Quantitative spectrophotometric and EPR-determination of 1,1-diphenyl-2-picryl-hydrazyl (DPPH)

A first simultaneous EPR- and VIS-spectrophotometric study is reported on the interaction of the stable free radical 1,1-diphenyl-2-picryl-hydrazyl (DPPH) dissolved in ethanol with thioglycolic acid (HSCH₂CO₂H, TGA). The results of the kinetic studies at room temperature permit to assume 1:1 stoichiometry of the reaction between DPPH and TGA giving 1,1-diphenyl-2-picryl-hydrazine (DPPH₂) and thioglycolic disulphide. The linear plots of EPR- and UV/Vis responses vs. the quantity of added TGA are used to find the DPPH molar absorptivity at 520 nm to be 12350 ± 3% l · mol^–1· cm^–1 which may be used as a criterion for the purity of the material itself. It was also found that the paramagnetic and optical properties of a 30 year old sample give results suggesting that in the solid state DPPH is a fairly stable material. Received: 12 October 1996 / Revised: 6 December 1996 / Accepted: 12 December 1996     

A rheological investigation of aqueous solutions of poly (vinyl alcohol) during aging. Part IV: Repeated aging of concentrated solutions

Aging of aqueous solutions of poly (vinyl alcohol) obtained by melting of gels, formed in the aging process from solutions prepared by the dissolution of the polymer in hot water, was investigated using non-Newtonian viscometry and normal stress measurement. It was shown that, if the gels undergo melting at the same temperature at which the original solutions were prepared, aging of such solutions proceeds in the same way as in the case of the original solutions. If melting occurred due to heating at lower temperature, the resulting solutions aged more quickly.     

Synthesis and mesomorphic properties of four ring,rod-like fluorene derivatives – the influence of the lateral substitution on mesomorphic properties of 2,7-bis(4-alkylphenyl)-fluorenes

ABSTRACT

This work presents new rod-like compounds being fluorene derivatives linked with other parts of the core at 2 and 7 positions – its synthesis and properties. The fluorene moiety is located in the central position of the four rings molecular core. The chain system in most cases was symmetrical and limited to pentyl or hexyl chains. To study the influence of the lateral substituents on mesomorphic properties two types of substituents have been incorporated, centrally located various short alkyl groups at fluorene’s 9,9 positions and outer core fluorosubstitutions located at side phenyl rings. All synthesised compounds exhibit liquid crystalline properties, where for laterally non-substituted and fluorosubstituted derivatives the dominant phases are smectics, while the nematics phases (nematic and chiral nematic – observed mostly on cooling cycle) occurs for compounds having alkyl substituents at 9,9 positions of fluorene. The synthetic methodology and mesomorphic properties of title compounds will be presented in detail as well as photophysical properties such as UV-visible absorption spectra and fluorescence spectra.     

Rheological investigation of aqueous solutions of poly(vinyl alcohol) during aging II. Influence of experimental conditions on dissolution and aging

The influence of the temperature and time of heating during dissolution on the aging of concentrated aqueous solutions of poly(vinyl alcohol) and aging at different temperatures are described. Changes occuring during aging are interpreted on the basis of non-Newtonian viscosity and normal stress measurements.     

Trimethylsilyl fluorosulfonyldifluoroacetate (TFDA): a new, highly efficient difluorocarbene reagent

TFDA is readily prepared from the reaction of fluorosulfonyldifluoroacetic acid with trimethylsilyl chloride, and it is a very effective and efficient source of difluorocarbene for use in addition reactions to alkenes of a broad scope of reactivities. Acid-sensitive substrates may require an additional purification step involving treatment of the distilled TFDA with sufficient Et₃N to remove the acid impurity. Other trialkylsilyl fluorosulfonyldifluoroacetates can also be prepared, and they have been found to have reactivities similar to TFDA. The triethyl derivative, TEFDA is more convenient to prepare in a pure state and has similar reactivity to TFDA. Thus, it may prove to be a superior reagent.     

Vibrational studies of the solid imidazole and pyridine adducts of metal(II) saccharinates. III. Zn(II) and Hg(II) imidazole saccharinates

Adducts of bis(o-sulfobenzimidato)zinc(II) and mercury(II) with imidazole are synthesized for the first time and their mid-infrared vibrational spectra at ambient conditions and at 77 K are coupled with the earlier spectra-structural inferences to predict aspects of the respective solid-state structures. The spectrum of the H2O-matrix isolated OD fundamentals in the hydrated zinc compound is also investigated. The structure of the latter adduct contrasts the octahedral isostructural tetrad of mixed imidazole-saccharinates [M(H2O)2(C3H4N2)4](C7H4NO3S)2 [M = Mn(II), Fe(II), Co(II) and Ni(II)] in that it bears only a single crystallographic type of hydrogen bonded C2v water molecules and at least two structurally different o-sulfobenzimidate ligands, some of them likely utilized in a bridging fashion. The rotation and the partial ionic character of a pair of N-monodentate o-sulfobenzimidato ligands placed about 212-214 pm from the metal accommodates another pair of imidazole molecules in the tetrahedral arrangement around the metal in the neutral unhydrous mercury complex.     

Effects of Addition of Ion-Pair Reagent to the Mobile Phase on Electroosmotic Flow Velocity in Pressurized Planar Electrochromatography

JPC – Journal of Planar Chromatography – Modern TLC - In the paper, the influence of the addition of different ion-pair reagents — sodium-1-heptane sulfonate (HS),...     

Impact of Mercury(II) on proteinase K catalytic center: investigations via classical and Born-Oppenheimer molecular dynamics

Mercury(II) has a strong affinity for the thiol groups in proteins often resulting in the disruption of their biological functions. In this study we present classical and first-principles, DFT-based molecular dynamics (MD) simulations of a complex of Hg(II) and proteinase K, a well-known serine protease with a very broad and diverse enzymatic activity. It contains a catalytic triad formed by Asp39, His69, and Ser224, which is responsible for its biological activity. It was found previously by X-ray diffraction experiments that the presence of Hg(II) inhibits the enzymatic action of proteinase K by affecting the stereochemistry of the triad. Our simulations predict that (i) the overall structure as well as the protein backbone dynamics are only slightly affected by the mercury cation, (ii) depending on the occupied mercury site, the hydrogen bonds of the catalytic triad are either severely disrupted (both bonds for mercury at site 1, and the His69–Ser224 contact for mercury at site 2) or slightly strengthened (the Asp39–His69 bond when mercury is at site 2), (iii) the network of hydrogen bonds of the catalytic triad is not static but undergoes constant fluctuations, which are significantly modified by the presence of the Hg(II) cation, influencing in turn the triad’s ability to carry out the enzymatic function—these facts explain the experimental findings on the inhibition of proteinase K by Hg(II).