<Emphasis Type="Italic">Brønsted</Emphasis> Acids in Ionic Liquids: Fundamentals,Organic Reactions,and Comparisons

Summary. A background for studying acids in various solvents is developed, emphasizing the importance of knowing to what extent a solvent conducts electricity and is therefore ionized, the dissociation equilibria of common molecular solvents and the acidic and basic species generated by solvent leveling. Acidity measurements in the atypical solvent water are discussed and the common method of expressing acidity in other systems – by Hammett values – is introduced. Representative examples of reactions involving Br?nsted acids in ionic liquids are presented and attention paid to the questions of speciation and acidity values. It is found that the gas phase proton affinity of a base is often a better guide to the acidity of its conjugate acid in an ionic liquid than is the dissociation constant of the said acid in water.     

Phenanthroline complexes bearing diamide-anion recognition sites

The synthesis and anion binding properties of new ruthenium(II) and cobalt(II) phenanthroline complexes, containing two amide subunits are described. Evidence for anion binding in dimethyl sulfoxide (DMSO) solution was obtained from u.v.–vis titration experiments. Results indicated that these receptors showed strong affinity for F⁻ and AcO⁻, and showed weak affinity for OH⁻ and H₂PO ₄ ⁻ , and showed no affinity for Cl⁻, Br⁻, I⁻. These receptors interacted with various anions examined through hydrogen-bond formation.     

Sensitively probing the cofactor redox species and photo-induced electron transfer of wild-type and pheophytin-replaced photosynthetic proteins reconstituted in self-assembled monolayers

An ultrathin, ordered, and packed protein film, consisting of the 2-mercaptoacetic acid (MAA), polydimethyldiallylammonium chloride (PDDA), and wild-type (WT) photosynthetic reaction center (RC; termed as WT-RC) or its pheophytin (Phe)-replaced counterpart (termed as Phe-RC), was fabricated by self-assembling technique onto gold electrode for facilitating the electron transfer (ET) between RC and the electrode surface. Near-infrared (NIR)-visible (Vis) absorption and fluorescence (FL) emission spectra revealed the influence of pigment substitution on the cofactors arrangement and excitation relaxation of the proteins, respectively. Square wave voltammetry (SWV) and photoelectric tests were employed to systematically address the differences between the WT-RC films and mutant ones on the direct and photo-induced ET. The electrochemical results demonstrated that ET initiated by the oxidation of the primary donor (P) was obviously slowed down, and the formed P⁺ had more population as well as more positive redox potential in the Phe-RC films compared with those in the WT ones. The photoelectrochemical results displayed the dramatically enhanced photoelectric performances of the mutant ones, further suggesting the slow-down formation of final charge-separated state in Phe-RC. The functionalized protein films introduced in this paper provided an efficient approach to sensitively probe the redox cofactors and ET differences resulting from only minor changes in pigment arrangement in the pigment–protein complex. The favored ET process observed for the membrane proteins RC was potentially valuable for a deep understanding of the multi-step biological ET process and development of versatile bioelectronic devices.     

Development of a non-invasive method for the determination of the macroscopic neutron cross sections of a sample matrix in large-sample prompt-gamma neutron activation analysis

In order to correct for neutron self-shielding in large-sample prompt gamma NAA, a method has been developed to determine the macroscopic scattering and absorption cross sections, i.e., Σ _a and Σ _s, using four Cu flux monitors placed around the sample. With Monte Carlo computations, the neutron densities throughout the sample and the resulting and the corresponding self-shielding factor as calculated from the Σ _a and Σ _s as obtained through the Cu monitors were compared to the true values. The derived Σ _a and Σ _s were found to be sufficiently accurate as long as Σ _t = Σ _a + Σ _s was less than 0.6 cm⁻¹ and Σ _s/Σ _t was greater than 0.1.     

Thermal analysis and microscopical characterization of cholesterol in gallstones

Summary Cholesterol constitutes the major component of most gallstones. It was identified and determined in gallstones by thermal analysis technique (DSC and TG-DTA), mainly by the use of the melting temperature (T_onset=145°C and T_max=149°C) and by DTG peak decomposition (T_max=364°C). Cholesterol anhydrous (ChA), which showed endothermic polymorphic peak, T_max=40°C, without mass loss, was differentiated from cholesterol monohydrate (ChH), which showed a broad endothermic peak, T_max=59°C, attributed to loss of water of crystallization (theoretical 4.45%). Morphological studies of gallstones were performed by optical microscopy and scanning electron microscopy (SEM). The stones consisted of a pigmented core with a variably-sized irregular central cavity, surrounded by a radially arranged deposits of plate-like ChH. The outer part of the stones showed ChA crystal arborescences. X-ray microanalysis gave a typical spectrum rich in C and O, and in some instances the presence of P, which was attributed to the presence of phospholipids. CaCO₃ was easily characterized by TG with the use of DTG decomposition peak at 674°C.     

Photocatalytic oxidation of phenol in aqueous solutions with oxygen catalyzed by supported metallophthalocyanine catalyst

In this paper, zinc tetraaminophthalocyanine (Zn-APc) was immobilized on cellulosic fiber by covalent bond to obtain a novel cellulosic fiber supported metallophthalocyanine, named Zn-TDTAPc-F. At pH 11, upon visible light irradiation for 6 h in the presence of O2, Zn-TDTAPc-F was found to be highly effective for the degradation of phenol in aqueous solution, and the degradation rate of phenol was more than 95%. HPLC was used to confirm formic acid, fumaric acid and maleic acid as its main degradation products.     

Paradigms and paradoxes: patterns and estimation of the entropy of formation of aqueous hydrogen containing mono and polynuclear oxyanions

“Simple” energetic patterns, where simple means the use of parameters derived only from the stoichiometry of these species, are relatively rarely discussed in the literature. In addition, entropy studies have been dominated by derivation of the absolute quantity S° rather than the entropy of formation (TΔ_f S ^o). Relationships between the entropy of formation and different parameters such as negative value of the charge of the species, the number of oxygen atoms, the natural logarithm of the molecular weight, the total number of atoms and the number of central atoms that are gases were recently discussed by us for aqueous polynuclear oxyanions. As shown here hydrogen containing anions do not follow this pattern. In this study, new approaches for the estimation of the entropy of formation of aqueous hydrogen containing mono and polynuclear oxyanions are suggested, evaluated and recommended.     

Ferromagnetism in Metallocene-Doped Fullerenes

 Ferromagnetism in fullerene-based systems doped with metallocenes is reviewed. These compounds form a ferromagnetic state by spin-coupling between π electrons on fullerene units, while the metallocene molecules do not contribute to the spin ordering. One of these compounds has the highest critical temperature (19 K) for this class of compound. The magnetic properties of these materials are very strongly dependent on the crystallization conditions. Corresponding author. E-mail: Dragan.Mihailovic@ijs.si Received September 4, 2002; accepted September 6, 2002     

PHOTOSENSITIZING PROPERTIES OF BACTERIOCHLOROPHYLLIN a and BACTERIOCHLORIN a, TWO DERIVATIVES OF BACTERIOCHLOROPHYLL a

Abstract The photosensitizing properties of two water soluble derivatives of bacteriochlorophyll a , bacteriochlorophyllin a and bacteriochlorin a (lacking the central Mg-ion) were investigated and compared to those of hematoporphyrin derivatives. At physiological pH the oxygen consumption rate of histidine, tryptophan, dithiothreitol and guanosine upon illumination was 3 to 4 times higher when bacteriochlorin a was used as photosensitizer than when hematoporphyrin derivatives were used. Especially bacteriochlorin a proved to be an effective sensitizer for the killing of L929 cells. Because bacteriochlorin a has an absorption maximum at 765 nm in phosphate buffered saline (allowing a light penetration in tissue about ten times larger than at 630 nm) and a high molar absorption coefficient (32 000 M cm⁻¹) it has promising possibilities for the application in photodynamic therapy.