Zur Kenntnis der Ortho-Strontiumphosphate

Zusammenfassung Die für den Einbau in die Calciumphosphate der Knochensubstanz in Frage kommenden Strontiumphosphate wurden auf ihre Existenzbedingungen untersucht. Oktacalciumphosphat tauscht in verd. Lösungen einige Prozente des Calciums gegen Strontium aus. Obwohl der Struktur nach apatitartige Strontiumphosphate zwischen Sr/P=1.33 und 1.67 erhältlich sind, läßt sich ein röntgenoptisch reines Strontiumoktaphosphat nicht isolieren, jedoch ein solches mit kleinem Carbonatgehalt und — leicht — die den Calciumsalzen analogen Strontiumphosphatcarbonate verschiedener Zusammensetzung. Im Hydrothermalbereich (375^o) sind je nach relativer Zusammensetzung des Strontiumphosphat-Systems SrHPO₄, Sr₂P₂O₇, Sr₂(PO₄)₂ und Sr₅(PO₄)₃OH stabil und gut kristallin erhältlich. Das Salz Sr₆H₃(PO₄)₅ läßt sich aus Lösungen von Strontiumphosphaten in Kohlensäure-Wasser, H₂S-Wasser und in einem Barbiturat-Puffersystem rein darstellen.

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Ortho strontium phosphates

Strontium phosphates which possibly are being incorporated into the calcium phosphates of bony tissue were investigated. Octacalcium phosphate in dilute solutions exchanges a few percent of calcium against strontium. While strontium phosphates with apatite-like structures, and with ratios of Sr/P between 1.33 and 1.67 can be prepared, no pure strontium octaphosphate, as a distinctive X-ray phase can be isolated. Only preparations with small amounts of carbonate, as well as strontium phosphate carbonates analogous to the corresponding calcium salts can be obtained. At hydrothermal conditions (375^o), the compounds SrHPO₄, Sr₂P₂O₇, Sr₃(PO₄)₂ and Sr₅(PO₄)₃OH are stable, and can be prepared in well cristallized form, depending on the relative composition of the strontium phosphate system. The salt Sr₆H₃(PO₄)₅ can be prepared in a pure state from solutions of strontium phosphates in aqueous solutions of carbonic acid, H₂S and barbiturate buffer systems.

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Herrn Prof. Dr. Dr. h. c.Hans Nowotny gewidmet.     

Clinical usefulness of a trypsin radioimmunoassay kit

From the clinical use of RIA-gnost trypsin kit, the following results were obtained. 1. Standard curve showed a steep and good curve was shown. 2. Incubation: The condition for the first incubation was set at the room temperature for 10-24 hours and that for the second incubation at the room temperature for 3-5 hours. With these settings, satisfactory results were obtained. 3. Reproducibility and recovery: The C.V. of the reproducibility and the recovery were considered superior, and the values were below 10% and +/- 3%, respectively. 4. Correlation between trypsin and serum elestase-1: An excellent positive correlation (coefficient of correlation r = 0.889) was shown. 5. Serum trypsin concentration of normal and pancreatic diseases: The normal range was from 100 to 500 ng/ml. Acute pancreatitis rose obviously. Diabetes mellitus and chronic pancreatitis was below 500 ng/ml and the pancreatic cancer showed a tendency to scatter in the range of 50-1,250 ng/ml. The above results indicated that serum trypsin can be easily measured with high precision by using this method. Thus the method is considered useful for the diagnosis of pancreatic diseases.     

Syntheses and biological activities of renin inhibitors containing statine analogues

Syntheses and biological activities of dipeptide renin inhibitors that contain statine analogues are described. The key steps of the synthetic approach to dipeptide renin inhibitors are the asymmetric synthesis of 2(R)-substituted-3-aminocarbonylpropionic acids and the diastereoselective syntheses of (3S,4S)-statine analogues. These inhibitors (2,14-40) inhibited human renin in the 3-140 nM range. Inhibitor ES 6864 (2) was found to be a highly potent inhibitor of human renin (IC50: 4.6 x 10(-9) M) and showed high enzyme specificity. Oral administration of ES 6864 at 3 mg/kg to conscious, sodium-depleted marmosets inhibited plasma renin activity (PRA) more than 80% after 1 h.     

Determination of molecular weight of native proteins by polyacrylamide gradient gel electrophoresis

An improved method for the estimation of molecular weights of native proteins by polyacrylamide gel electrophoresis, in 9 cm x 9 cm x 0.05 mm 4-20% T fabric reinforced gradient gels, is described. Plotting the logarithm of the relative mobilities of proteins versus gel concentrations produces lines whose slopes are related to molecular weights.     

Determination of catecholamines in pheochromocytoma cell (PC-12) culture medium by microdialysis-microbore liquid chromatography

An in vitro microdialysis system was constructed for the measurement of catecholamines in pheochromocytoma cell culture medium. The novel microdialysis device is composed of a petri dish, a dialysis membrane and two transmission tubes. The dialysis membrane is located in the space of a petri dish such that it is immersed in the culture medium. Catecholamines contained in the culture medium diffused into a designed dialysis membrane with sufficient recovery (about 60%). Dialysates were collected by a sampling loop and introduced by an on-line injector to a microbore liquid chromatographic system for analysis of catecholamines. This assay yielded a detection limit of 0.2–0.5 pg/injection with acceptable intra- and inter-assay reproducibilities in 5 μl of dialysates. To evaluate the on-line microdialysis system, PC-12 cells were cultured in a petri dish within an incubator. The baseline concentration of dopamine in PC-12 cell culture medium was about 0.29 ng/ml which was elevated to 2.43 ng/ml after treatment with 0.5 mM potassium cyanide. In conclusion, the present microassay provides for the sensitive, direct measurement of catecholamines in culture medium while minimizing pretreatment procedures for sample preparation.     

Ruling out harmonic couplings as a possible origin of an anomalous isotope effect on the ν5modes in H bonds

Measurements of the transition probabilities of all the IR bands of adipic acid crystals, polarized in the a, c plane and having frequencies in the range 1000–4000 cm^?1show that the anomalous value P_H/P_D= 2 found for the ratio of the transition probabilities of ν_s bands

and

cannot be due to a harmonic coupling of ν_s vibrations with other vibrations.     

Head-to-head polymers—I. The preparation and some properties of head-to-head polypropylene

Samples of head-to-head polypropylene have been prepared by the hydrogenation of two polydienes; 1,4-poly(2,4-hexadiene) and 1,4-poly(2,3-dimethyl-1,3-butadiene). Glass transition temperatures were found to be marginally lower than for conventional polypropylene suggesting that the head-to-head placements in the chain increased the polymer flexibility.     

Electrochemical oxidation of alkyl-substituted allenes in methanol

Mono-, di- and tri-alkyl-substituted allenes were potentiostatically oxidized in methanol at graphite and Pt anodes. At the former electrode, α-methoxylated ketones (due to 4F/mole electricity consumption) and esters (6F/mole) were the major products. At a Pt anode, intermediate products such as vinyl-ether derivatives (2F/mole) were characterised too. Unlike the anodic oxidation of alkenes and alkynes previously reproted in the literature, dimerisation is not a typical process in the allenes' oxidation, since of all the products obtained only a sole dimer has been observed. The mechanism for the formation of most products is discussed.     

Octahedral cobalt(III) complexes of the chloropentammine type. XVII. Association and reaction of some halogenopentamminecobalt(III) and halogenopentamminechromium(III) cations with hydroxide in aqueous dioxan

The replacement, by hydroxide ion, of the coordinated halide from some halogenopentamminecobalt(III) and -Chromium(III) cations in aqueous dioxan has been studied over a range of alkali concentrations up to 0.1 M. With excess of hydroxide ion at constant ionic strength, pseudo first-order rate constants were obtained. The results support a pre-equilibrium association of complex and hydroxide ions in these media, but do not provide distinction as to whether the resulting ion-pair subsequently reacts by direct exchange or by proton removal. The extents of ion association are found to be greater for the cobalt(III) than for the chromium(III) system, increasing with the amount of dioxin in the solvent mixture.     

A surface adsorption model for electroless cobalt alloy thin films

Thin cobalt alloy films have been obtained using electroless deposition solution with two reducing agents: dimethylamine borane (DMAB) and sodium hypophosphite. This system allows spontaneous and self-activated deposition of barrier layers on Cu lines and via contacts for ultra large scale integration (ULSI) interconnects applications. This work presents a study of the solution composition effects on the material properties and composition of the films. First, we present the deposition rates, the electrical resistance, the various element profiles in the thin film, and the thin film roughness. Next, we discuss the film’s composition and its dependence on the ratio between the reducing agents composition in the solution. The experimental results suggest that the film phosphorous and boron composition is determined by the surface adsorption rates of the reducing agents. Therefore, a surface co-adsorption model of the two reducing agents is proposed, formulated, analyzed, and compared to the experimental results. Finally, we discuss the model and its significance to the formation of high-quality ultra-thin barrier layers. Dedicated to Professor Dr. Algirdas Vaskelis on the occasion of his 70th birthday.