On the reactivity of benzidinesulfonic acids and their applications in analysis: Reaction of cupric salts with o-benzidinemonosulfonic acid in presence of alkali thiocyanate

In the present work a new method for the detection of coppcr(II) is described. It is based on the reaction of this ion with the alkali salts of o-benzidinemonosulfonic acid, alkali thiocyanate being present. The sensitivity of this test is $\text{1}\text{500,000}$ (l0^-5.7); it ia specific for the Cu⁺² ion and can also be used to distinguish quickly the above-mentioned acid from the benzidine o-o'-disulfonic and benzidine m-m' '-disulfonic acids. It is believed that the mechanism of the reaction can be explained by an oxidation process.     

HPLC-Electrochemical detection with graphite-poly (tetrafluoroethylene) electrode Determination of the fungicides thiram and disulfiram

The suitability of composite graphite-poly(tetrafluoroethylene) (Teflon) electrodes as amperometric indicator electrodes in HPLC detection is demonstrated. The determination of the fungicides thiram and disulfiram in the presence of ziram has been chosen as an analytical problem. The optimization of working conditions, such as the choice of the organic solvent used in the mobile phase as well as its percentage, the potential applied to the composite electrode, and the time elapsed between mixing the carbamates and the injection, has been accomplished by using the wall-jet flow-cell configuration. The effect of the acetonitrile percentage used in the mobile phase on the retention of thiram, disulfiram, ziram and phenol was evaluated. Resolution up to the baseline can be achieved with 45% acetonitrile. The sensitivity of the determination of thiram and disulfiram in the presence of a constant concentration of ziram is slightly better when using a wall-jet cell; however, the background current is higher, as well as the baseline noise and the time necessary to achieve stabilization of the baseline before the injection. Lower limits of detection for both fungicides, as well as a better repeatability, were obtained when using a thin-layer flow cell configuration. As an application, the determination of thiram in spiked apple samples, at a level of 0.5 mg thiram kg(-1) apple, has been carried out with a mean recovery of 97 +/- 3% for a significance level of 0.05.     

The kinetics of radical polymerization—XXVII. Investigation of the radical reactivity of 3,3′- and 4,4′-disubstituted azobenzenes in the polymerization of vinylacetate

A study was made on the inhibition by some 3,3′- and 4,4′-disubstituted azobenzenes of the polymerization of vinylacetate initiated by azoisobutyronitrile at 50°. The inhibitory effects of these substances can be attributed to their ability to engage in radical addition giving a less reactive hydrazyl type radical. The mechanism of the inhibition has been established by ESR and kinetic (stoichiometric) measurements. The value of k₅/k₂ (characteristic of the reactivity of an inhibitor) was determined for 9 substituents. The radical reactivity of the aromatic azo group was decreased by electron donor substituents and increased by electron acceptors. The substituent effect can be well interpreted by the Hammett equation; the value of the reaction constant was ? = +0.53.     

Effect of the specific activity of the tracer on rat luteinizing hormone radioimmunoassay

Rat luteinizing hormone /LH/ was labelled with¹²⁵I by the Chloramine T method.¹²⁵I-LH, used as tracer in radioimmunoassay, was separated from the labelling reaction mixture by gel filtration. By using the proper protein/radioiodine ratio in the labelling reaction mixture the specific activity of¹²⁵I-LH was adjusted to 2.5–20.5 MBq g^–1. The influence of the specific activity on the assay parameters as well as on the tracer stability was investigated.     

Characterisation of Tokaj wines based on free amino acids and biogenic amines using ion-exchange chromatography

Summary Tokaj wines (Szamorodni and Aszu wines) of Hungarian origin were investigated on the basis of free amino acids and biogenic amines. The separation and determination of these compounds was performed by an amino acid analyser equipped with an ion-exchange resin column. The total amount of free amino acids and biogenic amines was higher in Aszu wines than in Szamorodni wines. The main amino acids were proline and arginine, while the major biogenic amines were tyramine and putrescine. The free amino acid and biogenic amine content of Aszu wines depended on the vineyards the wines originated from. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001     

Thermal rearrangements of 2-vinylcyclopropylidene to cyclopentadiene and vinylallene: a theoretical investigation

In an attempt to clarify the favored rearrangement reaction of vinylcyclopropylidenes, the prototype thermal rearrangements of singlet 2-vinylcyclopropylidene (1) leading to 1,3cyclopentadiene (2) and 1,2,4-pentatriene (vinylallene) (3) were investigated by means of ab initio quantum-mechanical electronic-structure calculations. The B3LYP functional with the 6-31G(d) basis set was employed for geometry optimization of the equilibrium and transition-state structures relevant to the two reaction pathways and for computing their harmonic vibrational frequencies. Final energies were evaluated by single-point calculations at the CCSD(T) level of theory with the 6-311 + G(3df,2p) basis set. The rearrangement of s-cis 1 to 2 is found to occur by a three-step pathway. The first step involves the formation of a nonclassical carbene (5), which is an internal pi complex between the pi molecular orbital of the double bond and the empty p atomic orbital of the carbene carbon. In the second step, the nonplanar five-membered ring geometry of 5 flattens to reach the planar structure of 3-cyclopentenylidene (4). The last step is the 1,2-migration of a alpha-hydrogen atom to the carbene center in 4. The rate-determining step for the rearrangement of s-cis 1 to 2 is the formation of 5, with a predicted global deltaG++(220 K) of only 0.6 kcalmol(-1). The rearrangement of s-trans 1 to 2 requires an initial conversion of s-trans 1 to the s-cis conformer, with a predicted deltaG++(220 K) of 1.8 kcalmol(-1). The transition structure for the ring-opening of s-trans 1 into s-trans 3 (deltaG++(220 K)=4.7 kcalmol(-1)) is more energetic than that for the ring-opening of s-cis 1 into s-cis 3 (deltaG++(220 K)=2.5 kcalmol(-2)) due to larger repulsive nonbonded H...H interactions in the former transition structure. On the basis of these results, it is suggested that if the reaction of 1,1-dibromo-2-vinylcyclopropane with methyllithium at -78 degrees C leads to the initial formation of carbene 1, then the reaction should yield 2 as the main product together with small amounts of 3. This theoretical prediction nicely agrees with experimental findings.     

Selective liquid adsorption and structural properties of montmorillonite and its hexadecylpyridinium derivatives

Summary An X-ray diffraction method was used to study the structures of montmorillonites, the surfaces of which were covered to a systematically increasing extent with hexadecylpyridinium (HDP) cations. It was found that, depending on the degree of cover of the surface, the HDP cations form a mono- or bimolecular layer in the interlayer space. A detailed investigation was made of the selective sorption of binary mixtures on montmorillonite and on HDP-montmorillonites with different surface coverages. The adsorption excess isotherms were determined, as were the adsorption capacities from analysis of the isotherms, and also the equivalent specific surface areas.It was established that from benzene-n-heptane mixtures the benzene is adsorbed only on the external surface of montmorillonite, while in the case of organocomplexes it causes moderate disaggregation.From benzene, alcohols with different numbers of carbon atoms are also preferentially adsorbed on the internal surfaces of montmorillonite; with the rise in the number of carbon atoms, the extent of interlamellar adsorption decreases. In the case of HDP-montmorillonites in methanol-benzene mixtures, the adsorption capacity exhibits a monotonous increase with the degree of organopbility in the range under consideration. In the event of optimum organophility the disaggregation of the organocomplex is complete, and the equivalent specific surface area is 764-778 m² · g^–1. The swelling of the organocomplex, which can be characterized by X-ray diffraction measurement, is in close correlation with the interlamellar liquid adsorption. The results show modification of the surface of montmorillonite with HDP cations fundamentally determines the nature and extent of the selective liquid adsorption.

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Zusammenfassung Die Struktur von mit Hexadecyl-pyridinium(HDP)-Kationen im systematisch gesteigerten Maße bedeckten Montmorilloniten wurde mit der Röntgendiffraktions-Methode untersucht. Es wurde festgestellt, daß die HDP-Kationen, von der Bedeckung der Oberfläche abhängend, im Schichtzwischenraum eine mono- bzw. bimolekulare Schicht bilden. Die selektive Sorption binärer Gemische wurde an Montmorilloniten und an HDP-Montmorilloniten verschiedener Bedeckung eingehend untersucht. Es wurden die Adsorptionsisothermen von Flüssigkeitsgemischen und aus deren Analyse die Adsorptionskapazitäten und die äquivalenten spezifischen Oberflächen bestimmt.Es wurde festgestellt, daß aus Benzol-n-Heptan-Gemischen das Benzol nur an der äußeren Montmorillonite-Oberfläche adsorbiert wird, während es bei Organokomplexen eine mäßige Desaggregation verursacht. Die Adsorption von Alkoholen verschiedener Kohlenstoffzahl aus Benzol erscheint auch an inneren Montmorillonit-Oberflächen bevorzugt; mit zunehmender Kohlenstoffzahl nimmt das Ausmaß der interlamellaren Adsorption ab. Bei HDP-Montmorilloniten zeigt die Adsorptionskapazität aus Methanol-Benzol-Gemischen mit zunehmender Organophilität im untersuchten Gebiet eine monotone Steigerung. Im Falle optimaler Organophilität ist die Desaggregation vollständig, die äquivalente spezifische Oberfläche beträgt 764-778 m²/g. Die durch Röntgenn-diffraktionsmessung charakterisierbare Quellung des Organokomplexes steht mit der interlamellaren Flüssig-keitsadsorption in engern Zusammenhang. Unsere Ergebnisse zeigen, daß Charakter und Ausmaß der selektiven Flüssigkeitsadsorption durch die Modifizierung der Montmorillonit-Oberfläche mit HDP-Kationen grundlegend verändert wird.

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With 14 figures and 4 tables     

A new regularization of equilibrium problems on Hadamard manifolds: applications to theories of desires

In this paper, we introduce a new proximal algorithm for equilibrium problems on a genuine Hadamard manifold, using a new regularization term. We first extend recent existence results by considering pseudomonotone bifunctions and a weaker sufficient condition than the coercivity assumption. Then, we consider the convergence of this proximal-like algorithm which can be applied to genuinely Hadamard manifolds and not only to specific ones, as in the recent literature. A striking point is that our new regularization term have a clear interpretation in a recent “variational rationality” approach of human behavior. It represents the resistance to change aspects of such human dynamics driven by motivation to change aspects. This allows us to give an application to the theories of desires, showing how an agent must escape to a succession of temporary traps to be able to reach, at the end, his desires.

     

Asymptotic Analysis of Finite-Source M/GI/1 Retrial Queueing Systems with Collisions and Server Subject to Breakdowns and Repairs

Methodology and Computing in Applied Probability - This paper deals with a retrial queuing system with a finite number of sources and collision of the customers, where the server is subject to...     

Fairness in ambulance routing for post disaster management

Central European Journal of Operations Research - Disaster management generally includes the post-disaster stage, which consists of the actions taken in response to the disaster damages. These...