Re-Evaluation of the Activity Coefficients of Aqueous Hydrochloric Acid Solutions up to a Molality of 2.0 Using Two-Parameter Hückel and Pitzer Equations. Part I. Results at 25°C

Simple two-parameter Hückel and Pitzer equations were used for the calculation of the activity coefficients of aqueous hydrochloric acid at 25°C up to a molality of 2.0 mol-kg^–1. The data obtained by Harned and Ehlers^(12,13) from galvanic cells without liquid junction were used in the analysis and the parameters obtained were compared to those obtained from all reliable data presented in the literature for HCl at this temperature. A good agreement between the parameters was always observed. The activity coefficients obtained by the new equations were compared to those suggested by Robinson and Stokes,⁽⁸⁾ Hamer and Wu,⁽¹⁾ and Pitzer and Mayorga,⁽⁹⁾ and good agreement was also found. The data from the most important literature data sets for HCl were also predicted using the new activity coefficient equations, and the magnitude of the resulting errors was close to the precision of the measurements, the errors forming an almost random pattern for all data sets.     

Observation of topical catalysis by sphingomyelinase coupled to microspheres

Sphingomyelinase, SMase (EC 3.1.4.12), was coupled onto amino-derivatized acrylate microspheres and was shown to retain its catalytic activity. The immobilized enzyme allows one to carry out topical enzymatic reaction in a controlled manner. Accordingly, these spheres were held with a micropipet and using micromanipulator brought into contact with a giant liposome membrane composed of phosphatidylcholine and sphingomyelin (SOPC/C16:0-SM, 0.75:0.25, molar ratio), representing the substrate for the immobilized enzyme. The macroscopic consequences of the enzyme reaction were visualized using fluorescence microscopy as well as differential interference contrast microscopy. The surface contact of the giant vesicle and immobilized enzyme causes membrane microdomain formation and domain clustering (capping) in the membrane and subsequent shedding of small vesicles from the membrane into the interior of the giant liposome. The method described represents a novel approach to study enzymatic reactions and allows manipulating giant vesicles as well as cultured cells in a spatially controlled manner.     

Electron ionization mass spectra of some norbornane/ene-fused 2-N-phenyliminoperhydro-1,3-oxazines

The 70 eV electron ionization (EI) mass spectra were recorded for eight norbornane/ene-fused 2-N-phenyl-iminoperhydro-1,3-oxazines, and the fragmentation patterns were studied by metastable ion analysis and exact mass measurement. Whereas the stereoisomeric unsaturated compounds could not be distinguished on the basis of their EI mass spectra, the stereoisomeric saturated compounds gave rise to clearly different spectra. The ionized unsaturated compounds decomposed mainly by two consecutive retro-Diels-Alder (RDA) reactions. A methyl substituent on the ring nitrogen strongly influenced the charge distribution on the RDA fragments. The ionized saturated compounds fragmented through several pathways. Loss of cyclopentadiene from the molecular ion was the energetically favoured fragmentation reaction for the saturated di-endo-fused compounds but was unimportant for the di-exo-fused compounds.     

Equations for calculation of the pH of buffer solutions containing sodium or potassium dihydrogen phosphate, sodium hydrogen phosphate, and sodium chloride at 25°C

Published thermodynamic data measured in aqueous mixtures of sodium or potassium dihydrogen phosphate with hydrogen phosphate and chloride at 25°C were used to test recently developed methods for calculation of the pH of phosphate buffer solutions. Equations for ionic activity coefficients are used in these methods. It is shown that all data used in the tests up to an ionic strength of about 0.5 mol-kg^-1 can be accurately predicted by the two methods recommended. In one of these methods, equations of the Hückel type are used for ionic activity coefficients and in the other equations of the Pitzer type. Several sets of phosphate buffer solutions are recommended,e.g., for calibrations of glass electrode cells. In the recommended sets, the pH of the buffer solutions can be calculated either by the Hückel or Pitzer method, and the pH predictions of these methods agree in most cases within 0.005 at least up to ionic strengths of about 0.2 mol-kg^-1. The pH values of the two primary pH standards endorsed by IUPAC based on aqueous mixtures of KH₂PO₄ and Na₂HPO₄,i.e., pH values of 6.865 and 7.413, can also be accurately predicted by the equations recommended in this study.     

Ultraviolet B Irradiation Modulates the Immune System of Fish (Rutilus rutilus, Cyprinidae). I. Phagocytes

Roach ( Rutilus rutilus ) were irradiated with a single dose of ultraviolet B (UVB) radiation (0.4 J/cm²) in order to study the effects of UVB on the nonspecific immune defense mechanisms of fish. Neutrophils and macrophages were isolated from the head kidney of fish on days 1–14 postirradiation. Both random and directed migration of neutrophils, studied by migration under agarose assay, were suppressed on day 1 after UVB irradiation. The respiratory burst of phorbol 12-myristate 13-acetatestimulated neutrophils and macrophages was also suppressed at days 1 and 2 after UVB irradiation. The suppression of migration and respiratory burst were restored or the responses were even enhanced later, but on the other hand spontaneous cytotoxicity of neutrophils toward ⁵¹chromium-labeled K562 target cells stayed suppressed throughout the 14 day follow-up. This study indicates that UVB radiation has the potential to suppress the functioning of phagocytes and to compromise the immune system of fish.     

Novel coordination of a hydroxamic acid : Crystal structures of bis(glycinohydroxamoto)nickel(II) and tris(glycinohydroxamoto)cobalt(III)

The structures of two glycinohydroxamoto (GHA) complexes of Ni(II) and Co(III) have been determined by single-crystal X-ray diffraction methods. The crystals of Ni(GHA)₂ are monoclinic with a = 5.360(1), b = 7.315(4), c = 10.194(4) Å, β = 96.57(3), Z = 2, and space group P2₁/c. The crystals of Co(GHA)₃•1/2 H₂O are monoclinic with a = 22.467(19), b = 8.041(4), c = 13.700(11) Å, β = 116.01(7), Z = 8, and space group C2/c. The values of the final residuals R for Ni(GHA)₂ and Co(GHA)₃•1/2 H₂O are 0.0275 and 0.032, respectvely. The molecular structures of Ni(GHA)₂ and Co(GHA)₃ consist of a square planar and an octahedral coordination, respectively, with the glycinohydroxamato (NH₂CH₂CONOH⁻) ligands coordinating to the metal ion via the N (amino) and the N (NOH⁻). These two complexes are the first well-established cases of coordination of the NHO⁻ group of a hydroxamic acid to a transition metal via the nitrogen atom.     

Re-Evaluation of the Activity Coefficients of Aqueous Hydrochloric Acid Solutions up to a Molality of 2.0 Using Two-Parameter Hückel and Pitzer Equations. Part II. Results from 0 to 95°C

Simple two-parameter Hückel and Pitzer equations were used for the calculation of the activity coefficients of aqueous hydrochloric acid at temperatures 0–60°C up to a molality of 2.0 mol-kg^–1. The data obtained by Harned and Ehlers^(2,3) on galvanic cells without a liquid junction were used in the parameter estimations of these equations. These data consist of sets of measurements at the temperature intervals of 5°C. It was observed that all estimated parameters follow very simple equations with respect to temperature. They are either constant or depend linearly on the temperature. The values for the activity coefficient parameters calculated by these simple equations are recommended here. The recommended parameter values were tested by predicting the data of Gupta, Hills, and Ives,⁽⁵⁾ consisting of cell measurements from 5 to 45°C and molalities up to 1.0 mol-kg^–1, and the data of Bates and Bower,⁽⁴⁾ which extend to 95°C but measurements were only made on molalities less than about 0.1 mol-kg^–1. The activity coefficients obtained by the new equations were also compared to those calculated by the Pitzer equations with the parameter values determined by Saluja, Pitzer, and Phutela⁽⁶⁾ from calorimetric data. The agreement observed was excellent up to a molality of 1.5 mol-kg^–1 at temperatures from 0 to 60°C.     

Influence of the pore structure of MCM-41 and SBA-15 silica fibers on atomic layer chemical vapor deposition of cobalt carbonyl

Mesoporous high surface area MCM-41 and SBA-15 type silica materials with fibrous morphology were synthesized and used as support materials for the ALCVD (atomic layer chemical vapor deposition) preparation of Co/MCM-41 and Co/SBA-15 catalysts. Co/MCM-41 and Co/SBA-15 catalysts were prepared by deposition of Co2(CO)8 from the gas phase onto the surfaces of preheated support materials in a fluidized bed reactor. For both silica materials, two different kinds of preparation methods, direct deposition and a pulse deposition method, were used. Pure silica supports as well as supported cobalt catalysts were characterized by various spectroscopic (IR) and analytical (X-ray diffraction, Brunauer-Emmett-Teller, elemental analysis) methods. MCM-41 and SBA-15 fibers showed considerable ability to adsorb Co2(CO)8 from the gas phase. For MCM-41 and SBA-15 silicas, cobalt loadings of 13.7 and 12.1 wt % were obtained using the direct deposition method. The cobalt loadings increased to 23.0 and 20.7 wt % for MCM-41 and SBA-15 silicas, respectively, when the pulse deposition method was used. The reduction behavior of silica-supported cobalt catalysts was found to depend on the catalyst preparation method and on the mesoporous structure of the support material. Almost identical reduction properties of SBA-15-supported catalysts prepared by different deposition methods are explained by the structural properties of the mesoporous support and, in particular, by the chemical structure of the inner surfaces and walls of the mesopores. Pulse O2/H2 chemisorption experiments showed catalytically promising redox properties and surface stability of the prepared MCM-41- and SBA-15-supported cobalt catalysts.     

Optical sensing of parameters crucial for Japanese woodblock print making

Traditional Japanese woodblock printing is a centuries old art form. This time-honoured form of art is at risk of extinction as a consequence of the increasing lack of availability of wild cherry trees, which are a traditionally used woodblock material. Solutions for this material problem have been investigated for several years, but none of the tested materials has been sufficient when compared with the watercolour print quality imprinted by wild cherry woodblocks. To contribute to overcoming this material problem, we have investigated the physical properties of heat-treated woodblock materials made from different wood species. The International Commission on Illumination (CIE) tristimulus values, the CIELAB coordinates, the total reflectance, and the gloss, as well as, the water contact angle from the woodblock surface is observed to have a strong relation to the surface treatment of a woodblock. The surface treatment of a woodblock, in turn, relates to its water delivery, which is the basis for watercolour printing.     

A single-mode KrF laser

Single-mode operation of a KrF laser oscillator has been achieved for the first time. The laser medium is pumped by an electron beam which allows excitation for a much longer duration than with discharge pumping. The long excitation time, together with the use of a short oscillator cavity with a low single-pass gain, allows many roundtrips before saturation is reached. This makes line-narrowing easier and single-mode operation has been achieved using only two intracavity etalons.Technical Research Centre of Finland, Helsinki, Finland