A New Oxygen Containing Pyclen-Type Ligand as a Manganese(II) Binder for MRI and 52Mn PET Applications: Equilibrium,Kinetic, Relaxometric,Structural and Radiochemical Studies

A new pyclen-3,9-diacetate derivative ligand (H₂3,9-OPC2A) was synthesized possessing an etheric O-atom opposite to the pyridine ring, to improve the dissociation kinetics of its Mn(II) complex (pyclen = 3,6,9,15-tetraazabicyclo(9.3.1)pentadeca-1(15),11,13-triene). The new ligand is less basic than the N-containing analogue (H₂3,9-PC2A) due to the non-protonable O-atom. In spite of its lower basicity, the conditional stability of the [Mn(3,9-OPC2A)] (pMn = −log(Mn(II)), c_L = c_Mn(II) = 0.01 mM. pH = 7.4) remains unaffected (pMn = 8.69), compared to the [Mn(3,9-PC2A)] (pMn = 8.64). The [Mn(3,9-OPC2A)] possesses one water molecule, having a lower exchange rate with bulk solvents (k_ex²⁹⁸ = 5.3 ± 0.4 × 10⁷ s⁻¹) than [Mn(3,9-PC2A)] (k_ex²⁹⁸ = 1.26 × 10⁸ s⁻¹). These mild differences are rationalized by density-functional theory (DFT) calculations. The acid assisted dissociation of [Mn(3,9-OPC2A)] is considerably slower (k₁ = 2.81 ± 0.07 M⁻¹ s⁻¹) than that of the complexes of diacetates or bisamides of various 12-membered macrocycles and the parent H₂3,9-PC2A. The [Mn(3,9-OPC2A)] is inert in rat/human serum as confirmed by ⁵²Mn labeling (nM range), as well as by relaxometry (mM range). However, a 600-fold excess of EDTA (pH = 7.4) or a mixture of essential metal ions, propagated some transchelation/transmetalation in 7 days. The H₂3,9-OPC2A is labeled efficiently with ⁵²Mn at elevated temperatures, yet at 37 °C the parent H₂3,9-PC2A performs slightly better. Ultimately, the H₂3,9-OPC2A shows advantageous features for further ligand designs for bifunctional chelators.     

Isolation of water-soluble organic matter from atmospheric aerosol

The development of a solid phase extraction (SPE) method is presented, which is capable of isolating approx. 60% of the water-soluble organic compounds from aerosol samples. The aqueous extracts of the filter samples were acidified then passed through an SPE column. Four silica-based and two polymeric reversed phase columns were tested and similar recoveries of the organic carbon were found. The isolated organic matter was nearly free from inorganic ions, which are major constituents of atmospheric aerosol. This fraction accounted for a major part of the UV absorption above 250 nm and fluorescence activity of the aerosol extract. The precision of the method was tested by performing three parallel sample preparations with Oasis HLB columns. It was found that the relative standard deviation of the carbon content of the isolated organic matter was better than 7%, which indicated the reliability of the method. In the atmospheric aerosol research the newly developed sample preparation method facilitates the physical and chemical characterisation of water-soluble organic compounds without the interference of inorganic constituents.     

Dissipation of the herbicide active ingredient glyphosate in natural water samples in the presence of biofilms

Dissipation of the herbicide active ingredient glyphosate was investigated in natural waters. To assess combined effects, glyphosate was applied in its pure form (glyphosate isopropylammonium salt) and in preparation Roundup Classic® formulated with polyethoxylated tallowamines (POEA). Standing and running surface water samples originated from Lake Balaton and River Danube between early May and mid-June of 2015. The kinetics of dissipation of glyphosate, measured by high-performance liquid chromatography combined with UV-VIS absorbance detection or tandem mass spectrometry, was investigated under laboratory conditions in aquaria with or without the presence of biofilms. The quantity and the biofilm structure of algal biomass were determined by in vivo fluorimetry and scanning electron microscopy. The presence of POEA affected the dissipation of glyphosate, and dissipation profiles differed in the investigated natural waters. Significantly higher initial concentrations of glyphosate were measured in River Danube for treatment with formulated glyphosate (101.4 ± 6.2 µg L^?1), than with glyphosate alone (79.9 ± 6.6 µg L^?1), and dissipation to a residual level (57.6 ± 1.4 µg L^?1) consequently took longer (approximately by 1 day). Degradation of glyphosate from the initial level (91.24 ± 5.9 µg L^?1) in Lake Balaton was not detected. Phytotoxic effects of glyphosate, particularly if enhanced by a formulant on algal biomass, were observed. Thus, 5–18% and 11–33% of algal biomass reduction was determined in River Danube upon treatments with glyphosate and Roundup Classic®, respectively. Corresponding biomass decreases in Lake Balaton were 1.3–13% and 9–14%, respectively, accompanied by an overall decay in the algal biofilms. In River Danube, treatments resulted in the occurrence of 1.4–5.8% of green algae in the algal biomass in 28 days, while green algae were not detected in the untreated control. The results indicate that glyphosate is capable of modifying the structure of the algal community and to induce increased secretion of extracellular polymeric substances matrix in the biofilms assessed.     

Quantum walk with jumps

We analyze a special class of 1-D quantum walks (QWs) realized using optical multi-ports. We assume non-perfect multi-ports showing errors in the connectivity, i.e. with a small probability the multi-ports can connect not to their nearest neighbor but to another multi-port at a fixed distance – we call this a jump. We study two cases of QW with jumps where multiple displacements can emerge at one timestep. The first case assumes time-correlated jumps (static disorder). In the second case, we choose the positions of jumps randomly in time (dynamic disorder). The probability distributions of position of the QW walker in both instances differ significantly: dynamic disorder leads to a Gaussian-like distribution, while for static disorder we find two distinct behaviors depending on the parity of jump size. In the case of even-sized jumps, the distribution exhibits a three-peak profile around the position of the initial excitation, whereas the probability distribution in the odd case follows a Laplace-like discrete distribution modulated by additional (exponential) peaks for long times. Finally, our numerical results indicate that by an appropriate mapping a universal functional behavior of the variance of the long-time probability distribution can be revealed with respect to the scaled average of jump size.     

Improved model for the analysis of back corona in pulse energised electrostatic precipitators

Formation of back corona and its effect on the voltage–current characteristics, etc., have been analysed by several authors. It has also been examined how the harmful effect of back corona can be reduced, for example by the application of pulse energisation. However, to find an optimal solution, modelling of the back corona effect is necessary. Different back corona models were created to estimate the time of its development, the change in current–voltage characteristics, the decrease in particle charge and finally, the collection efficiency of the ESP with back corona. In this paper the authors present an improved numerical ESP model that is capable of determining the parameters of back corona in such cases, when pulse energisation is applied for the power supply of the electrostatic precipitator. Based on the modular structure of the model, different modules calculate the distribution of gas velocity, electric field intensity, particle charging and particle movement. All these parameters are important to determine the properties of back corona while it feeds back on these parameters; therefore iteration is necessary to obtain reliable result. The harmful effects of back corona can be characterised with the help of the evaluation of calculated results.     

Notes on Semiarcs

The semiarcs are generalizations of semiovals. Estimates on the sizes of semiarcs, some characterization theorems of semiarcs with large collinear subsets, of semiarcs contained in the union of three concurrent lines and the complete classification of strong semiovals in PG(2, q), q odd, are given.     

Averaging of Systems with Slow Variables

We justify the averaging method for systems with delay described by both slow and fast variables. The results obtained are applied to the analysis of one problem in control theory.     

Asymptotic Expansions for the Distribution of the Maximum of Gaussian Random Fields

Some asymptotic results are proved for the distribution of the maximum of a centered Gaussian random field with unit variance on a compact subset S of ^N . They are obtained by a Rice method and the evaluation of some moments of the number of local maxima of the Gaussian field above an high level inside S and on the border S. Depending on the geometry of the border we give up to N+1 terms of the expansion sometimes with exponentially small remainder. Application to waves maximum is shown.     

Perturbations in the Spectra of the Rydberg Series of a Silver Atom

The main series of a silver atom with n = 5–70 are investigated. Perturbations of the np ² P _1/2,3/2 states with n = 10 and 17 caused by interaction with the selfionization 4d5s5p ⁴ P _1/2,3/2 states are detected. Energies of the selfionization states are determined.