New spectrophotometric method for the determination of trace amounts of palladium

Summary A simple, rapid, selective, and sensitive method for the spectrophotometric determination of palladium is developed based on the reaction of Pd(II) with 1-amino-4-hydroxyanthraquinone (AMHA). The reaction is carried out atpH 3.8 in 50% (v/v) ethanol-water medium. The molar absorptivity of the complexed ligand is 1.1 · 10⁴ l mol^–1 cm^–1 at 620 nm. Calibration plots are linear up to 17 µg Pd cm^–3. The optimum concentration range (Ringbom plot) is between 3–14.5 µg cm^–3. The spectral study of the reaction in solutions containing equimolar concentrations or an excess of one component, in thepH range 0.3–6.5, indicate the possible complex transitions that occur in solution. Complete graphical and logarithmic analysis of the absorbance-pH graphs was performed to demonstrate and characterize the complexation equilibria in solution. Under the optimum conditions, palladium can be determined as the noncharged complex Pd(AMHA)₂ in the presence of a large number of foreign ions. Interferences caused by zirconium(IV) could be masked with fluoride ions.

---

Eine neue spektrophotometrische Methode für die Bestimmung von Palladium in Spuren

Zusammenfassung Eine einfache, schnelle und empfindliche Methode für die spektrophotometrische Bestimmung von Palladium wurde auf der Basis der Reaktion von Pd(II) mit 1-Amino-4-hydroxyanthrachinon (AMHA) entwickelt. Die Reaktion wird in 50% (v/v) Ethanol/Wasser beipH 3.8 ausgeführt. Die molare Absorption des komplexierten Liganden beträgt 1.1 · 10⁴ l mol^–1 cm^–1 bei 620 nm. Kalibrierungskurven verlaufen bis zu 17 µg Pd cm^–3 linear. Der optimale Konzentrationsbereich (Ringbom-Plot) liegt zwischen 3 und 14.5 µg cm^–3. Spektroskopische Untersuchungen der Reaktion in Lösungen, entweder mit equimolaren Konzentrationen oder mit einem Überschuß an einer Komponente impH-Bereich 0.3–6.5, lassen Rückschlüsse auf mögliche Komplex-Übergänge in Lösung zu. Es wurde eine vollständige graphische, logarithmische Analyse der Absorptions-pH-Graphen durchgeführt, um die Komplexgleichgewichte in Lösung aufzuklären und zu charakterisieren. Unter den Optimalbedingungen kann Palladium als nichtgeladener Komplex Pd(AMHA)₂ in Gegenwart einer großen Anzahl an Fremd-Ionen bestimmt werden. Schwierigkeiten mit Zirkonium(IV) konnte durch Maskierung mit Fluorid-Ionen umgangen werden.

     

Chemical composition and antimicrobial activity of the essential oils of Ferula latisecta and Mozaffariania insignis from Iran

The hydrodistilled oils from the aerial parts of Ferula latisecta and Mozaffariania insignis, which is endemic to Iran, were analyzed by GC and GC/MS. (Z)-Ocimenone (32.4%), (E)-ocimenone (20.3%), and cis-pinocarvone (11.4%) were the main components among the 22 constituents characterized in the oil of F. latisecta, representing 87.7% of the total components detected. Twenty-five compounds were identified in the oil of M. insignis, representing 99.0% of the total oil, with octyl acetate (41.1%), β-pinene (30.3%), and α-pinene (23.9%) as the main constituents. The essential oils were examined for their potential antimicrobial activities. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 561–563, November–December, 2006.     

N-halogeno-compounds. Part 9 [1]. Azoxy- and azo-arenes derived from 4-(dichloroamino)tetrafluoropyridine; crystal structure of trans-2,3,5,6-tetrafluoro-4-(2,4,6-trimethylphenyl-onn-azoxy)pyridine

The nitrosoarenes ArNO (Ar = C₆H₅, 2-MeC₆H₄, 2,4,6- Me₃C₆H₂ and C₆F₅) have been condensed with 4-(dichloroamino)- tetrafluoropyridine to provide the azoxy-compounds py_FN$\text{N}\text{+}$($\text{N}\text{-}$)Ar (py_F = 2,3,5,6-tetrafluoro-4-pyridyl); de-oxygenation of the first three with triphenylphosphine or triethyl phosphite gave the corresponding azo-compounds, and the reverse reaction was achieved in the case of py_FNNC₆H₂Me₃-2,4,6 using peroxytrifluoroacetic acid. Thermolysis of 4-azidotetrafluoropyridine in the presence of pentafluoronitrosobenzene provided the perfluorinated azoxy-compound py_FN$\text{N}\text{+}$($\text{O}\text{-}$)C₆F₅. X-Ray methods have been used to determine the molecular geometry of py_FN$\text{N}\text{+}$($\text{O}\text{-}$)C₆H₂Me₃-2,4,6.     

Influence of substitutions on asymmetric dihydroxychlorins with regard to intracellular uptake, subcellular localization and photosensitization of Jurkat cells

The search for new efficient sensitizers for photodynamic therapy (PDT) points to improve photophysical properties like absorption in the red region and singlet oxygen quantum yield as well as to control the localization of the sensitizer within the tumour cell. Depending on their physicochemical properties and their uptake mechanism, sensitizers can reach different intracellular concentrations and localize in different subcellular compartments. Moreover, the preferential localization of a sensitizer in target organelles, like mitochondria or lysosomes, could determine the cell death mechanism after PDT. This study aimed to investigate the influence of substitutions on dihydroxychlorins with regard to intracellular uptake, subcellular localization and cell death pathway. Moreover, the effect of a liposome-based delivery system was tested. The intracellular uptake was found to be strictly dependent on the sensitizer molecular structure and the means of its delivery. The most polar sensitizer in this study (compound 3) had, depending on incubation time, an intracellular concentration 2-8 times higher than the unsubstituted chlorin 1. All investigated photosensitizers localize predominantly in lysosomes but after longer incubation times weak fluorescence intensity was also detected in mitochondria and Golgi apparatus. The cell death pathway was found to be influenced by the sensitizer intracellular concentration and the applied light doses. In general, the increasing amphiphilicity of the sensitizer molecules is correlated with an increased sensitizer uptake and an increased rate of necrotic cells after irradiation.     

Reaction Mechanisms of Strontium Ferrites Synthesis

The reactions between strontium and iron nitrates have been studied in an open atmosphere system using three different molar ratios, 1:1 (I), 1:2 (II) and 2:1 (III) at different temperatures as pointed out from the DTA data. The reaction mechanism was discussed based on the chemical composition characterized by means of thermal analysis, X‐ray diffraction patterns, infrared spectra and magnetic susceptibility. It was found that the reaction products depend on both temperature of reaction and the ratio between reactants. The reaction products were found to be composed of a variety of iron compounds that possess different valences: SrFeO_2.86, SrFeO_2.97, SrFe₂O₄, SrFe₁₂O₁₉, Sr₂Fe₂O₅ and Sr₇Fe₁₀O₂₂ in addition to some accessory reaction products namely α‐Fe₂O₃ and FeO(OH).     

Computational complexity of LCPs associated with positive definite symmetric matrices

Murty in a recent paper has shown that the computational effort required to solve a linear complementarity problem (LCP), by either of the two well known complementary pivot methods is not bounded above by a polynomial in the size of the problem. In that paper, by constructing a class of LCPs—one of ordern forn 2—he has shown that to solve the problem of ordern, either of the two methods goes through 2 ⁿ pivot steps before termination.However that paper leaves it as an open question to show whether or not the same property holds if the matrix,M, in the LCP is positive definite and symmetric. The class of LCPs in whichM is positive definite and symmetric is of particular interest because of the special structure of the problems, and also because they appear in many practical applications.In this paper, we study the computational growth of each of the two methods to solve the LCP, (q, M), whenM is positive definite and symmetric and obtain similar results.This research is partially supported by Air Force Office of Scientific Research, Air Force Number AFOSR-78-3646. The United States Government is authorized to reproduce and distribute reprints for governmental purposes notwithstanding any copyright notation thereon.     

Synthesis of Some New Thiazole,Oxazole, Pyrimidine and Pyridazine Derivatives from 2‐cyano‐N‐octadecyl‐acetamide as Antimicrobial and Surface Active Agents

The motivation behind the present work is to synthesize some nonionic surfactants containing heterocyclic nucleus with intermediate fatty compounds for improving their surfactants properties. 2‐Cyano‐N‐octadecylacetamide was utilized as key intermediate for the synthesis of some new thiazole, pyrazole, oxazole, pyrimidine, 1,3‐dithiolane, thiophene, coumarin, oxazine and pyridazine derivatives. The newly synthesized compounds undergo propoxylation using propylene oxide to afford nonionic surface active agents. The antimicrobial and surface activities were evaluated and characterized through investigations of their spreading behavior in monolayer on water.     

Observation on Symmetry Properties of Sodium Zinc(II)-2,9,16,23-phthalocyanine Tetracarboxylate in Water:NaOH Solution

The shift of the Q-band of sodium zinc(II)-2,9,16,23-phthalocyanine tetracarboxylate (ZnPc(COONa)₄) to about 800 nm is attributed to the influence of the electron-donating property of the carboxylate groups substituted in the β–position. ZnPc(COONa)₄ which was found to have a symmetry of D _2h characterized by a splitting of the Q transition. This splitting was interpreted by the formation of dianionic symmetric ZnPc(COONa)₄ resulting from the dissociation of the pyrrole protons as well as the possibility of Na⁺ dissolution of ZnPc(COONa)₄ in the aqueous solution of NaOH.     

Performance investigation of an advanced tracked prime mover on the low bearing soil

This study has presented a performance investigation of an advanced tracked prime mover for the operation of agricultural goods and other operations on peat terrain. The maximum and continuous traction torque of the prime mover has been developed by designing an advanced controller for controlling the intelligent system. The prime mover’s mobility is studied with ultrasonic displacement sensor, torque transducer, National Instrument cRIO-9004 Compact-RIO Real-time Controller Unit (RCU), a National Instrument TPC 2106T Touch Panel Control (TPC), a Trimble AG132 GPS antenna and receiver unit, and a Dlink DIR-655 router. The fuzzy logic controller (FLC) has been equipped with the prime mover hydraulic system to increase the traction torque of the hydraulic motor when the prime mover’s sinkage is more than or equal to 70 mm. The prime mover’s design demonstrates good potential in traversing peat terrain as the measured tractive effort was found to be 48% of the vehicle’s gross weight while the recommended tractive effort is in the range of 30–36% of the vehicle’s gross weight.     

Chromium Trioxide Supported onto Wet Silica Gel: Rapid Oxidation of Alcohols to Carbonyl Compounds Under Microwave Irradiation in Solventless System

In an environmentally benign system, alcohols are rapidly oxidized to carbonyl compounds using CrO 3 supported onto wet silica gel as an oxidant under microwave irradiation.