Multistimuli-Responsive [3]Dioxaphosphaferrocenophanes with Orthogonal Switches

Novel multistimuli-responsive phosphine ligands comprising a redox-active [3]dioxaphosphaferrocenophane backbone and a P-bound imidazolin-2-ylidenamino entity that allows switching by protonation are reported. Investigation of the corresponding metal complexes and their redox behaviour are reported and show the sensitivity of the system towards protonation and metal coordination. The experimental findings are supported by DFT calculations. Protonation and oxidation events are applied in Rh-catalysed hydrosilylations and demonstrate a remarkable influence on reactivity and/or selectivity.     

Fast and simple online sample preparation coupled with capillary LC-MS/MS for determination of prostaglandins in cell culture supernatants

An online 2-D strong cation exchange (SCX)-RP capillary liquid chromatographic (cLC) method with IT mass spectrometric (IT-MS/MS) detection for the simultaneous determination of prostaglandin (PG) A(1), PGD(2), PGE(1), PGE(2), PGF(2a), 6-keto-(6k)PGF(1a), and 15-Delta(12,14)-deoxy-PGJ(2) (15dPGJ(2)) in cell culture supernatants was developed and validated. Pretreatment of the cell culture supernatants included dilution and filtration, and the analysis time including all sample preparation steps was less than 50 min per sample. Peptides/proteins contained in the matrix were removed by the SCX column. LODs in the range of 0.4-2.2 ng/mL cell culture supernatant, recoveries higher than 80% and within- and between-day precisions of less than 30% RSDs were obtained. Human mesenchymal stem cells (hMSCs) were stimulated with cytokine-containing supernatants derived from activated T lymphocytes, and PG production was analyzed using the developed method. PGE(2 )was found in cultures from both untreated and stimulated hMSCs, while PGE(1) was present above the detection limit only in stimulated cells.     

Highly effective electrochemical anion sensing based on oxoporphyrinogen

The effect of anion binding on the oxidation potential of an anion receptor, N₂₁,N₂₃-dibenzyl-5,10,15,20-(3,5-di-t-butyl-4-oxo-cyclohexa-2,5-dienylidene)porphyrinogen, 1 in o-dichlorobenzene is reported. The anion binding site of 1, at its inner pyrrolic amine hydrogens, is an integral part of the highly conjugated macrocycle, thus predicting larger potential shifts upon anion binding. Accordingly, cathodic shifts up to 600 mV are observed upon anion binding and such potential shifts correlate well with the anion binding constants.     

Diverse coordination of two ligands in ferromagnetic [Cu(μ-HCO2)2(3-pyOH)]n and [Cu2(μ-HCO2)2(μ-3-pyOH)2(3-pyOH)2(HCO2)2]n

Two novel polynuclear complexes with methanoate anions and 3-hydroxypyridine ligands [Cu(μ-HCO₂)₂(3-pyOH)]_n (1) and [Cu₂(μ-HCO₂)₂(μ-3-pyOH)₂(3-pyOH)₂(HCO₂)₂]_n (2), respectively, were synthesized and characterized. The central copper atom in 1 is surrounded by four methanoates and a 3-pyOH molecule, forming a square-pyramidal CuO₃NO chromophore. All the methanoates are bidentate and serve as bridges between the adjacent copper ions via syn-anti and anti–anti coordination. The basal square coordination axes are formed by O(syn), N(3-pyOH) (1.974(2), 2.016(2) Å) and O(anti), O(anti) (1.945(2), 1.960(2) Å), while the third O(anti) (2.247(2) Å) is on the top of the pyramid. A ferromagnetic transition with an exchange constant 2J/k_B = 9.2 cm⁻¹ is found for 1 below 20 K. This interaction probably takes place through two syn-anti methanoates extended in a chain through the 2D structure. On the other hand, two monoatomic Cu–O–Cu intra-dinuclear asymmetric (1.986(2), 2.415(2) Å) bridges of two methanoates in [Cu₂(HCO₂)₄(3-pyOH)₄] (2) are present. An elongated distorted octahedral coordination sphere around each copper(II) atom is completed by an additional monodentate terminal methanoate (1.975(2) Å), two N-coordinated 3-pyOH (2.005(2), 2.002(2) Å) and the third weakly O-coordinated 3-pyOH (2.732(2) Å). Although a shorter Cu?Cu distance is noticed in 2 than in 1 (4.690(1) Å 1, 3.442(1) Å 2), much weaker ferromagnetism is found in 2.     

Semi-Automated Production Systems under Disturbances

A production system operates at a speed which is a stationary stochastic process. Given the routine control point, the actual accumulated production observed at that point and the deterministic rate of demand, the decision-maker determines the timing of the next control point. The problem is applied to semiautomated production processes where the advancement of the process cannot be measured or viewed continuously, and the process has to be controlled in discrete points by the decision-maker. Since the cost of performing a single control is relatively high, the control should be carried out as rarely as possible but it also has to ensure a preset confidence probability of achieving production output no less than that required. Formulae for determining the next control point for an arbitrary distribution function of the stationary process with a certain autocorrelation function are presented. They depend on the status of the system (shortage or surplus), the relation between the rate of demand and the mean value of the speed, the variance of the speed, and on the confidence level 1-α. A practical numerical example from the mining industry will be given.     

Optimization of the T policy M/G/1 queue with server breakdowns and general startup times

This paper investigates the T$T$ policy M/G/1 queue with server breakdowns, and startup times. Customers arrive at the system according to a Poisson process. Service times, repair times, and startup times are assumed to be generally distributed. The server is turned on after a fixed length of time T$T$ repeatedly until at least one customer is present in the waiting line. The server needs a startup time before starting the service. We analyze various system performance measures and develop the total expected cost function per unit time in which T$T$ is a decision variable. We determine the optimum threshold T^∗$T^{\ast }$ and derive analytical results for sensitivity investigations. The sensitivity analysis is particularly valuable to the system analyst when evaluating future conditions. We also present extensive numerical computation for illustration purpose.     

Di‐μ‐formato‐1κ2O:2κ2O′‐di‐μ‐pyridin‐2‐olato‐1κO:2κN;1κN:2κO‐bis­[(2‐pyridone‐κO)copper(II)] acetonitrile 1.02‐solvate

In the title compound, [Cu₂(CHO₂)₂(C₅H₄NO)₂(C₅H₅NO)₂]·1.02CH₃CN, the dimeric unit is centrosymmetric, with two bidentate pyridin‐2‐olate and two bidentate formate syn–syn bridges, and two apical 2‐pyridone ligands coordinated through the O atoms. The N atom from the apical 2‐pyridone ligand is a donor of a hydrogen bond to the O atom of the bridging pyridinolate ligand of the same complex. The coordination polyhedron of the Cu atom is a distorted square pyramid.     

The complete infinite series solution of systems governed by the wave equation with boundary damping

A common method of solving initial boundary value problems is separation of variables, denoted as modal analysis in the field of flexible structures. For systems with undamped boundary conditions the method is well-established, but for systems with boundary damping it does not provide closed form solutions. In this paper the exact modal series solution for second order systems with damped boundaries is derived with explicit expressions for the series coefficients. Knowledge of these coefficients enables practical applications of the solution, such as finite dimension approximation. The key element of the derivation is a new orthogonality condition for the damped eigenfunctions. The modal series is also transformed into a traveling wave form. The solution, which is the extension of the classical D’Alembert formula, is represented by a single equivalent propagating wave. A component of the solution, denoted by “end waves”, is identified to provide the continuity of the systems displacement response.     

Interferometric spatial filtering

Spatial filters are realised interferometrically by the inclusion of a Mach-Zehnder interferometer in a spatial filtering system.