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)), cL = cMn(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 (kex298 = 5.3 ± 0.4 ´ 107 s−1) than [Mn(3,9-PC2A)] (kex298 = 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.

Effect of binary basicity on chromium occurrence in stainless steel slag

Comprehensive utilization of stainless-steel slag (SSS) is restrained due to the risk of Cr6+ leaching. Based on the studying the microstructure of synthetic slag (SS) containing Cr2O3with XRD, SEM-EDS?and Image pro, the effect of binary basicity on the chromium occurrence in SSS was investigated. The results indicated that the binary basicity had a significant impact on the properties of spinel crystals. There was a positive correlation between the calcium content in spinel crystals and the SS basicity. The size of spinel crystals varied from large to small and the precipitation occurrence changed with the basicity increase. Furthermore, the chromium occurrences changed with basicity. The chromium was produced in spinel crystals at lower basicity, but as the basicity increased to 3.0, the chromium precipitated as calcium chromate. In view of the relationship between the chromium leaching behavior and its occurrence, increasing basicity raised the Cr6+ leaching.

Interaction of 4-{[(tolyl(methane)sulphonyl)oxy]imino}cyclohexa-2,5-dien-1-ones with N-nucleophiles

Hydrazones of 1,4-benzoquinone, which have a wide range of biological activities, can be synthesized in the reactions of 4-{[(arylsulfonyl)oxy]imino}cyclohexa-2,5-diene-1-ones or N-(4-oxocyclohexa-2,5-diene-1-ylidene)arylsulfonamides with N-substituted hydrazines. In this study, the reaction of 2,6-disubstituted 4-{[(tolyl(methane)sulfonyl)oxy]imino}cyclohexa-2,5-diene-1-ones with aroylhydrazides gave N'-(3,5-dialkyl-4-oxocyclohexa-2,5-diene-1-ylidene)aroylhydrazides, which can be obtained by cross-synthesis in the reaction of N-(3,5-dialkyl-4-oxocyclohexa-2,5-dien-1-ylidene)arylsulfonamides with aroylhydrazides. As a result of the reaction of 4-{[(tolyl(methane)sulfonyl)oxy]imino}cyclohexa-2,5-dien-1-ones with phenylhydrazine, stable 4-hydroxyanilinium tolyl(methane)sulfates were isolated. Their structures were confirmed by X-ray diffraction data. We suggested that at the first stage of the reaction between 4-{[(tolyl(methane)sulfonyl)oxy]imino}cyclohexa-2,5-diene-1-ones and hydrazines, the N–O bond of starting 4-(oxyimino)cyclohexa-2,5-diene-1-one was broken forming sulfonic acid and corresponding quinoneimine. The latter either can be reduced to corresponding aminophenol under reaction conditions or can react with an excess of N-substituted hydrazine yielding corresponding hydrazide. The formation of N'-(4-oxocyclohexa-2,5-diene-1-ylidene)arohydrazides is facilitated by a lower basicity of hydrazide and a lower redox potential of quinoneimine.

Dissolving Cellulose in 1,2,3-Triazolium- and Imidazolium-Based Ionic Liquids with Aromatic Anions

We present 1,2,3-triazolium- and imidazolium-based ionic liquids (ILs) with aromatic anions as a new class of cellulose solvents. The two anions in our study, benzoate and salicylate, possess a lower basicity when compared to acetate and therefore should lead to a lower amount of N-heterocyclic carbenes (NHCs) in the ILs. We characterize their physicochemical properties and find that all of them are liquids at room temperature. By applying force field molecular dynamics (MD) simulations, we investigate the structure and dynamics of the liquids and find strong and long-lived hydrogen bonds, as well as significant π–π stacking between the aromatic anion and cation. Our ILs dissolve up to 8.5 wt.-% cellulose. Via NMR spectroscopy of the solution, we rule out chain degradation or derivatization, even after several weeks at elevated temperature. Based on our MD simulations, we estimate the enthalpy of solvation and derive a simple model for semi-quantitative prediction of cellulose solubility in ILs. With the help of Sankey diagrams, we illustrate the hydrogen bond network topology of the solutions, which is characterized by competing hydrogen bond donors and acceptors. The hydrogen bonds between cellulose and the anions possess average lifetimes in the nanosecond range, which is longer than found in common pure ILs.

Chromous capacities of ferrochromium and matte smelting slags

Purpose: of this paper is to extend the slag capacity concept to sparingly soluble cationic species encountered for example in matte smelting and ferrochromium processing in terms of chromous capacities. Design/methodology/approach: In this context in order to develop the chromous capacity the experimental data on slag-metal equilibrium for ferrochromium smelting and on chromium distribution between slag and matte phases encountered in sulphide smelting of PGM (Platinum Group Metals) and chromium containing copper nickel concentrates were used. Findings: The calculated chromous capacities were in the 10-8 range for ferrochrome smelting slags and 10-4 range for matte smelting slags. These values indicate the very low and moderate chromous ion dissolving ability of ferrochromium smelting slags and matte smelting slags respectively. Research limitations/implications: Due to highly reducing conditions in ferrochromium smelting and the imposed low oxygen partial pressures in sulphide smelting of chromium and PGM containing concentrates chromium in the slag was assumed to be in its divalent state. The slag-metal/matte reaction for dissolution of chromium into the slag as a cation under reducing conditions -in contrast to reactions for dissolution of species such as sulphur and phosphorus into the slag as anions under oxidizing conditions – required the release of electrons. Thus to maintain charge neutrality the dissolution of chromium from the metal or the matte phases into the slag as Cr2+ ions was accompanied by consumption of these electrons by reduction of Fe2+ ions in the slag into metallic Fe which dissolved in the metal/ matte phase. This was supported by the experimental equilibrium data. Hence the slagmetal/ matte reaction defining the chromous capacity involved both O2- and Fe2+ ions of the slag phase. Moreover for matte smelting the thermodynamic activities of species in the matte phase were assumed to conform to ideal associated solution model due to lack of data. For future work it is advisable to determine such activities. Practical implications: The calculated chromous capacities were in the 10-8 range for ferrochrome smelting slags and 10-4 range for matte smelting slags. The results clearly indicate that in matte smelting lower basicity slags would be preferable to render chromium more soluble in the slag in contrast to ferrochromium smelting where higher basicity slags would be suitable to minimize chromium losses to the slag. Originality/value: This research and hence the paper is probably the first on dissolution of chromium as chromous ion in slags, thus it is novel and original.

Complexes of trimethylsilyl trifluoromethanesulfonate with nitrogen, oxygen, and phosphorus donors

The Lewis acceptor chemistry of Me3SiOTf with p-block Lewis bases has been explored and a library of complexes has been characterized by spectroscopic and, where possible, crystallographic methods. Compounds with the generic formula [Me3Si(L)][OTf] (L = 4-dmap, pyr, imz, OPMe3, OPCy3, OPPh3, OpyrMe, dmso, PMe3) were isolated from 1:1 mixtures of Me3SiOTf and the respective ligand in CH2Cl2. Characterization by NMR spectroscopy confirmed the solution stability of all but [Me3Si(PMe3)][OTf], with indications that the latter dissociates into PMe3 and Me3SiOTf. Solid-state structures of [Me3Si(4-dmap)][OTf], [Me3Si(pyr)][OTf], [Me3Si(OPCy3)][OTf], [Me3Si(OPPh3)][OTf], [Me3Si(OpyrMe)][OTf], and [Me3Si(PMe3)][OTf] were elucidated by single crystal X-ray diffraction, confirming the envisaged ionic formulations resulting from the displacement of the OTf anion from the silicon center of Me3SiOTf by the incoming ligand. Mixtures of Me3SiOTf with other related donors, including ChPPh3 (Ch = S or Se), NEt3, SMe2, PPh3, 2,2′-bipy, or Me2CO, show no evidence of reaction under ambient conditions, reflecting the lower basicity and (or) greater steric encumbrance of these ligands. Reactions of Me3SiOTf with bis-donor ligands yielded complexes of the generic formulae [Me3Si(L–L)SiMe3][OTf]2 (L–L = 4,4′-bipy, tmeda, dmpe) and [Me3Si(L–L)][OTf] (L–L = 4,4′-bipy, tmeda, dmpe). The tmeda and dmpe complexes, however, were found to dissociate in solution, with complexes only prevailing in the solid phase. X-ray diffraction studies of [Me3Si(4,4′-bipy)SiMe3][OTf]2 and [Me3Si(dmpe)SiMe3][OTf]2 confirmed the expected connectivities and ionic formulations, with Si–ligand bond lengths comparable to those observed in [Me3Si(pyr)][OTf] and [Me3Si(PMe3)][OTf], respectively.

Comparison of Hydration Mechanism between Cements from Two Different Residual Muds

Steel slags are byproduct of steel making process in blast oxidizing furnace (BOF) and electric arc furnace (EAF), including BOF slag, EAF slag. Residual slag mud is discharged after recover of iron from steel slag by magnetic separation after a wet grinding process. The wet disposal process has higher efficiency than dry process but would deteriorate cementitious reactivity of wet residual mud. For residual EAF slag mud and residual BOF slag mud have different composition, effects of wet disposal process on their reactivity and hydration mechanism of related cements were researched in the paper. Analyses of microstructure and testes of mechanical properties for cements from the two different mud showed that the cements composed of 25 % of different mud respectively can reach the national standard of 42.5 grade cements. But residual EAF slag mud has better reactivity. Cement composed of residual EAF slag mud had a higher increase of compressive strength during 28 days of hydrations, and fluffy C-S-H gel and needlelike AFt crystal would increase obviously. Reactivity of BOF slag would degraded more in wet disposal process for its quicker hydration than EAF slag which resulted in more Ca(OH)2 and C-S-H gel formed in the discharged mud,. EAF had lower basicity, content of less f-CaOand C3S, more P2O5 and C2S, which would contribute to its stability in the wet disposal process. EAF slag is more suitable for wet-disposal process.

Tetrazole substituted polymers for high temperature polymer electrolyte fuel cells

Tetrazole (TZ) has lower basicity than imidazole and may not be fully protonated by phosphoric acid. DFT calculations suggest that the basicity of TZ groups can be increased by introducing a 2,6-dioxy-phenyl-group in position 5.

Structural and functional analysis of a novel haloalkane dehalogenase with two halide-binding sites

The crystal structure of the novel haloalkane dehalogenase DbeA fromBradyrhizobium elkaniiUSDA94 revealed the presence of two chloride ions buried in the protein interior. The first halide-binding site is involved in substrate binding and is present in all structurally characterized haloalkane dehalogenases. The second halide-binding site is unique to DbeA. To elucidate the role of the second halide-binding site in enzyme functionality, a two-point mutant lacking this site was constructed and characterized. These substitutions resulted in a shift in the substrate-specificity class and were accompanied by a decrease in enzyme activity, stability and the elimination of substrate inhibition. The changes in enzyme catalytic activity were attributed to deceleration of the rate-limiting hydrolytic step mediated by the lower basicity of the catalytic histidine.