Demixing in polystyrene/methylcyclohexane solutions

Cloudpoint data for polystyrene/methylcyclohexane solutions extending over moderate ranges of pressure and molecular weight are available in the literature. Those data are supplemented with new results from this laboratory to fill in gaps and extend the MW range (to 761 ≤ MW/amu ≤ 2 × 10⁷). The resulting data net is discussed and reasons to extend studies to higher pressure are presented. © 1996 John Wiley & Sons, Inc.     

Kinetics and mechanism of the reaction between hypochlorous acid and tetrathionate ion

The reaction has been studied spectrophotometrically monitoring the absorbance in the 240–400 nm wavelength range. The spectra of the reactants, intermediates, and products in this system are overlapping; thus special programs [ 1 , 2 ] have been used (and tested) to unravel the kinetics and mechanism of the reaction. The stoichiometry of the reaction in excess hypochlorous acid is S₄O₆²⁻ + 7HOCl + 3H₂O → 4SO₄²⁻ + 7Cl⁻ + 13H⁺. Various experiments are presented to show that—in excess tetrathionate—the reaction produces a light‐absorbing intermediate identified as S₂O₃Cl⁻. The intermediate slowly hydrolyzes into sulfur and sulfate and it yields pentathionate in excess tetrathionate. The rate‐determining steps and their rate constants are The further oxidation of S₂O₄²⁻ and SO₃²⁻ by HOCl to sulfate are fast processes. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 395–402, 2000     

Poly(vinylferrocenium) coated disposable pencil graphite electrode for DNA hybridization

Poly(vinylferrocenium) (PVF⁺) modified electrode was developed in this study for the electrochemical sensing of DNA based on the oxidation signals of polymer, adenine and guanine. Experimental parameters, such as; polymeric film thickness, DNA immobilization time and DNA concentration were examined in order to obtain more sensitive and selective electrochemical signals. After optimization studies, DNA hybridization was investigated.     

Challenges and Opportunities of Implementing Data Fusion in Process Analytical Technology—A Review

The release of the FDA’s guidance on Process Analytical Technology has motivated and supported the pharmaceutical industry to deliver consistent quality medicine by acquiring a deeper understanding of the product performance and process interplay. The technical opportunities to reach this high-level control have considerably evolved since 2004 due to the development of advanced analytical sensors and chemometric tools. However, their transfer to the highly regulated pharmaceutical sector has been limited. To this respect, data fusion strategies have been extensively applied in different sectors, such as food or chemical, to provide a more robust performance of the analytical platforms. This survey evaluates the challenges and opportunities of implementing data fusion within the PAT concept by identifying transfer opportunities from other sectors. Special attention is given to the data types available from pharmaceutical manufacturing and their compatibility with data fusion strategies. Furthermore, the integration into Pharma 4.0 is discussed.     

Diffusion model of solute dynamics in a membrane channel: mapping onto the two-site model and optimizing the flux

The steady-state flux through a singly occupied membrane channel is found for both discrete and continuum models of the solute dynamics in the channel. The former describes the dynamics as nearest-neighbor jumps between N sites, while the latter assumes that the molecule diffuses in a one-dimensional potential of mean force. For both models it is shown that the flux is the same as that for a simple two-site model with appropriately chosen rate constants, which contain all the relevant information about the more detailed dynamics. An interesting consequence of single occupancy is that the flux has a maximum as a function of the channel-solute interaction. If this interaction is too attractive, the molecule will never leave the channel, thus blocking it for the passage of other molecules. If it is too repulsive, the solute molecule will never enter the channel. Thus the flux vanishes in the two limits and, hence, has a maximum somewhere in-between. In the framework of the diffusion model, we find the optimal intrachannel potential of mean force that maximizes the flux using the calculus of variations. For a symmetric channel this potential is flat and occupies the entire channel. In the general case of an asymmetric channel, the optimal potential is obtained by tilting the optimal flat potential for the corresponding symmetric channel around the channel center, so that the solute is driven towards the reservoir with the lower solute concentration by a constant force. This implies that the flux is higher when the solute binding near the channel exit is stronger than that near the entrance.     

Perturbative treatment of the electron-correlation contribution to the diagonal Born-Oppenheimer correction

A perturbative scheme for the treatment of electron-correlation effects on the diagonal Born-Oppenheimer correction (DBOC) is suggested. Utilizing the usual Moller-Plesset partitioning of the Hamiltonian formulas for first and second orders (termed as MP1 and MP2) are obtained by expanding the wave function in the corresponding coupled-cluster expressions for the DBOC[J. Gauss et al., J. Chem. Phys. 125, 144111 (2006)]. The obtained expressions are recast in terms of one- and two-particle density matrices in order to take advantage of existing analytic second-derivative implementations for many-body methods. Test calculations show that both MP1 and MP2 recover large fractions (on average 90% and 95%, respectively) of the coupled-cluster singles and doubles (CCSD) electron-correlation corrections to the DBOC and thus render the suggested MP treatments cost-effective (though still accurate) alternatives to high-level coupled cluster (CC) treatments. The applicability of the MP1 and MP2 schemes for treating DBOC is demonstrated in calculations for the atomization energies of benzene, naphthalene, anthracene, and tetracene. The corresponding corrections are surprisingly large (about 0.6 kJmol for benzene, 1.1 kJmol for naphthalene, 1.5 kJmol for anthracene, and 1.8 kJmol for tetracene) with the electron-correlation corrections reducing the corresponding Hartree-Fock self-consistent field values by 25%-30%.     

Functionalization of the pyridazin-3(2H)-one ring via palladium-catalysed aminocarbonylation

5-Iodo- and 4,5-dibromo-2-methylpyridazin-3(2H)-ones were aminocarbonylated in the presence of various amines including amino acid methyl esters in a palladium-catalysed reaction. The iodo derivative afforded the corresponding amides with complete conversion and high isolated yields. The dibromo derivative has shown unexpectedly high reactivity in this reaction, resulting in 4,5-dicarboxamides using primary amines as N-nucleophiles. Monoaminocarbonylation has not been observed, i.e., neither 4-bromo-5-carboxamide nor 4-carboxamido-5-bromo derivatives have been formed. However, the use of secondary amines such as piperidine and morpholine resulted in the formations of mixtures of amino-substituted bromopyridazinones. That is, no carbon monoxide insertion took place in these cases. Some mechanistic details of the formation of aminocarbonylation and amination products are also discussed.     

Microwave-assisted selective protection of glutaraldehyde and its symmetrical derivatives as monoacetals and -thioacetals

Six monoprotected acetals and -thioacetals of glutaradehyde and its symmetrical dimethyl derivatives were synthesized. Microwave-assisted heating proved to be a substantially more selective method for monoprotection than conventional heating. All reactions were efficient and only traces of diprotected material were formed.     

Theoretical study of hyaluronan oligosaccharides

The structure and energetics of hyaluronan oligomers from di- to decasaccharides have been studied by density functional theory calculations at the B3LYP/6-31G** level. The study covered selected conformers of the sodium salt, anionic disaccharides, and neutral acids in the isolated state and in aqueous solution using the PCM model approach. We investigated the structural changes of the hyaluronan chain when the Na⁺ ion is removed or replaced by proton. These processes result in some characteristic changes in the glycosidic torsional angles and hydrogen bonding interactions. We evaluated the folding for the hyaluronan chains and obtained values between 2.2 and 3.2, somewhat smaller than reported for the crystals. We found a contraction of the hyaluronan chains upon enlargement in most derivatives attributed partly to the helical character of hyaluronan. The energy consequences of the enlargement have been modeled by isodesmic reactions. The enlargement processes proved to be exothermal and the energies consistent within the gradual enlargement.     

LC-UV Assay of Tolperisone HCl from Sustained Release Matrix Tablets

Tolperisone HCl is a central muscle relaxant, which was incorporated in a matrix system formulated with poly(ethylene oxide)–PEO, in order to achieve adequate gastric residence time. This tablet presents considerable analytical difficulties in the quantitative determination of the drug, because the PEO matrix causes significant increase of viscosity in the samples. Our purpose was to develop a reproducible sample preparation method, which is adapted from parameters of the in vitro dissolution test and validate an LC-UV analytical method, which allows good recovery of the drug (99.97%). The developed analytical method was suitable for quantitative analysis of tolperisone HCl in matrix tablets.