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The main aim of this paper is to investigate relationships between selected macroeconomic variables – interest rate, price level, money supply and real GDP – in the Czech Republic in order to find out definite implications of its interactions and give recommendations to macroeconomic policy authorities. Two implemented vector autoregression models with different lag length reached slightly different conclusions. VAR(1) suggests that three pairs of Granger causality exist, in particular between price level and interest rate, between real GDP and interest rate and between real GDP and price level. VAR(2) uncovered two more pairs of Granger causality between money supply and interest rate and between money supply and price level. Despite better prediction power of VAR(2) in case of money supply, low correlation coefficient comprising variable money supply raises doubts about the factual existence of causality between money supply and other variables. However, both models allow forecasting the direction of change in case of variables interest rate and real GDP with the same success rate nearly 82 %. Both VARs also agreed that interest rate could be changed by change of price level and that interest rate could be changed by change of real GDP. These conclusions represent potential recommendations to macroeconomic policy authorities. For the purpose of further research, exchange rate variable will be included in the model instead of interest rate, because effect of interest rate turned out to be limited in times of weakened state of Czech economy.

Copper radioisotopes can be used for imaging as well as for therapy and, thus, can form ideal theranostic pairs. The Cu(II) complexes of cross-bridged cyclam (cb-cyclam) derivatives are considered to be highly stable in vivo . However, the complexes are mostly formed under harsh conditions not compatible with sensitive biomolecules. Here, a new class of cb-cyclam derivatives, cross-bridged bis(phosphinate)cyclams ("cb-BPC"), were investigated. Ligands with one or two methylene-bis(phosphinate) -CH 2 -PO 2 H-CH 2 -PO 2 H(R) (R = H, OH, substituted alkyl) pendant arms were synthesized. Bifunctionalization on the distant phosphorus atom was carried out by employing P -nitrobenzyl (R = CH 2 -Ph-4-NO 2 ) precursors and/or, for cb-BPC with two bis(phosphinate) pendant arms, by reactions of silyl-phosphites obtained by silylation of their P(O)-H fragments. The reactive bifunctional groups include amine, carboxylate, azide, isothiocyanate, maleimide and/or tetrazine, and also their orthogonally reactive combination in a single molecule of chelator. The cb-BPCs with one bis(phosphinate) arm were not efficiently radiolabelled with 64 Cu. The cb-BPCs with two pendant arms were radiolabelled even at room temperature and with only a small excess of chelator, leading to a high specific activity. Radiolabelling was fully comparable with that of analogous bis(phosphinate) derivatives of cyclam and identical radiolabelling of cyclam and cb-cyclam derivatives was observed for the first time. The cb-BPCs with two bis(phosphinate) pendant arms represent a new class of rigid chelators for copper radioisotopes that are easily synthetically modifiable, highly hydrophilic and radiolabelled under mild conditions.

Biological phosphates can coordinate metal ions and their complexes are common in living systems. Dynamics of mutual oxygen atom exchange in the tetrahedral group in complexes has not been investigated. Here, we present a direct experimental proof of exchange ("phosphonate rotation") in model Ln(III) complexes of monophosphonate H 4 dota analogue which alters phosphorus atom chirality of coordinated phosphonate monoester. Combination of macrocycle-based isomerism with P-based chirality leads to several diastereoisomers. (Non)-coordinated oxygen atoms were distinguished through 17 O-labelled phosphonate group and their mutual exchange was followed by various NMR techniques and DFT calculations. The process is sterically demanding and occurs through bulky bidentate (κ 2 -PO 2 ) - coordination and was observed only in twisted-square antiprism (TSA) diastereoisomer of large Ln(III) ions. Its energy demands increase for smaller Ln(III) ions ( 298 ΔG ≠ (exp./DFT)=51.8/52.1 and 61.0/71.5 kJ mol -1 for La(III) and Eu(III), respectively). These results are helpful in design of such complexes as MRI CA and for protein paramagnetic NMR probes. It demonstrates usefulness of 17 O NMR to study solution dynamics in complexes involving phosphorus acid derivatives and it may inspire use of this method to study dynamics of phosphoric acid derivatives (as e. g. phosphorus acid-based inhibitors of metalloenzymes) in different areas of chemistry., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Aminoalkyl- H -phosphinic acids, also called aminoalkylphosphonous acids, are investigated as biologically active analogues of carboxylic amino acids and/or as valuable intermediates for synthesis of other aminoalkylphosphorus acids. Their synthesis has been mostly accomplished by phospha-Mannich reaction of a P-H precursor, an aldehyde and an amine. The reaction is rarely clean and high-yielding. Here, reaction of H 3 PO 2 with secondary amines and formaldehyde in wet AcOH led to aminomethyl- H -phosphinic acids in nearly quantitative yields and with almost no by-products. Surprisingly, the reaction outcome depended on the basicity of the amines. Amines with p K a > 7-8 gave the desired products. For less basic amines, reductive N -methylation coupled with oxidation of H 3 PO 2 to H 3 PO 3 became a relevant side reaction. Primary amines reacted less clearly and amino-bis(methyl- H -phosphinic acids) were obtained only for very basic amines. Reaction yields with higher aldehydes were lower. Unique carboxylic-phosphinic-phosphonic acids as well as poly( H -phosphinic was illustrated in P-H bond oxidation and its addition to double bonds, and in selective amine deprotection. Compounds with an ethylene-diamine fragment, H -phosphinic was illustrated in P-H bond oxidation and its addition to double bonds, and in selective amine deprotection. Compounds with an ethylene-diamine fragment, e.g. most common polyazamacrocycles, are not suitable substrates. The X-ray solid-state structures of seventeen aminoalkyl-phosphinic acids were determined. In the reaction mechanism, N -hydroxyalkyl species R 2 NCH 2 OH and [R 2 N(CH 2 OH) 2 ] + , probably stabilized as acetate esters, are suggested as the reactive intermediates. This mechanism is an alternative one to the known phospha-Mannich reaction mechanisms. The conditions can be utilized in syntheses of various aminoalkylphosphorus compounds., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A series of lanthanide(iii) complexes of a monophosphinate analogue of H4dota, 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic-10-methyl[(N,N-dibenzylamino)methyl]phosphinic acid (H4do3apDBAm = H4L1), were prepared and their solid-state structures were studied using single-crystal X-ray diffraction. In all structures, the ligand anion was octadentately coordinated to the Ln(iii) or Sc(iii) ions similarly to other DOTA-like ligands, i.e. forming parallel N4- and O4-planes. The lighter lanthanide(iii) complexes (till dysprosium) were nonacoordinated in the twisted square-antiprismatic (TSA) configuration with the apical coordination of water molecules or oxygen atoms from the neighbouring complex unit. The heavier lanthanide(iii) complexes (from terbium) were found as the "anhydrous" octacoordinated twisted square-antiprismatic (TSA') isomer. For the terbium(iii) ion, both forms were structurally characterized. The structural data of the Ln(iii)-H4L1 complexes and complexes of several related DOTA-like ligands were analysed. It clearly showed that the structural parameters for the square-antiprismatic (SA) isomers were clustered in a small range while those for the TSA/TSA' isomers were significantly more spread. The analysis also gave useful information about the influence of various pendant arms on the structure of the complexes of the DOTA-like ligands. The twist angle (torsion) of the chelate ring containing a larger phosphorus atom was similar to those of the remaining three acetate pendants. It led to a larger separation of the N4O4 planes and to smaller trans-O-Ln-O angles than the parameters found in the complexes of H4dota and its tetraamide derivatives dotam(R). It resulted in a relatively long bond between the metal ion and the coordinated water molecule. It led, together with the negative charge of the oxygen atoms forming the O4-plane, to an extremely fast water exchange rate reported for the Gd(iii)-H4L1 complex and, generally, to a fast water exchange of Gd(iii) complexes with the monophosphorus acid analogues of H4dota, H5do3ap/H4do3apR.