Päijänteen yhteenvetotutkimus II : Nykytila ja siihen johtanut kehitys ; biologiset selvitykset

English summary: Lake Päijänne research II

Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

Antipyrine and pyridine n-oxide complexes of iron(II)

Iron(II) complexes of 1-phenyl-2,3-dimethyl-5-pyrazolone (antipyrine, Apy) and pyridine N-oxide (PyO), having the formulae [Fe(Apy)6](ClO4)2, Fe(Apy)2Cl2, Fe(Apy)2Br2, Fe(Apy)4I2, [Fe(PyO)3Cl3]2 . 2H2O, [Fe(PyO)Cl2 . 2H2O]2, [Fe(PyO)3Br2]2 and [Fe(PyO)6]I2 have been prepared and characterized. [Fe(Apy)6](ClO4)2 in nitrobenzene and [Fe(PyO)6]I2 in acetonitrile behave as 1:2 electrolytes; Fe(Apy)4I2 shows considerable dissociation while Fe(Apy)2Cl2 and Fe(Apy)2Br2 are non-electrolytes and monomeric in nitrobenzene. [Fe(PyO)3Cl2]2 . 2H2O and [Fe(PyO)3Br2]2 in nitrobenzene and [Fe(PyO)Cl2 . 2H2O]2 in acetonitrile behave as non-electrolytes. All the complexes are spin-free. The i.r. spectra show that the oxygens of the CO and NO groups are the donors in the Apy and PyO complexes. A large decrease in the NO stretching frequency in [Fe(PyO)Cl2. 2H2O]2 suggests PyO acts as a bridge forming a binuclear complex. The chloro and the bromo complexes of Apy have been assigned pseudo tetrahedral structures while the rest of the complexes have octahedral or near octahedral configurations around the iron(II) on the basis of the magnetic moments and the electronic transitions.

Synthesis, characterisation and thermal analysis of copper (II) and chromium (II, III) hydrazine carboxylates

Copper(II) hydrazine carboxylate monohydrate, Cu(N2H3COO)2·H2O and chromium (II, III) hydrazine carboxylate hydrates, Cu(N2H3COO)2·H2O and Cu(N2H3COO)2·3H2O have been prepared and characterised by chemical analysis, IR, visible spectra and magnetic measurements. Thermal analysis of the copper complex yields a mixture of copper metal and copper oxide. Chromium complexes on thermal decomposition yield Cr2O3 as residue. Decomposition of chromium(HI) complex under hydrothermal conditions yield CrOOH, a precursor to CrO2.

Enzyme catalysed non-oxidative decarboxylation of aromatic acids II. Identification of active site residues of 2,3-dihydroxybenzoic acid decarboxylase from Aspergillus niger

In order to understand the mechanism of decarboxylation by 2,3-dihydroxybenzoic acid decarboxylase, chemical modification studies were carried out. Specific modification of the amino acid residues with diethylpyrocarbonate, N-bromosuccinimide and N-ethylmaleiimide revealed that at least one residue each of histidine, tryptophan and cysteine were essential for the activity. Various substrate analogs which were potential inhibitors significantly protected the enzyme against inactivation. The modification of residues at low concentration of the reagents and the protection experiments suggested that these amino acid residues might be present at the active site. Studies also suggested that the carboxyl and ortho-hydroxyl groups of the substrate are essential for interaction with the enzyme.

Optimal design of multiproduct batch chemical plant using NSGA-II

The optimal design of a multiproduct batch chemical plant is formulated as a multiobjective optimization problem, and the resulting constrained mixed-integer nonlinear program (MINLP) is solved by the nondominated sorting genetic algorithm approach (NSGA-II). By putting bounds on the objective function values, the constrained MINLP problem can be solved efficiently by NSGA-II to generate a set of feasible nondominated solutions in the range desired by the decision-maker in a single run of the algorithm. The evolution of the entire set of nondominated solutions helps the decision-maker to make a better choice of the appropriate design from among several alternatives. The large set of solutions also provides a rich source of excellent initial guesses for solution of the same problem by alternative approaches to achieve any specific target for the objective functions

Flow Generated By Pitched Blade Turbines Ii: Simulation Using Κ-Ε Model

Experimental data on average velocity and turbulence intensity generated by pitched blade downflow turbines (PTD) were presented in Part I of this paper. Part II presents the results of the simulation of flow generated by PTD The standard κ-ε model along with the boundary conditions developed in the Part 1 have been employed to predict the flow generated by PTD in cylindrical baffled vessel. This part describes the new software FIAT (Flow In Agitated Tanks) for the prediction of three dimensional flow in stirred tanks. The basis of this software has been described adequately. The influence of grid size, impeller boundary conditions and values of model parameters on the predicted flow have been analysed. The model predictions successfully reproduce the three dimensionality and the other essential characteristics of the flow. The model can be used to improve the overall understanding about the relative distribution of turbulence by PTD in the agitated tank

X-Ray structure of a ternary complex, copper(II)–lnosine 5-monophosphate–benzimidazole. The first example for the absence of direct metal–nucleotide interaction

The unprecedented absence of direct metal–nucleotide interaction has been observed in the X-ray structure of the ternary metal nucleotide system [Cu(bzim)(H2O)5]2+[IMP]2–·3H2O [IMP = inosine 5-monophosphate(2–), bzim = benzimidazole). The complex crystallizes in the space group P21 with a= 7.013(2), b= 13.179(9), c= 14.565(9)Å, = 94.82(4)°, and Z= 2. The structure was solved by the heavy-atom method and refined by full-matrix least squares on the basis of 1 761 observed (I? 3i) reflections to final R and R values of 0.034 and 0.036 respectively. The CuII has a distorted octahedral co-ordination with a nitrogen of the bzim ligand [Cu–N 1.947(5)Å] and three oxygens of water molecules in the basal plane [mean Cu–O 2.017(3)Å] and two more water oxygens at axial positions [Cu–O 2.194(6) and 2.732(5)Å]. The nucleotide base stacks with the bzim ligand at an average distance of 3.5 Å and an angle of 22°. In the lattice, N(7) of the base is linked to a lattice water through a hydrogen bond, while all the phosphate oxygens are involved in hydrogen bonds with co-ordinated as well as lattice water molecules. The co-ordination behaviour of IMP to CuII is compared in structures containing different -aromatic amines in order to assess the influence of the ternary ligand in complex formation. The present results indicate that, apart from the commonly observed phosphate binding, other modes of co-ordination are possible, these being influenced mainly by the -accepting properties of the ternary ligand.