up to the annealing temperature of at least 110 K. The first-principles simulations reveal various energetically stable periodic chain structures containing cis-FA conformers. These chain structures contain either purely cis or both cis and trans forms. The vibrational frequencies of the calculated structures were compared to the experiment and a tentative assignment is given for a novel solid composed of cis-FA.     

Rotational isomerism in acetic acid: the first experimental observation of the high-energy conformer

The high-energy conformer of acetic acid (cis-AA) is produced in an Ar matrix by vibrational excitation of the OH stretching overtone of the ground conformational state (trans-AA). IR-absorption spectroscopy provides a clear identification of the reaction product. cis-AA converts back to trans-AA in a time scale of minutes at 8 K by tunneling.     

Enhanced stability to decomposition of a cobalt-dioxygen adduct supported in a copolymer matrix

Summary The decomposition of the Co^II complex of a macrocyclic cyclidene ligand is reported both in solution and when bound to a copolymer support. E.s.r. studies show that the decomposition of the complex in pyridine solution, under an atmosphere of O₂, has an estimated half-life of ca. 36 h at 295 K. This suggests that decomposition of the O₂ adduct is the second step observed in earlier electronic spectroscopic studies, and infers that the cyclidene O₂ adducts are much longer lived than originally thought. The Co^II cyclidene complex forms a coordinate bond to the pyridine group of n-butyl methacrylate/4-vinyl pyridine copolymers and the resulting five-coordinate complexes undergo reversible oxygenation. The polymer-supported O₂ adducts are much more stable to decomposition than those in the solution phase and have an estimated half-life of ca. 30 days at 295 K. The enhanced stability to decomposition of the complexes in the polymer matrix is attributed to the low mobility of the complexes in the glassy polymer.     

Enhanced stability of the columnar matrix in a discotic liquid crystal by insertion of ZnO nanoparticles

An experimental characterisation of dispersions of ZnO nanoparticles (NPs) in the columnar matrix of a discotic liquid crystal has been carried out. Thermophysical properties have been investigated by absorbance spectroscopy, differential scanning calorimetry, polarising optical microscopy, dielectric measurements, dc conductivity, X-ray diffraction and infrared (IR) dichroism technique. The experimental results show that inclusion of ZnO NPs into the columnar matrix enhances the orientational order in the columnar phase and does not affect the two-dimensional hexagonal lattice. The alignment in homeotropic samples is also found to be better with the addition of the NPs. The real (?′) and imaginary parts (?′′) of the permittivity increase by a small amount in the dispersions. The order parameter measured using the IR dichroism technique in the face-on geometry (homeotropic alignment) shows an enhancement for the composite system. The dc conductivity is also found to increase by an order of magnitude by addition of the NPs. These results suggest an improved stacking of the disc-like molecules within the columns by the insertion of the ZnO NPs possessing high charge mobility. Such composite systems would be highly beneficial for potential applications such as organic conductors.     

Mesoionic compounds with a bridged nitrogen atom. 18. Cyclization of (2-quinazolinylthio)acetic acids

It was established that mesoionic thiazoloquinazolinium oxides are formed in the action of acetic anhydride on (2-quinazolinylthio)acetic and -phenylacetic acids. The structures of the products were confirmed by their spectral characteristics and chemical transformtions.See [1] for Communication 17.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 817–822, June, 1989.     

Analysis of conformer stability for 1,3,8-trihydroxynaphthalene: natural substrate of fungal trihydroxynaphthalene reductase

1,3,8-Trihydroxynaphthalene is one of the substrates in the fungal melanin biosynthesis pathway. We present theoretical studies on energies of its tautomeric forms and their rotamers. Several theory levels and solvent models have been tested using experimental results obtained in water-acetone mixtures as the reference point. Our results indicate that the best agreement with these data is obtained with density functional theory levels when the continuum solvation model uses the united atom topological cavity. We also noticed a fairly good performance of the semiempirical AM1 method that makes it a promising alternative for studies of large systems.     

Enhanced stability of Pt electrocatalysts by nitrogen doping in CNTs for PEM fuel cells

Electrochemical stabilities of Pt deposited on carbon nanotubes (CNTs) and nitrogen-doped carbon nanotubes (CN_x) of different nitrogen contents are compared with accelerated durability tests (ADT) for the first time. Transmission electron microscopy (TEM) images reveal the different structures of CNTs and CN_x, and the decrease of Pt particle size with the nitrogen incorporation into CNTs. Based on the loss of electrochemical surface area (ESA) and TEM images, Pt/CN_x exhibited much higher stability than Pt/CNTs, and the Pt stability increases with the increase of nitrogen contents in the CN_x supports.     

Electrosynthesis of anisidines in aqueous sulfuric and acetic acids

The influence of the concentrations of acetic and sulfuric acids on the efficiency of anisole amination by means of hydroxylamine and Ti(IV)/Ti(III) mediator was studied. Ortho- and para-anisidines were obtained with the total yields of about 79% by current and hydroxylamine. Original Russian Text ? Yu.A. Lisitsyn, L.V. Grigor’eva, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 3, pp. 596–597.     

Determination of pK(a) of acetic and benzoic acids in pyridine

The pK(a)'s of acetic acid and benzoic acid in pyridine as solvent are found to be 10.1 and 9.8, respectively, at 25 degrees . These results are based on measurements of hydrogen ion activities in mixtures of the acids and their tetrabutylammonium salts. Supplementary studies of differential vapour pressure characteristics of solutions of the acids and the acid-salt mixtures, and conductance of tetrabutylammonium benzoate solutions are also incorporated.     

Cyclization of 4-ureidobutanoic acids in acetic anhydride

A simple method is proposed for synthesizing 1-carbamoyl-2-pyrrolidones by cyclization of 4-ureidobutanoic acids in acetic anhydride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 33–38, January, 1995.     

Uncommon oxidative transformations of acetic and propionic acids

The oxidative decarbonylation of acetic and propionic acids with the formation of the corresponding alcohol and alkyl carboxylate is observed in the Rh^III/Cu^I,II/Cl⁻ catalytic system in the presence of O₂ and CO. The decarbonylation of propionic acid in a deuterated solvent results in the substitution of hydrogen atoms by deuterium in the alkyl part of the products to form CH₂DCOOD (CHD₂COOH) and CHD₂COOD (CD₃COOH). The subsequent decarbonylation of deuterated acetic acids affords the corresponding deuteromethanols detected as esters with propionic and deuteroacetic acids. The substitution of the hydrogen atom by deuterium in the alkyl part of molecules of the products of oxidative decarbonylation of propionic acid, when the reaction is carried out in a deuterated solvent, indicates that propionic acid behaves as saturated hydrocarbon and blocks the oxidation of poorly soluble methane. Unlike propionic acid, acetic acid enters only the oxidative decarbonylation reaction and does not block methane oxidation.     

Mixed anhydride of acetic and formic acids in the synthesis of chromones

A study was carried out on the reaction of -substituted 2-hydroxyacetophenones with the mixed anhydride of acetic and formic acids in the presence of bases of different strength. Chromones containing a conjugated electron-withdrawing substituent at C₍₃₎ are formed in close to quantitative yield in the presence of triethylamine. The preparation of chromones containing an unconjugated substituent under these conditions is recommended only for 5-hydroxy chromones.For Communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 595–600, May, 1992     

Dissolution enthalpy of phosphoric and acetic acids in water-dimethylformamide mixtures

Dissolution enthalpies of phosphoric and acetic acids were experimentally determined (concentration of acid, up to 3 mol/kg) in water—dimethylformamide (DMF) mixtures (molar part of DMF, from 0 to 1) at 298.15 K. Standard dissolution enthalpies of acids in the mixed water-DMF solvent were estimated on the basis of the obtained data.     

UV and IR photoisomerization of acetylacetone trapped in a nitrogen matrix

UV- and IR-induced photoisomerization of acetylacetone trapped in a nitrogen matrix at 4.3 K have been carried out using a tunable optical parametric oscillator type laser, or a mercury vapor lamp, coupled with Fourier Transform IR and UV spectroscopies. After deposition, the main form present in the cryogenic matrix is that chelated (enol). Upon UV irradiation, the intramolecular H bond is broken leading to nonchelated isomers among seven possible open forms. These forms have then been irradiated by resonant pi* <-- pi UV irradiation, or by resonant nuOH irradiation. The selective UV irradiation allows us to suggest a first vibrational assignment while the nuOH irradiation leads us to observe interconversions between the nonchelated isomers. In order to support our vibrational assignment, we have carried out theoretical calculations at the B3LYP/6-311++G(2d,2p) level of theory. This study shows that only five isomers are observed among eight postulated.     

Enhanced stability of a protein with increasing temperature

The unusual stability of a structured but locally flexible protein, human growth hormone (hGH) at pH 2.7, was investigated using the temperature dependence of the nanosecond-picosecond dynamics of the backbone amide groups obtained from (15)N NMR relaxation data. It is found that the flexibility of the backbone of the helices decreases with temperature in the range from 24 °C to ～40 °C, corresponding to an increasing stability. A concomitant increase with temperature of the electrostatic interactions between charged residues forming an interhelical network of salt bridges at the center of the four-helix core suggests that these interactions give rise to the decreasing flexibility and increasing stability of the protein. However, numerous hydrophobic interactions in the interior of the four-helix core may also contribute. Above ～40 °C, where the thermal energy overcomes the electrostatic and hydrophobic interactions, a substantial increase in the flexibility of the helix backbones results in a highly positive contribution from the local conformational heat capacity, C(p,?conf), of the helix backbones to the total heat capacity, C(p), of the protein. This reduces the change in heat capacity upon unfolding, ΔC(p), increases the change in the Gibbs free energy, ΔG(unfold), and stabilizes the protein at high temperatures. A similar decrease in flexibility is found near other salt bridges in hGH and in Calmodulin and may be of general importance for the thermostability of proteins and, in particular, of the salt bridge intensive thermophilic proteins.