Absolute configuration in 4-alkyl- and 4-aryl-3,4-dihydro-2(1H)-pyrimidones: a combined theoretical and experimental investigation

Structural features (orientation of the carboxyl group, ring puckering), electronic absorption, and circular dichroism spectra of 4-alkyl- and 4-aryl-dihydropyrimidones 1-5 are calculated by semiempirical (AM1, INDO/S), ab initio (HF/6-31G, CIS/6-31G, RPA/6-31G), and density functional theory (B3LYP/6-31G) methods. These calculations allow an assignment of the absolute configuration by comparison of simulated and experimental CD spectra. Although the ab initio methods greatly overestimate electronic transition energies, the general appearance of the experimental CD spectra is quite nicely reproduced by these calculations. Thus, comparison of experimental with calculated CD spectra is a reliable tool for the assignment of the absolute configuration. For 4-methyl derivatives 1, the first enantiopure DHPM examples with no additional aromatic substituent, the stereochemistry at C4 provided by the theoretical results is confirmed by X-ray structure determination of the diastereomeric salt 6. Additional support is the consistent HPLC elution order found for all investigated DHPMs on a cellulose-derived chiral stationary phase.     

Isomere Diamino-alkoxy-pyridin-carbonitrile — ihre Trennung und Verwendung als Kupplungskomponenten

The isomeric 4,6-diamino-2-alkoxy- (3), and 2,4-diamino-6-alkoxy-3-pyridine-carbonitriles (4) are obtained by treatment of 2-amino-1,1,3-tricyanopropene (1) with sodium alkoxides. Separation is based on their differentpK _a -values (3 a=2.01,4 a=4.17). Coupling reaction of3 a-c with benzenediazonium chloride in strong acidic medium leads to the yellow azo dyes5 a-c, whereas coupling of4 a requires a buffered solution (pH 4–6) to yield6. The UV-VIS spectra of the isomer pyridines and the azo dyes are discussed.     

Synthesis of novel tetra-substituted benzimidazole compounds containing certain heterostructures with antioxidant and anti-urease activities

A new series of 5,6-dimethyl-2-phenyl-1H-benzimidazole derivatives was synthesized. The antioxidant activities of the synthesized compounds were determined according to the cupric reducing antioxidant capacity (CUPRAC), ABTS, and DPPH assays. Many of the target compounds showed good antioxidant activity. Among these compounds, it has been determined that the carbothioamide and 1,2,4-triazole derivatives had a very good antioxidant capacity. Also, all compounds were screened for in vitro inhibitory activity against Jack bean urease. Among the synthesized molecules, the starting compound, acetate, and acetohydrazide derivatives (with IC₅₀ values 12.02, 11.40, and 8.04 μg/mL, respectively) had a higher inhibitory effect on urease and exhibited a lower IC₅₀ values than acetohydroxamic acid (IC₅₀: 20.50 μg/mL) and thiourea (IC₅₀: 14.04 μg/mL) as a reference inhibitors.     

An extensive FPGA-based realization study about the Izhikevich neurons and their bio-inspired applications

This study is aimed at analysing damping and gyroscopic effects on the stability of parametrically excited continuous rotor systems, taking into account both external (non-rotating) and internal (rotating) damping distributions. As case-study giving rise to a set of coupled differential Mathieu–Hill equations with both damping and gyroscopic terms, a balanced shaft is considered, modelled as a spinning Timoshenko beam loaded by oscillating axial end thrust and twisting moment, with the possibility of carrying additional inertial elements like discs or flywheels. After discretization of the equations of motion into a set of coupled ordinary differential Mathieu–Hill equations, stability is studied via eigenproblem formulation, obtained by applying the harmonic balance method. The occurrence of simple and combination parametric resonances is analysed introducing the notion of characteristic circle on the complex plane and deriving analytical expressions for critical solutions, including combination parametric resonances, valid for a large class of rotors. A numerical algorithm is then developed for computing global stability thresholds in the presence of both damping and gyroscopic terms, also valid when closed-form expressions of critical solutions do not exist. The influence on stability of damping distributions and gyroscopic actions is then analysed with respect to frequency and amplitude of the external loads on stability charts in the form of Ince–Strutt diagrams.

     

Über einen Versuch zur Berechnung der Fragmentation von β-Lactamen mittels der EHT-Methode

Zusammenfassung Die Fragmentation von -Lactamen ergibt massenspektroskopisch sowie thermisch entweder die Ausgangsverbindungen Keten und Azomethin oder bevorzugt Äthylene und Isocyanate. Dabei brechen jeweils zwei gegenüberliegende Bindungen. Eine Berechnung der Überlappungsenergien im Ring mittels der EHT-Methode zeigt, daß der induktive Einfluß der Substituenten die Richtung des Zerfalls bestimmt. Es kann auch bei anderen Vierring-Ketonen eine bevorzugte Fragmentation des Ketenbestandteiles nachgewiesen werden.

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An attempt to calculate the fragmentation of -lactams by the EHT method

Both mass spectroscopic and thermal fragmentation of -lactams yield either the reactants (ketenes and azomethines), or preferentially ethylenes and isocyanates. In each case two opposite bonds are broken. Calculation of the overlap energies in the ring by the EHT method shows that the direction of fragmentation is determined by the inductive influence of the substituents. Preferential fragmentation of the ketene constituent can also be demonstrated in other four-membered ring ketones.

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Mit 4 Abbildungen

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Herrn Prof. Dr. techn. Dr. h. c.O. Kratky, Vorstand des Institutes für Physikalische Chemie der Universität Graz, zum 70. Geburtstag gewidmet.     

Calculation of multicentre nuclear attraction integrals over Slater-type orbitals using unsymmetrical one-range addition theorems

Using the unsymmetrical one-range addition theorems introduced by one of the authors with the help of complete orthonormal sets of Ψα-exponential type orbitals(α = 1,0,1,2,...),this paper presents the sets of series expansion relations for multicentre nuclear attraction integrals over Slater-type orbitals arising in Hartree-Fock-Roothaan equations for molecules.The final results are expressed through multicentre charge density expansion coefficients and basic integrals.The convergence of the series is tested by calculating concrete cases for arbitrary values of parameters of orbitals.     

An effective method for the reduction of the device utilization amount in experimental realization of a fractional-order system

This study focuses on the experimental realization of the fractional-order FitzHugh–Nagumo (FHN) neuron model. Firstly, a second-order approximation function is included to the FHN neuron model to satisfy the fractional-order definition. Since these approximation functions can meet the response of the ideal system only in a limited frequency band, the identification of their center frequency is very critical. Thus, the center frequency ‘ω_c’ of this second-order approximation functions is swept until getting the spiking responses of this neuron model for the first time in this study. After the center frequency is determined, this approximation function is transferred into the ‘z’ domain by employing the Tustin discretization operator. This achieved discrete defined and fractional-order FHN neuron model becomes suitable for implementation on the digital platforms. To verify the proficiency of the proposed sweeping process experimentally, the fractional-order FHN model in ‘z’ domain is implemented on the FPGA platform. After these applications, the order of the approximation function is reduced to one. Once this followed frequency sweeping process is repeated for the first-order approximation, the fractional-order FHN neuron model, which is built by this least-order approximation function, is also implemented with the FPGA. Therefore, the reductions of the device utilization amounts by using this least-order approximation function and the importance of the specific frequency identification process are seen clearly.

     

Application of fuzzy optimization to a supply chain network design: A case study of an edible vegetable oils manufacturer

This study applies fuzzy sets to integrate the supply chain network of an edible vegetable oils manufacturer. The proposed fuzzy multi-objective linear programming model attempts to simultaneously minimize the total transportation costs. The first part of the total transportation costs is between suppliers and silos; and rest one is between manufacturer and warehouses. The approach incorporates all operating realities and actual flow patterns at production/distribution network with reference to demands of warehouses, capacities of tin and pet packaging lines. The model has been formulated as a multi objective linear programming model where data are modeled by triangular fuzzy numbers. Finally, the developed fuzzy model is applied for the case study, compiled the results and discussed.     

Crystal structure of (S,S)-diphenylethanediammonium (R,R)-tartrate

Summary The crystal structure of (–)-diphenylethanediammonium-(R,R)-tartrate was determined. From this structure determination, the (S,S) configuration was assigned to the (–)-diphenylethanediamine. The asymmetric unit of the crystal structure contains two units of the title compound plus one molecule of ethanol and one water molecule, which form an intricate network of 19 hydrogen bonds.

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Die Kristallstruktur von (S,S)-Diphenylethandiammonium-(R,R)-tartrat

Zusammenfassung Es wurde die Kristallstruktur von (–)-Diphenylethandiammonium-(R,R)-tartrat bestimmt. Aus dieser Strukturbestimmung ergab sich die Zuordnung der (S,S)-Konfiguration zum (–)-Diphenylethandiamin. Die asymmetrische Einheit der Kristallstruktur besteht aus zwei Formeleinheiten der Titelverbindung sowie einem Molekül Ethanol und einem Wassermolekül, welche ein komplexes Netzwerk von insgesamt 19 Wasserstoffbrücken bilden.