Copper(II) Complexes of ω‐Hydroxy‐Functionalized N‐Salicylidenehydrazides show pH‐Controlled Switching between Dicationic Dimers and Neutral One‐Dimensional Coordination Polymers

New copper(II) complexes of the hydrazone ligands H₂salhyhb, H₂salhyhp, and H₂salhyhh, derived from salicylaldehyde and ω‐hydroxy carbonic acid hydrazides, have been synthesized and physically characterized. Two fundamental structures were found in solid state depending on the pH‐value of the reaction solution. Acidic conditions lead to the formation of the di‐μ‐phenoxo‐bridged dicationic complex dimers [{Cu(Hsalhyhb)}₂]²⁺ ( 1a ), [{Cu(Hsalhyhp)}₂]²⁺ ( 2a ), and [{Cu(Hsalhyhh)}₂]²⁺ ( 3a ), isolated as perchlorate salts. The dimeric complexes show strong antiferromagnetic coupling with J = ?399 ( 1a ), ?410 ( 2a ), and ?311 cm^?1 ( 3a ). Higher pH‐values resulted in the aggregation of neutral copper ligand fragments to the one‐dimensional coordination polymers [{Cu(salhyhb)}_n] ( 1b ), [{Cu(salhyhp)}_n] ( 2b ), and [{Cu(salhyhh)}_n] ( 3b ). 3b has been examined by means of X‐ray crystallography and represents the first example of a structurally characterized neutral copper(II) N‐salicylidenehydrazide complex without additional ligands. The magnetic interactions in the polymers are also antiferromagnetic with J = ?125 ( 1b ), ?136 ( 2b ), and ?148 cm^?1 ( 3b ), but strongly reduced compared to the corresponding dimeric complexes. The two basic structure types can be reversibly interconverted simply by pH‐control.     

Dinuclear amine-thiophenolate complexes coligated by ferrocenemonocarboxylate and 1,1'-ferrocenedicarboxylate anions: preparation, characterization and structures of trinuclear [LMII 2(O2CC5H4FeCp)]+ and Pentanuclear [(LMII 2)2(O2CC5H4)2Fe]2+ complexes (M=Co, Ni, Zn)

A series of novel tri- and pentanuclear complexes composed of dinuclear LM(2) units (M=Co, Ni, Zn; L=24-membered macrocyclic hexaazadithiophenolate ligand) and ferrocenecarboxylate ([CpFeC(5)H(4)CO(2)](-)) or 1,1'-ferrocenedicarboxylate ([Fe(C(5)H(4)CO(2))(2)](2-)) groups is reported. The complexes [LM(II) (2)(O(2)CC(5)H(4)FeCp)](+) (M=Co (6), Ni (7), Zn (8)) and [(LM(II) (2))(2)(O(2)CC(5)H(4))(2)Fe](2+) (M=Co (9), Ni (10)) have been prepared by substitution reactions from labile [LM(II) (2)L'](+) precursors (L'=Cl, OAc) and the respective ferrocenecarboxylate anions in methanol. Mixed-valent [(LCo(II)Co(III))(2)(O(2)CC(5)H(4))(2)Fe](4+) (11) was prepared by oxidation of 9 with bromine. Complexes 7[BPh(4)], 8[BPh(4)], 9[BPh(4)](2), 10[BPh(4)](2), and 11[ClO(4)](4) have been characterized by X-ray crystallography; showing that the ferrocenyl carboxylates act as bidentate (7, 8) or bis-bidentate (9-11) bridging ligands towards one or two bioctahedral LM(2) subunits, respectively. The structures are retained in solution as indicated by NMR spectroscopic studies on the diamagnetic Zn(2)Fe complex 8[ClO(4)]. Electrochemical studies reveal significant anodic potential shifts for the oxidation potential of the ferrocenyl moieties upon complexation and the magnitude of the potential shift appears to correlate with the charge of the LM(2) subunits. This is qualitatively explained in terms of destabilizing electrostatic (Coulomb) interactions between the M(2+) ions of the LM(2) unit and the proximate ferrocenium fragment. An analysis of the temperature-dependent magnetic susceptibility data for 10[BPh(4)](2) shows the presence of weak ferromagnetic magnetic exchange interactions between the Ni(II) ions in the LNi(2) units. The exchange coupling across the ferrocenedicarboxylate bridge is negligible.     

Multiple Eigenvalues in Spectral Analysis for Solving QBD Processes

A number of authors have recently suggested solving quasi birth-and-death (QBD) processes through the use of eigenvalue-based methods. These methods take on a special form when there are multiple eigenvalues present. We investigate this problem in a general setting as well as in the context of a specific preemptive priority queueing model.      

A Kolmogorov-type competition model with multiple coexistence states and its applications to plant competition for sunlight

It is demonstrated that a Kolmogorov-type competition model featuring species allocation and gain functions can possess multiple coexistence states. Two examples are constructed: one in which the two competing species possess rectangular allocation functions but distinct gain functions, and the other in which one species has a rectangular allocation function, the second species has a bi-rectangular allocation function, and the two species share a common gain function. In both examples, it is shown that the species nullclines may intersect multiple times within the interior of the first quadrant, thus creating both locally stable and unstable equilibrium points. These results have important applications in the study of plant competition for sunlight, in which the allocation functions describe the vertical placement of leaves for two competing species, and the gain functions represent rates of photosynthesis performed by leaves at different heights when shaded by overlying leaves belonging to either species.     

Conception of a new technique in cell cultivation using a lab-on-chip aided miniaturised device with calibratable electrochemical sensors

Continuous electrochemical sensing is often carried out in order to track the growth of cells as an alternative to optical monitoring. Planar sensors and multi-sensor chips are applied in case of adhered growing cells, and usually introduced into lab-on-chip systems. Repeated recalibration is necessary with most chemosensors so far and this limits the operational lifetime of such lab-on-chip systems to a few days. An assembly is presented here that eliminates this disadvantage and enables the monitoring of a long-term cultivation of tissue. Cell cultures and sensor are arranged such that they can be separated or contacted at variable times without having an impact on the growth of the cells. The use of a biocompatible nano-porous membrane is especially important. A multi-well system is described where each well is supplied with a planar multi-sensor chip below the adhered cells to determine (a) pH, (b) glucose, (c) oxygen, and—optionally—impedance, for example during the cultivation of cartilage tissue.