Study of the interaction between caesium bromide and kaolinite by differential thermal analysis

The reaction occurring during the wet grinding of kaolinite with CsBr was studied by simultaneous Differential Thermal Analysis -Thermogravimetry (DTA-TG), supplemented by infrared spectroscopy of isothermally treated CsBr disks. The DTA and TG curves were compared with those of untreated kaolinite and of kaolinite mixed or air ground with different alkali halides. A new endothermic DTA peak at 75–115°, accompanied by weight loss, is due to the desorption of surface and interparticle water located mainly at the interface between the mineral and the salt. A second endothermic peak at about 500° represents the simultaneous dehydroxylation of the clay and thermal hydrolysis of CsBr. The presence of a separate CsBr phase was identified from two endothermic peaks which characterize melting and boiling of the salt; only mixtures with more than 140 mmol CsBr per 100 g kaolinite show the presence of this phase. All of the CsBr below this concentration occurs in the CsBrHOH-kaolinite intercalation complex. This degree of saturation is smaller than that obtained previously for CsCl.

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Zusammenfassung Mittels simultaner DTA-TG wurde die sich während des Naßmahlens von Kaolinit mit CsBr stattfindende Reaktion untersucht, ergänzt durch IR-spektroskopische Untersuchungen von isotherm wärmebehandelten CsBr-Plättchen. Die DTA und TG Kurven wurden mit denen von unbehandeltem Kaolinit und von Kaolinit, vermischt oder an Luft gemahlen mit verschiedenen Alkalihalogeniden. Ein neuer endothermer DTA-Peak bei 75–115°C., begleitet von einem Gewichtsverlust, wird der Desorption von Oberflächen- oder interpartikelgebundenem Wasser zugeschrieben, das hauptsächlich an den Übergangsflächen Mineral/Salz lokalisiert ist. Ein zweiter endothermer Peak bei 500°C steht für die gleichzeitige Dehydroxylierung der Tonerde und die thermische Hydrolyse von CsBr. Aus zwei für Schmelzen und Sieden des Salzes charakteristischen endothermen Peaks konnte auf eine separate CsBr-Phase geschlossen werden; nur Gemische mit mehr als 141 mmol CsBr pro 100 g Kaolinit zeigen die Gegenwart einer solchen Phase. Unterhalb dieser Konzentrationsgrenze ist alles CsBr in CsBr-HOH-Kaolinit Durchdringungskomplexen vorhanden. Dieser Sättigungsgrad ist niedriger als der für CsCl.

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Dedicated to Professor Dr. H. J. Seifert on the occasion of his 60^th birthday

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S. Y. and A. N. are grateful to the Internal Fund of the Hebrew University of Jerusalem for financial support.     

The Mordell-Lang conjecture for function fields

We give a proof of the geometric Mordell-Lang conjecture, in any characteristic. Our method involves a model-theoretic analysis of the kernel of Manin's homomorphism and of a certain analog in characteristic .

     

Coupled-mode analysis of fiber-optic add drop filters for dense wavelength-division multiplexing

We present a coupled-mode theory of fiber-optic add-drop filters, which involve directional coupling between two fibers combined with fiber Bragg gratings defined inside the coupling region. The analysis self-consistently accounts for both the directional and the reflection coupling, and the propagation constants and structure of the supermodes of the combined structure are derived. We present a detailed analysis of a filter design based on identical fibers. The calculated device parameters satisfy the requirements for dense wavelength-division multiplexing applications.     

Catalytic asymmetric synthesis of chiral allylic amines. Evaluation of ferrocenyloxazoline palladacycle catalysts and imidate motifs

Palladium(II) catalysts based on a ferrocenyloxazoline palladacyclic (FOP) scaffold were synthesized and evaluated for the rearrangement of prochiral allylic N-(4-methoxyphenyl)benzimidates. When iodide-bridged dimer FOP precatalysts are activated by reaction with excess silver trifluoroacetate, the allylic rearrangement of both E and Z prochiral primary allylic N-(4-methoxyphenyl)benzimidates takes place at room temperature to give the corresponding chiral allylic N-(4-methoxyphenyl)benzamides in high yield and good ee (typically 81-95%). Several allylic imidate motifs were evaluated also. Because the corresponding enantioenriched allylic amide products can be deprotected in good yield to give enantioenriched allylic amines, allylic N-aryltrifluoroacetimidates were identified as promising substrates.     

Synthesis and thermo-XRD-analysis of the organo-clay color pigment

An intense blue organo-clay color pigment was obtained by adding naphthyl-1-ammonium chloride to a Na-montmorillonite aqueous suspension followed by treatment with sodium nitrite. This treatment resulted in the synthesis of the azo dye 4-(1-naphthylazo)-1-naphthylamine adsorbed onto the clay. The pigment was subjected to thermo-XRD-analysis and the diffractograms were curve-fitted. Heating naphthylammonium-montmorillonite at 360°C resulted in the evolution of the amine at temperatures lower than those required for the formation of charcoal and consequently the clay collapsed. On the other hand, heating the pigment at 360°C resulted in the conversion of the adsorbed azo dye into charcoal. The clay did not collapse, thus proving that the azo dye was located inside the interlayer space. Before the thermal treatment a short basal spacing in the pigment compared with that in the ammonium clay (1.28 and 1.35 nm, respectively) indicated stronger surface π interactions between the clayey O-plane and the azo dye than between this plane and naphthylammonium cation. The amount of dye after one aging-day of the synthesis-suspension increased with [NaNO₂]/[C₁₀H₇NH₃] ratio but did not increase with naphthylammonium when the [NaNO₂]/[C₁₀H₇NH₃] ratio remained 1. After 7 and 56 aging days it decreased, indicating that some of the dye decomposed during aging.     

Structure-Activity and Mechanism Studies on Silicon Phthalocyanines with Plasmodium falciparum in the Dark and Under Red Light

Syntheses for the new photosensitizers HOSiPc-OSi(CH₃)₂(CH₂)₃N(CH₂)₁ or ₃(CH₃)₂, Pc 34 and Pc 25, have been developed and the order of activity of these photosensitizers and the previously reported photosensi-tizer Pc 4, HOSiPcOSi(CH₃)₂(CH₂)₃N(CH₃)₂, in the dark and with broad-band red light toward Plasmodium falciparum in red blood cell (RBC) suspensions has been studied. The order of activity has been found to be Pc 4 Pc 34 Pc 25. Thus, the activity of the photosensitizers under both sets of conditions is inversely proportional to the length of their terminal amino alkyl chains. The 50% inhibition dye concentration (IC₅₀) in the dark for the parasites in RBC suspension with Pc 4 is 24 nM and the dye concentration and light fluence that yield:3 log₁₀ of parasite inactivation with Pc 4 are 2 mM and 3 J/cm², respectively. The synthesis of DNA and proteins by the parasites in culture was strongly inhibited by Pc 4 in the dark while parasite lactate dehydrogenase (pLDH) activity was unaffected. With Pc 4 and light, DNA and protein synthesis of the parasites in culture was strongly inhibited, pLDH activity of the parasites was moderately inhibited and ribosome density of the parasite cells was reduced. Gel electrophoresis studies showed that synthesis of all parasite proteins was inhibited to a similar extent. These results suggest that Pc 4 both in the dark and with light inactivates the cells by disturbing their machinery for the synthesis of not just one but a whole series of proteins. It is concluded that Pc 4 and light may be able to serve as a practical sterilization combination not only for HIV and other viruses but also for malaria parasites in RBC concentrates, and that Pc 4 by itself may have potential as a chemotherapeutic agent toward malaria.     

Thermal study of an aged dredged sludge

A dredged sludge was studied to investigate the influence of ageing and of pretreatment on its drying rate, water sorption/retention, thermal mass loss, XRD and microstructure (SEM).Ageing caused change in particle thickness and specific surface, a gradual aggregation to form units of the size 10–50 m, formation of macropores of similar size, unhomogeneity and fissures between aggregates and super-aggregates. Macropores were detectable by the initial drying rate especially at 45°C. They indicated a tendency of collapsing at a lower drying rate at 30°C. This is consistent with SEM observations. With ageing the aggregates were more compact and less sensitive to drying.The aggregated system indicated a higher initial drying rate (higher permeability), whereas stirring induced a lower drying rate, favouring the formation of compact laminar structure.XRD peak intensity was lowered with ageing due to decrease in crystallinity (stacking faults and/or decrease in crystallite size). The content of amorphous material was lowered as well, reducing water sorption/desorption, which indicated that the specific surface is lower.From the suitable microstructure induced by ageing some new phases may form (feldspar, zeolites), preferably in the coarser fraction of the sludge. This is disturbed by stirring which operation expels also carbonates from the particle edges and this may reduce the structural strength of the sludge. In aged bentonite suspension a similar tendency was observed of formation of specific microstructures capable of phase transformation, e.g. to feldspar.     

Catalytic thermal reactions of cumene over sepiolite and palygorskite

The catalytic activity of sepiolite and palygorskite in cracking and disproportionation reactions of cumene was studied. The formation of benzene, diisopropylbenzene and propylene characterizes Brönsted acid sites whereas that of ethylbenzene characterizes Lewis acid sites. At 150 and 250°C the reactions are determined mainly by the presence of acid sites in the channels of these clays. The yields are significantly higher in sepiolite as compared to palygorskite. The concentration of acid sites and their strength increase with the thermal loss of zeolitic and part of the bound water. At 350°C the reactions are determined by the acidity of the external surface of both minerals and yields are only slightly higher in sepiolite. At 150°C most acid sites are of the Brönsted type. With the rise in temperature the relative concentration of Lewis acid sites increases.

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Zusammenfassung Es wurde die katalytische Aktivität von Sepiolith und Palygorskit in Krack- und Disproportionierungsreaktionen von Kumol untersucht. Die Bildung von Benzol, Diisopropyl-benzol und Propylen charakterisieren Aziditätsstellen nach Bronsted, während die Bildung von Ethylbenzol Aziditätsstellen nach Lewis charakterisiert. Bei 150°C und 250°C werden die Reaktionen hauptsächlich durch die Gegenwart von Aziditätsstellen in den Tunnelgebilden dieser Tonerden bestimmt. Bezogen auf Palygorskit sind die Ausbeuten bei Sepiolith eindeutig höher. Die Konzentration der Aziditätsstellen und ihre Stärke nehmen mit der thermischen Abgabe von zeolithischem und eines Teiles des gebundenen Wassers zu. Bei 350°C werden die Reaktionen durch die Azidität der externen Oberfläche beider Mineralien bestimmt und die Ausbeuten sind in Sepiolith kaum höher. Bei 150°C sind die meisten Aziditätsstellen vom Brönsted-Typ. Mit ansteigender Temperatur nimmt auch die relative Anzahl von Lewis-Aziditätsstellen zu.

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Dedicated to Prof. Dr. H. J. Seifert on the occasion of his 60^th birthday     

Infrared study of the effects of thermal treatment on montmorillonite-benzidine complexes

Transition metal montmorillonites were saturated with benzidine (BEN) and heated gradually to 200°C, in a vacuum cell supported by KBr windows. IR spectra were recorded before and after the thermal treatment and at various temperatures during this treatment. X-ray diffractions were recorded before and after the thermal treatment. Hg clay shows properties similar to those of Mg and Ca clays. In the interlayer BEN is bound to Hg through a water molecule bridge, either by proton accepting (typeA) or by proton donation (typeB). Some BEN is also protonated (typeD). Initially typeA predominates, but after the thermal treatment, when the film is rehydrated, the amounts of typesB andD increase. With Mn-, Co-, Ni-, Zn- and Cd-montmorillonite a direct coordination of the benzidine by the dehydrated metallic cation is obtained (typeC), in addition to small amounts of typesA,B andD. During the thermal treatment water is evolved and associationsA andB are completely transformed toC. At elevated temperatures the following associations were identified in trace amounts, ammonium-amine, BEN bound to non-structured water, hydrophobic adsorbed BEN and BEN bound to the oxygen plane (typesE, F, H andJ, respectively). During the thermal treatment of Co and Cd clays some of the benzidine was oxidized, probably to semiquinone and quinoidal cation.     

Bounded variation of {V n } and its limit

This note studies relations between limV _n and the lower long-run average value ( \(\underline V \) ) in dynamic programming. It is shown that a certain bounded variation conditions of {V _n } implies that limV _n = \(\underline V \) .