In situ infrared study of SBA-15 functionalized with carboxylic groups incorporated by a co-condensation route

Two samples of SBA-15 mesoporous silica with a different content of carboxylic groups (-COOH) were prepared by a co-condensation route, using 4-(triethoxysilil)butyronitrile as the organosilane agent, then treating the samples with sulfuric acid, which removes the template and simultaneously hydrolyses the -CN to -COOH groups, as shown by IR spectroscopy. Both incorporation of organosilane agents and subsequent acid treatment do not affect the ordered SBA-15 structure. The proton-donor ability of carboxylic groups, as well their accessibility to reactants, has been studied in the IR by dosing ammonia, which forms reversibly COO- groups and NH4+ ions. The related equilibrium constants have been determined by elaboration of IR data. Outgassing the samples at progressively increasing temperatures destabilizes to an increasing extent the ammonium/carboxylate ion pair, because of the decrease in surface polarity brought about by dehydration: this decreases the related equilibrium constants. The amount of carboxylic groups undergoing reaction appears instead to be constant with dehydration, and to coincide with the whole population of COOH groups. Titration with alkali solutions yielded surface concentrations for the two samples of ca. 1.0 and 0.45 COOH/nm2. Proportionality between the surface concentrations and the intensities of the C=O IR band is observed: this suggests that COOH groups are noninteracting with each other and allows the computation of the related extinction molar coefficient.     

Influence of structural changes on the ion selectivities of magnesium ionophores based on malonic acid diamides

In an investigation of octamethylene bis(malonic acid diamides) and their selectivities for magnesium, it was found that presence of secondary amides within the particular ionophore played a considerable role in the enhancement of magnesium selectivity. Similar effects in other ionophores, i.e. tris(malonic acid diamides), were thus systematically looked at with the help of selectivity measurements with the hope of optimizing the number of secondary and tertiary amides so as to improve the magnesium selectivity. The syntheses of several investigated tris(malonic acid diamide) isologues are equally reported.Deceased in November 1992     

Epitaxial growth of sexiphenyl on Al(111): from monolayer to crystalline films

A combination of in situ surface sensitive-techniques, UV photoemission and low energy electron diffraction, with ex situ bulk sensitive X-ray diffraction reveals the formation of epitaxial thin films of sexiphenyl on Al(111) starting from the first monolayer. For room temperature growth, highly ordered films are formed with a unique alignment of the sexiphenyl molecules with the long axes of all molecules aligned parallel to both the surface and the <10> azimuthal directions of Al(111). This is related to a densely packed highly commensurate first monolayer, which acts as a template for the unique (21) crystallite orientation observed.     

Electron impact and chemical ionization mass spectra of alkyldiphenylphosphine oxides

In the 70 e V electron impact mass spectra of a series of alkyldiphenylphosphine oxides (R?₂PO, R = Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, t-Bu, neopentyl, n-decyl), molecular ions of low abundance are observed and [M + H]⁺ ions are formed to a small extent at high sample pressures. The major ions include [?₂PO]⁺, [?₂POH]⁺; [?₂CH₂PO]⁺ and [?₂CH₂POH]⁺ which are formed by rearrangement and cleavage processes. The chemical ionization mass spectra obtained with methane and isobutane reagents consist of [M + H]⁺ ions. The proton affinity of R?₂PO was found to be 219 ± 2.5 kcal mol^?1.     

Influence of phytohormones on polar and hydrophobic parts of mixed phospholipid monolayers at water/air interface

Surface parameters--the limiting area, collapse pressure, and compressibility modulus for monolayers of phospholipids containing a determined hydrophobic part (16:0) but different polar parts (PPL) and a determined polar part (PC) but different fatty acids (HPL), characteristic of nonembryogenic (NE) and embryogenic (E) winter wheat calli--were evaluated at 15 degrees C. These parameters were dependent on the kind of hydrophilic group and the size of the hydrophobic part of phospholipids. In the case of PPL, higher values of Alim and picoll were noticed for NE phospholipids. In the case of HPL, lower Alim and higher picoll were detected for NE than for E monolayers. All investigated phospholipid systems stimulated the adsorption of phytohormones from the water subphase. The influence of phytohormones of anionic (IAA, 2-4-D), cationic (kinetin, zeatin), and nonionic character (zearalenone) was examined. It appeared that the surface activity of phytohormones depended strongly on the kind of tissue from which the phospholipid mixture was extracted and, in a lesser degree, on their charge. In PPL systems with a determined hydrophobic part (16:0), no great differences in phytohormone influence on NE and E monolayers were observed (except of IAA). The greatest phytohormone influence on NE monolayers in HPL systems was related to the structure of the hydrophobic part of phospholipids. IAA, the most active (with the highest Alim values) among the phytohormones examined, influenced both HPL and PPL monolayers. This indicated the interactions of IAA with polar groups of phospholipids. Phytohormones also changed the monolayer stability against collapse process and the direction of changes depended on the kind of tissue (embryogenic or nonembryogenic).     

Regiospecific synthesis of mono-N-substituted indolopyrrolocarbazoles

[reactions: see text] Two complementary and efficient strategies have been developed for the regiospecific synthesis of unsymmetrical indolopyrrolocarbazoles (IPCs) mono-N-substituted with a pentacycle. A halogen in position 2 of the intermediate bisindolylmaleimides 3a-e allows a selective Mitsunobu coupling by exploiting the increased acidity of the 2-chloro-substituted indole nitrogen. It also promotes an easier cyclization of bisindolylmaleimides 4a-e and 7b-e to IPCs. Alkylation of the 2-unsubstituted indole-3-carboxamides 2a,b and further processing to the corresponding IPCs gives access to the opposite regioisomers.     

Phlogophites intercalated with Al2O3 pillars and modified with transition metals as catalysts of the DeNOx process

Natural phlogophite, pre-treated with acids and intercalated with alumina pillars, was used as catalytic support. Transition metals (Fe, Cu) were deposited on the surface of the modified clay materials by an ion-exchange method. The obtained samples were characterized with respect to structure (XRD), texture (BET), composition (EPMA) and chemical nature of the deposited transition metals species (UV-vis-DRS). The phlogophite based materials have been found to be active and selective catalysts of the DeNOx process. The Fe-containing samples were catalytically active at lower temperatures than the clays modified with copper. A competitive ammonia oxidation by oxygen decreased the effectiveness of the DeNOx process in the high temperature range.     

SITES OF PHOTODAMAGE in vivo and in vitro BY A CATIONIC PORPHYRIN

Abstract— Localization and photodynamic efficacy of a monocationic porphyrin (MCP) were assessed using murine leukemia cells in culture. This sensitizer localized at surface membrane loci and catalyzed selective photodamage to membrane structures. Although both cationic and hydrophobic, this porphyrin was not recognized by the multidrug transporter, which excludes many cationic agents from cells that express multidrug resistance. Photodynamic studies with the murine radiation-induced fibrosarcoma tumor model indicated moderate photosensitization of neoplastic lesions in vivo at 3 h, but not at 24 h after sensitizer administration. Pharmacokinetic studies indicate that plasma levels, not tissue levels were the major determinant of photodynamic therapy (PDT) response. Consistent with this observation, vascular damage and disturbances of tissue perfusion followed PDT. These effects were more pronounced in tumor-bearing skin than in normal skin. The therapeutic response to MCP appeared to be related mainly to secondary, probably vascular, effects.     

Fundamental and applied investigations in plasma-source mass spectrometry for elemental analysis

The current status of plasma source-mass spectrometry (PS-MS) is reviewed. An overview of interference effects that exist, alternative plasma sources available, and mass spectrometer interface studies is provided. A discussion of current and future development areas in plasma source mass spectrometry is also included.     

Spectrochemical Properties of Noncubical Transition Metal Complexes in Solution. XII. Angular Overlap Studies of Salicylideneethylenediamine Cu(II) Complex in Various Solvents

As a part of our general interest in the UV-Vis spectroscopy of multidentate mixed-donor ligands, the (salicylideneethylenediamine)Cu(II) complex has been prepared and characterized by elemental analyses, solubility in common solvents, molar conductivities, and ultraviolet (UV), and visible (Vis) spectroscopy. The combined results of spectrophotometric measurements and EPR spectra, as well as known the X-ray structure for solids, were used to determine the structure of the investigated complex in solutions. The spectra of [Cu(salen)] (H₂salen = salicylideneethylenediamine), were measured in various solvents at room temperature, resolved by Gaussian analysis, and angular overlap model (AOM) treated in C _2v symmetry. Because of overparametrization problems, the bis(salicylaldehyde)Cu(II) complex has been characterized and AOM treated. The results of this have been used for AOM studies of [Cu(salen)]. The effect of the solvents upon the - and -bonding ligand abilities is discussed.