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141.
Zusammenfassung Am Beispiel des Aerosils wurde die Ver?nderung der Oberfl?che des Siliciumdioxids bei der Entwicklung verschiedener hydrolytischer
Agentien untersucht. Die Oberfl?che des Aerosils enthielt ursprünglich neben Silanolgruppen in erheblichem Umfang Siloxangruppen.
Mit kaltem Wasser, mit ammoniakalischer Brenzkatechin-L?sung und bei kürzerer Einwirkung von siedendem Wasser wurde eine teilweise
Hydrolyse der Siloxan-Bindungen erreicht, doch, wurden nie mehr als 3.3 Silanolgruppen pro 100 ?2 erhalten.
Nach l?ngerer Einwirkung von siedendem Wasser wurde eine Abnahme der spez. Oberfl?che und der Zahl der Silanolgruppen pro
Fl?cheneinheit beobachtet. Im Elektronenmikroskop zeigten die Teilchen dieser Aerosile Hüllen geringerer Dichte aus feinporigem
Siliciumdioxid. Infolge der extrem engen Poren wurde ein erheblicher Teil der Oberfl?che und der Silanolgruppen bei den Messungen
nicht erfa?t. Konz. Ammoniak und in geringerem Ma?e auch lange Lagerung an der Atmosph?re hatten ?hnliche Wirkung.
überhitzter Wasserdampf katalysierte bei 200° die Abspaltung von Wasser aus Silanolgruppen. Die Pr?parate verloren dabei mehr
Wasser als bei gleicher Temperatur im Hochvakuum.
Die Ergebnisse und die Mechanismen der Ver?nderungen werden diskutiert.
Herrn Prof.U. Hofmann zum 60. Geburtstag gewidmet.
Herrn Prof. Dr.U. Hofmann sind wir für stete F?rderung und gro?zügige Unterstützung unserer Arbeiten zu gro?em Dank verpflichtet. Dem Fonds der Chemie und dem Landesgewerbeamt des Landes Baden-Württemberg danken wir für finanzielle Unterstützung. 相似文献
Summary The influence of various agents on the surface of Aerosil, a fine particle size silicia was studied. Originally, siloxane as well as silanol groups were present in the Aerosil surface. Partial hydrolysis of the siloxane bonds was achieved with cold water, ammoniacal pyrocatechol solution and after shorter contact with boiling water. The number of silanol groups per 100 ?2 never exceeded 3.3. On prolonged action of boiling water a significant decrease of the surface area and of the number of silanol groups was observed. Electron microphotographs show that the particles became coated by a layer of less dense porous silicia. As a result of the extremely narrow pores part of the surface and of the silanol groups escaped detection. Ammonia and, to a lesser extent, prolonged storing at atmospheric conditions had similar effects. At 200 °C the condensation of silanol groups to siloxane bonds was catalyzed by superheated steam as evidenced by a greater loss of silanol groups than in a high vacuum at the same temperature. The results and the mechanisms of the changes in the silica surface are discussed.
Herrn Prof.U. Hofmann zum 60. Geburtstag gewidmet.
Herrn Prof. Dr.U. Hofmann sind wir für stete F?rderung und gro?zügige Unterstützung unserer Arbeiten zu gro?em Dank verpflichtet. Dem Fonds der Chemie und dem Landesgewerbeamt des Landes Baden-Württemberg danken wir für finanzielle Unterstützung. 相似文献
142.
Summary Observation of the phenomena resulting from heating a substance first in air and then in hydrogen is recommended for the preliminary examination of small specimens of inorganic matter. It may permit immediate identification of simple compounds of the heavy metals. Reduction by heating in hydrogen is also recommended for the investigation of acid insoluble residues.
Dedicated to Prof.Hans Lieb on occasion of his 70th birthday. 相似文献
Zusammenfassung Das Verhalten beim Erhitzen in Luft und dann in einer Wasserstoff-atmosphäre eignet sich für die Vorprüfung kleiner Mengen anorganischer Substanz. In einzelnen Fällen können einfache Verbindungen der Schwermetalle daran erkannt werden. Die Reduktion durch Erhitzen in einer Wasserstoffatmosphäre empfiehlt sich ferner für die Untersuchung säureunlöslicher Rückstände.
Résumé L'observation du phénomène résultant du chauffage d'une substance dans l'air puis dans l'hydrogène est recommandée comme examen préliminaire de petits échantillons minéraux. Elle peut permettre l'identification immédiate de composés simples des métaux lourds. La réduction par chauffage dans l'hydrogène est également recommandée pour l'examen de résidus insolubles dans les acides.
Dedicated to Prof.Hans Lieb on occasion of his 70th birthday. 相似文献
143.
Rainer Telle Ai Momozawa Jochen M. Schneider 《Journal of solid state chemistry》2006,179(9):2850-2857
MAX-phases being usually composed of transition metals, group A elements and carbon/nitrogen are considered interesting materials for many applications because of their tremendous bulk modulus, “reversible” plasticity, and machinability. This is mainly due to their unique kind of bonding comprising covalent, ionic as well as metallic bonds providing “easy” planes of rupture and deformability due to the layered crystal structures.In transition metal boride systems, similar types of bonding are available. In particular the W2B5-structure type and its stacking variations allow the synthesis of strongly layered crystal structures exhibiting unique delamination phenomena.The paper presents ab initio calculations showing the similarities of bonding between the ternary carbides and the corresponding ternary or quaternary borides. Formation of boride-based nano-laminates from auxiliary liquid phases, from the melt as well as during sintering and precipitation from supersaturated solid solutions will be discussed by means of SEM and TEM studies. The role of impurities weakening the interlayer bonding will be addressed in particular. The pronounced cleavage parallel to the basal plane gives rise for crack deflection and pull-out mechanisms if the laminates are dispersed in brittle matrices such as boron carbide, silicon carbide or other transition metal borides. 相似文献
144.
Hans‐Dietrich Stachel Barbara Zimmer Eduard Eckl Katharina Semmlinger Wolfgang Weigand Ralf Wünsch Peter Mayer 《Helvetica chimica acta》2005,88(6):1208-1220
The 1,2‐dithiolosultam derivative 14 was obtained from the (α‐bromoalkylidene)propenesultam derivative 9 (Scheme 1). Regioselective cleavage of the two ester groups (→ 1b or 2b ) allowed the preparation of derivatives with different substituents at C(3) in the dithiole ring (see 27 and 28 ) as well as at C(6) in the isothiazole ring (see 17 – 21 ; Scheme 2). Curtius rearrangement of the 6‐carbonyl azide 21 in Ac2O afforded the 6‐acetamide 22 , and saponification and decarboxylation of the latter yielded ‘sulfothiolutin’ ( 30 ). Hydride reductions of two of the bicyclic sultams resulted in ring opening of the sultam ring and loss of the sulfonyl group. Thus the reduction of the dithiolosultam derivative 14 yielded the alkylidenethiotetronic acid derivative 33 (tetronic acid=furan‐2,4(3H,4H)‐dione), and the lactam‐sultam derivative 10 gave the alkylidenetetramic acid derivative 35 (tetramic acid=1,5‐dihydro‐4‐hydroxy‐2H‐pyrrol‐2‐one) (Scheme 3). Some of the new compounds ( 14, 22, 26 , and 30 ) exhibited antimycobacterial activity. The oxidative addition of 1 equiv. of [Pt(η2‐C2H4)L2] ( 36a , L=PPh3; 36b , L=1/2 dppf; 36c , L=1/2 (R,R)‐diop) into the S? S bond of 14 led to the cis‐(dithiolato)platinum(II) complexes 37a – c . (dppf=1,1′‐bis(diphenylphosphino)ferrocene; (R,R)‐diop={[(4R,5R)‐2,2‐demithyl‐1,3‐dioxolane‐4,5‐diyl]bis(methylene)}bis[diphenylphosphine]). 相似文献
145.
An europium-sensitized time-resolved luminescence (TRL) method was developed to determine oxytetracycline (OTC) in cultivated catfish muscle. Extraction of OTC from fish muscle was performed with pH 4.0 ethylenediaminetetraacetic acid (EDTA)-McIlvaine buffer and clean up with hydrophilic-lipophilic balanced copolymer solid phase extraction (SPE) cartridges. The eluate was used without further concentration for TRL measurement in pH 9.0 micellar tris(hydroxylmethyl)aminomethane (TRIS) buffer. Cetyltrimethylammonium chloride (CTACl) was used as surfactant and EDTA as a co-ligand. The excitation and emission wavelengths were set at 388 and 615 nm, respectively. The linear dynamic range was 0-1000 ng g−1 (R2=0.9995). The recovery was 92-112% in the fortification range of 50-200 ng g−1 and the limits of detection (LOD) ranged from 3 to 7 ng g−1. Incurred catfish samples were used to demonstrate the performance of the method around 100 ng g−1, the European Union maximum residue level. 相似文献
146.
Antonio L. Braga Helmoz R. Appelt Claudio C. Silveira Ludger A. Wessjohann Paulo H. Schneider 《Tetrahedron》2002,58(52):10413-10416
The enantioselective alkynylation reaction of aldehydes with alkynes and diethylzinc, catalyzed by chiral disulfide–oxazolidine ligands, provides a simple, practical and inexpensive method to access chiral propargylic alcohols in good yields and satisfactory ee's. 相似文献
147.
Stripelike domains of Langmuir monolayers formed by surfactants with partially fluorinated lipid anchors (F-alkyl lipids) are observed at the gas-liquid phase coexistence. The average periodicity of the stripes, measured by fluorescence microscopy, is in the micrometer range, varying between 2 and 8 microm. The observed stripelike patterns are stabilized due to dipole-dipole interactions between terminal- CF(3) groups. These interactions are particularly strong as compared with nonfluorinated lipids due to the low dielectric constant of the surrounding media (air). These long-range dipolar interactions tend to elongate the domains, in contrast to the line tension that tends to minimize the length of the domain boundary. This behavior should be compared with that of the lipid monolayer having alkyl chains, and which form spherical microdomains (bubbles) at the gas-liquid coexistence. The measured stripe periodicity agrees quantitatively with a theoretical model. Moreover, the reduction in line tension by adding traces (0.1 mol %) of cholesterol results, as expected, in a decrease in the domain periodicity. 相似文献
148.
149.
Crystal Structures of MgCrO4-type Li2VCl4 and Spinel-type Li2MgCl4 and Li2CdCl4 The crystal structures of the ternary lithium chlorides Li2MCl4 (M = Mg, V, Cd) have been determined firstly by X-ray single-crystal experiments. Li2MgCl4 and Li2CdCl4 crystallize in an inverse spinel structure (space group Fd3 m, Z = 8, a = 1 040.1(2) and 1 062.06(9) pm, structural parameters u = 0.25699(2) and 0.2550(1), R = 1.7 and 3.7% for 218 and 211 unique reflections). The Li? Cl distances of the tetrahedrally coordinated Li+ ions are significantly greater than calculated with Shannon's crystal radii ( > 238 ± 1 instead of 233 pm). Contrary to the results of X-ray powder data reported in the literature, Li2VCl4 crystallizes in the distorted spinel structure of MgCr2O4 type (space group F4 3m, Z = 8, a = 1 037.49(2) pm, R = 5.9% for 217 unique reflections). The decrease of the site symmetry of the octahedrally coordinated ions (V2+, Li+) from 3 m to 3m resulting in contracted and widened tetrahedral M4 entities of the spinel structure is obviously caused by V? V metal—metal bonds (shortest V? V distance 366.2(7) pm). 相似文献
150.