Synthesis and Thermal Decomposition of Mixed 2,4'-bipyridine-oxalato Complexes With Mn(II), Co(II), Ni(II) and Cu(II)

The mixed 2,4'-bipyridine-oxalato complexes of the formulae M(2,4'-bipy)₂ C₂ O₄ 2H₂ O (M (II)=Mn, Co, Ni, Cu; 2,4'-bipyridine=2,4'-bipy or L ; C₂ O^2– ₄ =ox) have been prepared and characterized. IR data show that the 2,4'-bipy coordinated with these metals(II) via the least hindered (4')N atom; that oxalate group acts as bidentate chelating ligand. Room temperature magnetic moments are normal for the orbital singlet states. The thermal decomposition of these complexes was investigated by TG, DTA and DTG in air. The endothermic or exothermic character of the decomposition of ML₂ (ox)2H₂ O was discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

New complexes of Mn(II), Co(II), Ni(II) AND Cu(II) with 2,2’- OR 2,4’-bipyridine and formates (Synthesis, thermal and other properties)

New mixed-ligand complexes with empirical formulae: Mn(2-bpy)_1.5L₂·2H₂O, M(2-bpy)₂L₂·3H₂O (M(II)=Co, Cu), Ni(2-bpy)₃L₂·4H₂O and M(2,4’-bpy)₂L₂·2H₂O (where 2-bpy=2,2’-bipyridine, 2,4’-bpy=2,4’-bipyridine; L=HCOO^– ) have been obtained in pure solid-state. The complexes were characterized by chemical and elemental analysis, IR and VIS spectroscopy, conductivity (in methanol and dimethylsulfoxide). The way of metal-ligand coordination discussed. The formate and 2,4’-bpy act as monodentate ligands and 2-bpy as chelate ligand. The new complexes with ligand isomerism were identified. During heating the complexes lose water molecules in one or two steps. Thermal decomposition after dehydration is multistage and yields corresponding metal oxides as final products. A coupled TG-MS system was used to analysis principal volatile thermal decomposition (or fragmentation) products of Ni(2,4’-bpy)₂(HCOO)₂·2H₂O under dynamic air or argon atmosphere.     

Nonlinear Dynamics of Floating Cranes

The nonlinear dynamic responses of moored crane vessels to regular wavesare investigated experimentally and theoretically. The main subject ofinterest are nonlinear phenomena like bifurcations and the existence ofmultiple attractors. In the experimental part of the work, a mooredmodel of a crane vessel has been excited by regular waves in a wavetank. A special mechanism has been developed to model the nonlinearbehavior of real mooring systems. The theoretical part of the workconcerns the mathematical modeling of the floating cranes. Twomathematical models of different levels of complexity are presented. Twodifferent tools are used to systematically determine the responses ofthe systems to periodic forcing of waves. Firstly, the path-followingtechniques in combination with numerical integration of equations ofmotion applied to a full nonlinear model give insight into the dynamicsin time domain. Secondly, the multiple scales method allows for ananalytical investigation of simplified nonlinear models in frequencydomain. Many results of computations for two crane vessels, barge andship, are presented. Special attention is paid to oscillations near thefrequencies of primary resonances and to subharmonic motions. Anexcellent agreement is found between the results of time-domain andfrequency-domain analysis. The computational examples chosen correspondto the models used not only in the present experiments but in theexperiments of others as well. The results presented in the work allow usto draw several important conclusions concerning the dynamic behavior offloating cranes during offshore operations. Both the developed modelsand the analytical tools can be used to identify the limits of theoperating range of floating cranes.     

Computing Interior Eigenvalues of Conservative Gyroscopic Problems

We propose a new method for computing a large number of eigenpairs in the interior of the spectrum for conservative gyroscopic eigenproblems by the nonlinear Arnoldi method combined with a localized version of safeguarded iteration. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Insight into the Sorption of 5-Fluorouracil and Methotrexate onto Soil–pH,Ionic Strength,and Co-Contaminant Influence

Nowadays anticancer drugs (ADs), like other pharmaceuticals, are recognized as new emerging pollutants, meaning that they are not commonly monitored in the environment; however, they have great potential to enter the environment and cause adverse effects there. The current scientific literature highlights the problem of their presence in the aquatic environment by publishing more and more results on their analytics and ecotoxicological evaluation. In order to properly assess the risk associated with the presence of ADs in the environment, it is also necessary to investigate the processes that are important in understanding the environmental fate of these compounds. However, the state of knowledge on mobility of ADs in the environment is still very limited. Therefore, the main aim of our study was to investigate the sorption potential of two anticancer drugs, 5-fluorouracil (5-FU) and methotrexate (MTX), onto different soils. Special attention was paid to the determination of the influence of pH and ionic strength as well as presence of co-contaminants (cadmium (Cd²⁺) and another pharmaceutical—metoprolol (MET)) on the sorption of 5-FU and MTX onto soil. The obtained distribution coefficient values (K_d) ranged from 2.52 to 6.36 L·kg⁻¹ and from 6.79 to 12.94 L·kg⁻¹ for 5-FU and MTX, respectively. Investigated compounds may be classified as slightly or low mobile in the soil matrix (depending on soil). 5-FU may be recognized as more mobile in comparison to MET. It was proved that presence of other soil contaminants may strongly influence their mobility in soil structures. The investigated co-contaminant (MET) caused around 25-fold increased sorption of 5-FU, whereas diminished sorption of MTX. Moreover, the influence of environmental conditions such as pH and ionic strength on their sorption has been clearly demonstrated.     

Practical Iron‐ and Cobalt‐Catalyzed Cross‐Coupling Reactions between N‐Heterocyclic Halides and Aryl or Heteroaryl Magnesium Reagents

The reaction scope of iron‐ and cobalt‐catalyzed cross‐coupling reactions in the presence of isoquinoline (quinoline) in the solvent mixture tBuOMe/THF has been further investigated. Various 2‐halogenated pyridine, pyrimidine, and triazine derivatives were arylated under these mild conditions in excellent yields. The presence of isoquinoline allows us to perform Fe‐catalyzed cross‐coupling reactions between 6‐chloroquinoline and aryl magnesium reagents. Furthermore, it was found that the use of 10 % N,N‐dimethylquinoline‐8‐amine increases the yields of some Co‐catalyzed cross‐coupling reactions with chloropyridines bearing electron‐withdrawing substituents.     

Image-Based Inertial Impact Test for Characterisation of Strain Rate Dependency of Ti6Al4V Titanium Alloy

Experimental Mechanics - In the present work Image-Based Inertial Impact (IBII) tests are performed on Ti6Al4V material. The IBII test uses an impact on the edge of the specimen to generate a short...     

Epoxy resins cured with ionic liquids as novel supports for metal complex catalysts

In this work, the application of an epoxy resin cured with ammonium ionic liquids as a support for palladium complex catalyst is reported. Supports based on epoxy resin were obtained as a result of the use of ionic liquids: didecyldimethylammonium tetrafluoroborate [d₂m₂am][BF₄], 1-methyltheobromine tetrafluoroborate [mthb][BF₄], didecyldimethylammonium theobrominate [d₂m₂am][thb], didecyldimethylammonium theophyllinate [d₂m₂am][thp] as cross-linking agents. The characterization of polymeric supports and heterogenized palladium catalysts has involved research methods like time-of-flight secondary ion mass spectrometry (TOF-SIMS), infrared spectroscopy (IR), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS). The activity and stability during long-term use of the investigated catalytic systems were tested in a model Heck reaction. The influence of the type of ILs used as epoxy hardeners on the catalytic properties of epoxy-supported palladium catalysts is discussed.     

Cadaverinium dichloride: a case of centro–non‐centrosymmetric ambiguity

In the title salt, also known as pentane‐1,5‐diammonium dichloride, C₅H₁₆N₂²⁺·2Cl⁻, the cation exists in an ideal fully extended conformation and lies on a mirror plane in the space group Pbam. In the crystal structure, layers of cations are hydrogen bonded with Cl⁻ anions, which occupy the space between the layers. This kind of packing leads to a short unit‐cell parameter of 4.463 (1) Å. This structure is another case of centro–non‐centrosymmetric ambiguity; the best results were obtained in a centrosymmetric space group, with the disordered NH₃ groups accounting for the non‐centrosymmetric `component'.     

Thermal characterization of new complexes of Zn(II) and Cd(II) with some bipyridine isomers and propionates

New mixed ligand complexes of the following stoichiometric formulae: M(2-bpy)₂(RCOO)₂·nH₂O, M(4-bpy)(RCOO)₂·H₂O and M(2,4’-bpy)₂(RCOO)₂·H₂O (where M(II)=Zn, Cd; 2-bpy=2,2’-bipyridine, 4-bpy=4,4′-bipyridine, 2,4′-bpy=2,4′-bipyridine; R=C₂H₅; n=2 or 4) were prepared in pure solid-state. These complexes were characterized by chemical and elemental analysis, IR and conductivity studies. Thermal behaviour of compounds was studied by means of DTA, DTG, TG techniques under static conditions in air. The final products of pyrolysis of Cd(II) and Zn(II) compounds were metal oxides MO. A coupled TG/MS system was used to analyse of principal volatile products of thermal decomposition or fragmentation of Zn(4-bpy)(RCOO)2·H2O under dynamic air and argon atmosphere. The principal species correspond to: C⁺, CH⁺, CH₃ ⁺, C₂H₂ ⁺, HCN⁺, C₂H₅ ⁺ or CHO⁺, CH₂O⁺ or NO⁺, CO₂ ⁺, ¹³C¹⁶O₂ ⁺ and ¹²C¹⁶O¹⁸O⁺ and others; additionally CO⁺ in argon atmosphere.