The Infrared and Raman Spectra of 4-Phenylpyridine and Its Hofmann Type Complexes.

Abstract

The Infrared and Raman spectra of 4-Phenylpyridine are reported for the first time in the 4000-400cm^?1 range. Vibrational assignments have been made for fundamental modes on the basis of frequency shifts of coordinated legend, infrared and Raman band contours and comparisons with the assignments for related molecules. The infrared spectra of M (4-Phenylpyridine) Ni(CN)₄ complexes (M=Mn, Ni or Cd) are reported. Their structure consists of polymeric layers of [M-Ni(CN)₄]_∞ with the 4-phenylpyridine molecules bound to metal (M), similar to the structure found in Hoffmann type host complexes.     

Conservation laws and double reduction of (2+1) dimensional Calogero–Bogoyavlenskii–Schiff equation

In this paper, we obtain conservation laws of (2+1) dimensional Calogero–Bogoyavlenskii–Schiff equation by non‐local conservation theorem method. Besides, exact solutions are obtained by the aid of the symmetries associated with conservation laws. Double reduction is used to obtain these exact solution of Calogero–Bogoyavlenskii–Schiff equation. Copyright © 2016 John Wiley & Sons, Ltd.     

Developing teachers' models for assessing students' competence in mathematical modelling through lesson study

Applications and modelling have gained a prominent role in mathematics education reform documents and curricula. Thus, there is a growing need for studies focusing on the effective use of mathematical modelling in classrooms. Assessment is an integral part of using modelling activities in classrooms, since it allows teachers to identify and manage problems that arise in various stages of the modelling process. However, teachers’ difficulties in assessing student modelling work are a challenge to be considered when implementing modelling in the classroom. Thus, the purpose of this study was to investigate how teachers’ knowledge on generating assessment criteria for assessing student competence in mathematical modelling evolved through a professional development programme, which is based on a lesson study approach and modelling perspective. The data was collected with four teachers from two public high schools over a five-month period. The professional development programme included a cyclical process, with each cycle consisting of an introductory meeting, the implementation of a model-eliciting activity with students, and a follow-up meeting. The results showed that the professional development programme contributed to teachers’ knowledge for generating assessment criteria on the products, and the observable actions that affect the modelling cycle.     

Decolorization Potential of Some Reactive Dyes with Crude Laccase and Laccase-Mediated System

In this study, decolorization of dyestuffs, such as Reactive Red 198, Rem Blue RR, Dylon Navy 17, Rem Red RR, and Rem Yellow RR was studied using laccase and laccase-mediated system. The laccases are known to have an important potential for remediation of pollutants. Among these dyestuffs, decolorization of Rem Blue RR and Dylon Navy 17 was performed with crude laccase under optimized conditions. Vanillin was selected as laccase mediator after screening six different compounds with Rem Yellow RR, Reactive Red 198, and Rem Red RR as substrates. However, Rem Yellow RR was not decolorized by either laccase or laccase-mediated system. It is observed that the culture supernatant contained high laccase activity after treatment with catalase that was responsible for the decolorization. Besides, culture supernatant with high laccase activity as enzyme source was treated with catalase; in this way, the hypothesis that laccase was the enzyme responsible for decolorization was supported. The Rem Blue RR was decolorized with 64.84% under the optimum conditions and Dylon Navy 17 with 75.43% with crude laccase. However, using the laccase and vanillin, the decolorization of Reactive Red 198 and Rem Red RR was found to be 62% and 68%, respectively. Our study demonstrated that the decolorization abilities of laccase and/or laccase mediator systems were based on the types of mediator, the dye structure, and the standard experimental conditions. Also, the electrochemical behaviors of some samples were studied. The redox potentials of these samples were determined using cyclic voltammetry on glassy carbon electrode in phosphate buffer (pH 6) solution.     

Direct enantioselective aldol reactions catalyzed by calix[4]arene-based l-proline derivatives in the water

Two novel p-tert-butylcalix[4]arene-based chiral organocatalysts derived from l-proline have been developed to catalyze direct aldol reactions between cyclohexanone and aromatic aldehydes in water. Under the optimal conditions, high yields (up to 95%), enantioselectivities (up to 90%), and moderate diastereoselectivities (up to 65:35) were obtained. Considering the catalytic inefficiency of sole proline for the aldol reaction in water, these results clearly display the enormous effect of the hydrophobic part of calix[4]arene of compound A.     

Relationship between current response and time in ion transport problem including diffusion and convection. 2. Numerical approach

The mathematical model related to controlled potential experiments in electrochemistry is studied. Ion transport is regarded as the superposition of diffusion and migration under the influence of an electric field. Modeling of the experiment leads to the nonlocal identification problem for nonlinear parabolic equation. It is shown that in some cases the nonlocal identification problem can be transformed to an initial value problem for nonlinear parabolic equation. The finite diference approximation of this problem, with the appropriate iteration algorithm, is derived. Based on these algorithms the solution of the identification problem is presented. The obtained results permits one to derive the behaviour of the current response , depending on time, also the relationship between the current response and Gottrellian is obtained in explicit form. An influence of the valences oxidised and reduced species is also analyzed.      

Reactivity of triruthenium thiophyne and furyne clusters: competitive S-C and P-C bond cleavage reactions and the generation of highly unsymmetrical alkyne ligands

The synthesis and reactivity of the thiophyne and furyne clusters [Ru3(CO)7(mu-dppm)(mu3-eta2-C4H2E)(mu-P(C4H3E)2)(mu-H)] (E = S, O) is reported. Addition of P(C4H3E)3 to [Ru3(CO)10(mu-dppm)] (1) at room temperature in the presence of Me3NO gives simple substitution products [Ru3(CO)9(mu-dppm)(P(C4H3E)3)] (E = S, 2; E = O, 3). Mild thermolysis in the presence of further Me3NO affords the thiophyne and furyne complexes [Ru3(CO)7(mu-dppm)(mu3-eta2-C4H2E)(mu-P(C4H3E)2)(mu-H)] (E = S, 4; E = O, 6) resulting from both carbon-hydrogen and carbon-phosphorus bond activation. In each the C4H2E (E = S, O) ligand donates 4-electrons to the cluster and the rings are tilted with respect to the mu-dppm and the phosphido-bridged open triruthenium unit. Heating 4 at 80 degrees C leads to the formation of the ring-opened cluster [Ru3(CO)5(mu-CO)(mu-dppm)(mu3-eta3-SC4H3)(mu-P(C4H3S)2)] (5) resulting from carbon-sulfur bond scission and carbon-hydrogen bond formation and containing a ring-opened mu3-eta3-1-thia-1,3-butadiene ligand. In contrast, a similar thermolysis of 3 affords the phosphinidene cluster [Ru3(CO)7(mu-dppm)(mu3-eta2-C4H2O)(mu3-P(C4H3O))] (7) resulting from a second phosphorus-carbon bond cleavage and (presumably) elimination of furan. Treatment of 4 and 6 with PPh3 affords the simple phosphine-substituted products [Ru3(CO)6(PPh3)(mu-dppm)(mu3-eta2-C4H2E)(mu-P(C4H3E)2)(mu-H)] (E = S, 8; E = O, 9). Both thiophyne and furyne clusters 4 and 6 readily react with hydrogen bromide to give [Ru3(CO)6Br(mu-Br)(mu-dppm)(mu3-eta2-eta1-C4H2E)(mu-P(C4H3E)2)(mu-H)] (E = S, 10; E = O, 11) containing both terminal and bridging bromides. Here the alkynes bind in a highly unsymmetrical manner with one carbon acting as a bridging alkylidene and the second as a terminally bonded Fisher carbene. As far as we are aware, this binding mode has only previously been noted in ynamine complexes or those with metals in different oxidation states. The crystal structures of seven of these new triruthenium clusters have been carried out, allowing a detailed analysis of the relative orientations of coordinated ligands.     

Synthesis, spectroscopic characterizations and quantum chemical computational studies of (Z)-4-[(E)-(4-fluorophenyl)diazenyl]-6-[(3-hydroxypropylamino)methylene]-2-methoxycyclohexa-2,4-dienone

In this study, the molecular structure and spectroscopic properties of the title compound were characterized by X-ray diffraction, FT-IR and UV-vis spectroscopies. These properties were also investigated using DFT method. The most convenient conformation of title compound was firstly determined. The geometry optimizations in gas phase and solvent media were performed by DFT methods with B3LYP adding 6-31G(d) basis set. The differences between crystal and computational structures are due to crystal packing in which hydrogen bonds play an important role. UV-vis spectra were recorded in different organic solvents. The results show that title compound exists in both keto and enol forms in DMSO, EtOH but it tends to shift towards enol form in benzene. The polar solvents facilitate the proton transfer by decreasing the activation energy needed for Transition State. The formation of both keto and enol forms in DMSO and EtOH is due to decrease in the activation energy. TD-DFT calculations starting from optimized geometry were carried out in both gas and solution phases to calculate excitation energies of the title compound. The non-linear optical properties were computed at the theory level and the title compound showed a good second order non-linear optical property. In addition, thermodynamic properties were obtained in the range of 100-500K.     

Synthetic, electrochemical, and theoretical studies of tetrairidium clusters bearing mono- and bis[60]fullerene ligands

Heating a mixture of Ir(4)(CO)(9)(PPh(3))(3) (1) and 2 equiv of C(60) in refluxing chlorobenzene (CB) affords a "butterfly" tetrairidium-C(60) complex Ir(4)(CO)(6){mu(3)-kappa(3)-PPh(2)(o-C(6)H(4))P(o-C(6)H(4))PPh(eta(1)-o-C(6)H(4))}(mu(3)-eta(2):eta(2):eta(2)-C(60)) (3, 36%). Brief thermolysis of 1 in refluxing chlorobenzene (CB) gives a "butterfly" complex Ir(4)(CO)(8){mu-k(2)-PPh(2)(o-C(6)H(4))PPh}{mu(3)-PPh(2)(eta(1):eta(2)-o-C(6)H(4))} (2, 64%) that is both ortho-phosphorylated and ortho-metalated. Interestingly, reaction of 2 with 2 equiv of C(60) in refluxing CB produces 3 (41%) by C(60)-assisted ortho-phosphorylation, indicating that 2 is the reaction intermediate for the final product 3. On the other hand, reaction of Ir(4)(CO)(8)(PMe(3))(4) (4) with excess (4 equiv) C(60) in refluxing 1,2-dichlorobenzene, followed by treatment with CNCH(2)Ph at 70 degrees C, affords a square-planar complex with two C(60) ligands and a face-capping methylidyne ligand, Ir(4)(CO)(3)(mu(4)-CH)(PMe(3))(2)(mu-PMe(2))(CNCH(2)Ph)(mu-eta(2):eta(2)-C(60))(mu(4)-eta(1):eta(1):eta(2):eta(2)-C(60)) (5, 13%) as the major product. Compounds 2, 3, and 5 have been characterized by spectroscopic and microanalytical methods, as well as by single-crystal X-ray diffraction studies. Cyclic voltammetry has been used to examine the electrochemical properties of 2, 3, 5, and a related known "butterfly" complex Ir(4)(CO)(6)(mu-CO){mu(3)-k(2)-PPh(2)(o-C(6)H(4))P(eta(1)-o-C(6)H(4))}(mu(3)-eta(2):eta(2):eta(2)-C(60)) (6). These cyclic voltammetry data suggest that a C(60)-mediated electron transfer to the iridium cluster center takes place for the species 3(3)(-) and 6(2)(-) in compounds 3 and 6. The cyclic voltammogram of 5 exhibits six well-separated reversible, one-electron redox waves due to the strong electronic communication between two C(60) cages through a tetrairidium metal cluster spacer. The electrochemical properties of 3, 5, and 6 have been rationalized by molecular orbital calculations using density functional theory and by charge distribution studies employing the Mulliken and Hirshfeld population analyses.     

Synthesis of hydroxyapatite by using calcium carbonate and phosphoric acid in various water-ethanol solvent systems

The purpose of the present study is to synthesize hydroxyapatite by using CaCO₃ and H₃PO₄ in various water-ethanol solvent systems. It was observed from experiments that formation of ammonium phosphate compounds hindered the formation of calcium phosphates in ethanol medium. Although the reactivity was better in aqueous medium, the carbonate contents of the products obtained were above 8.5%. Best results with a carbonate content as low as 3.82% was obtained in 50% ethanol containing mixed-aqueous medium at 80°C and the FTIR analysis showed that the product was a carbonated apatite with a calculated composition of 14CaO·4.2P₂O₅·CO₃·7.2H₂O. The amorphous and porous phosphate compound obtained with a BET surface area of 106.6 m² g⁻¹ seems to be useful as adsorbent in wastewater treatment. Upon sintering of the amorphous product at 750°C, crystalline hydroxyapatite with a BET surface area of 25.9 m² g⁻¹ is obtained that may be used in biomedical applications.