The molecular structure of anionic species of 2,4,5,7‐tetranitrofluorescein as studied by electrospray ionisation,nuclear magnetic resonance and X‐ray techniques

Among the fluorescein dyes, the behaviour of their nitro derivatives in solution is most unusual, and yet at the same time rarely studied. In this study, their ¹³C nuclear magnetic resonance and electrospray spectra are reported, which confirm, in concert with their ultraviolet‐visible spectra, the molecular structures of the neutral and ionic species of 2,4,5,7‐tetranitrofluorescein observed in different solvents and at various pH values. A peculiar property of this dye consists in its lactonisation of the double‐charged anion, contrary to the well‐known coloured and fluorescent dianions of fluorescein, eosin, etc. Also, this dianion‐lactone exhibits high ability for opening the pyran ring. This cleavage takes place at much lower pH values as compared with those for fluorescein and its halogen derivatives. The ruptured species can be formed as either lactone or carbinol; the latter appears as a result of the nucleophilic attack of a HO^? on the central carbon atom. The corresponding molecular structures are identified via the electrospray method and X‐ray analysis. The behaviour of some other nitrofluoresceins in alkaline media is also considered.     

Functionalized Cellulose for Water Purification,Antimicrobial Applications,and Sensors

As the most abundant natural polymer, cellulose presents a unique advantage for large‐scale applications. To fully unlock its potential, the introduction of desired functional groups onto the cellulose backbone is required, which can be realized by either chemical bonding or physical surface interactions. This review gives an overview of the chemistry behind the state‐of‐the‐art functionalization methods (e.g., oxidation, esterification, grafting) for cellulose in its various forms, from nanocrystals to bacterial cellulose. The existing and foreseeable applications of the obtained products are presented in detail, spanning from water purification and antibacterial action, to sensing, energy harvesting, and catalysis. A special emphasis is put on the interactions of functionalized cellulose with heavy metals, focusing on copper as a prime example. For the latter, its toxicity can either have a harmful influence on aquatic life, or it can be conveniently employed for microbial disinfection. The reader is further introduced to recent sensing technologies based on functionalized cellulose, which are becoming crucial for the near future especially with the emergence of the internet of things. By revealing the potential of water filters and conductive clothing for mass implementation, the near future of cellulose‐based technologies is also discussed.     

Stability and calorimetric studies of silico‐ferrites of calcium aluminum and magnesium

In a systematic study on silico‐ferrites of calcium aluminum and magnesium (SFCA phases) this investigation focuses on synthesis of silicon‐free SFCA‐type compounds with low‐MgO contents (~1.00 apfu—atoms per formula unit). Previous studies revealed the existence of iron‐rich SFCA phases similar to the SFCA‐I structure with the chemical composition Ca₃MgAl₆Fe₁₀O₂₈ (Metall Mater Trans B. 2017;48:2207). The experimental results in the quaternary Fe₂O₃‐CaO‐Al₂O₃‐MgO system confirm large stability fields of 2 silicon‐free ferrites FCAM‐I and FCAM‐III, which are members of the homologous series M_14+6nO_20+8n (n = 1, 2). Starting with compositions corresponding to Ca₃MgAl_xFe_16‐xO₂₈ (with increasing aluminum content from x = 0‐12 apfu), it was possible to synthesize these phases with an x‐value ≥2 apfu, which corresponds to Al₂O₃ contents ≥7.14 wt%. Synthesis of pure silicon‐free ferrites with n = 1 (FCAM‐I) and 2 (FCAM‐III) and silicon‐bearing ferrites with n = 0 (SFCA) was possible. Samples were characterized by electron probe microanalysis, powder diffraction, and subsequently studied using relaxation calorimetry measurements in combination with differential scanning calorimetry for determination of the heat capacities and standard entropies S°(298). The corresponding values are S°(298) = 650.3 ± 4.6 J/mol·K for SFCA, S°(298) = 864.5 ± 6.1 J/mol·K for FCAM‐I, and S°(298) = 1206.2 ± 8.4 J/mol·K for FCAM‐III. These thermodynamic data are a step toward a rigorous quantitative thermodynamic modeling of the iron ore sintering process.     

Vergleich von Nachweisverfahren für Stutzen in Zylinderschalen unter Innendruck und äußeren Lasten

Various methods for the verification of nozzles in cylindrical shells are described and the results of an example are compared. The example is carried out according to DIN EN 13445‐3, Sect. 16.5, in which the maximum permissible loads from internal pressure, axial force as well as moments in the longitudinal and circumferential direction are calculated. The results are compared with finite element computations performed with a 3D shell model, both with linear‐elastic material behavior and as limit‐load analyzes with ideal‐elastic ideal‐plastic material behavior.     

Simultaneous Multiple MS Binding Assays for the Dopamine,Norepinephrine, and Serotonin Transporters

In this work, we present label‐free, mass‐spectrometry‐based binding assays (MS Binding Assays), targeting the human dopamine, norepinephrine, and serotonin transporters (hDAT, hNET, and hSERT) in simultaneous binding experiments. Using a validated LC–ESI‐MS/MS method for quantification of the selective dopamine transporter inhibitor (R,R)‐4‐(2‐benzhydryloxyethyl)‐1‐(4‐fluorobenzyl)piperidin‐3‐ol ((R,R)‐D‐84), the selective norepinephrine transporter inhibitor (S,S)‐reboxetine, and the selective serotonin reuptake inhibitor (S)‐citalopram, binding affinities at the three monoamine transporters could be characterized simultaneously in a single binding experiment. The performed simultaneous saturation and competition experiments yielded results that are in good accordance with those determined in MS Binding Assays addressing the monoamine transporters individually. The results obtained from this study underscore the potential of MS Binding Assays for simultaneous affinity determination at different targets, which is difficult to accomplish with conventional radioligand binding assays.     

Synthesis of a Series of Structurally Diverse MB327 Derivatives and Their Affinity Characterization at the Nicotinic Acetylcholine Receptor

A novel series of 30 symmetric bispyridinium and related N‐heteroaromatic bisquaternary salts with a propane‐1,3‐diyl linker was synthesized and characterized for their binding affinity at the MB327 binding site of nicotinic acetylcholine receptor (nAChR) from Torpedo californica. Compounds targeting this binding site are of particular interest for research into new antidotes against organophosphate poisoning, as therapeutically active 4‐tert‐butyl‐substituted bispyridinium salt MB327 was previously identified as a nAChR re‐sensitizer. Efficient access to the target compounds was provided by newly developed methods enabling N‐alkylation of sterically hindered or electronically deactivated heterocycles exhibiting a wide variety of functional groups. Determination of binding affinities toward the MB327 binding site at the nAChR, using a recently developed mass spectrometry (MS)‐based Binding Assay, revealed that several compounds reached affinities similar to that of MB327 (pK_i=4.73±0.03). Notably, the newly prepared lipophilic 4‐tert‐butyl‐3‐phenyl‐substituted bispyridinium salt PTM0022 ( 3 h ) was found to have significantly higher binding affinity, with a pK_i value of 5.16±0.07, thus representing considerable progress toward the development of more potent nAChR re‐sensitizers.     

Copper-silica and copper-alumina alloys of high temperature interest

Utilizing relatively coarse copper powders and several sizes of silica and alumina powders, alloys containing up to 10 volume pct of oxide were made. The alloys were prepared by mechanical mixing of powders, followed by cold hydrostatic pressing, sintering, and hot extrusion. Measurements were made of room temperature tensile properties, recrystallization temperature, creep rupture properties from 250° to 450°C, and resistivity. In addition, metallographic studies were made of the resultant structures. Of particular interest was the stability of the structure with respect to temperature, time, and stress.     

Final solidification,centre segregation and precipitation phenomena in continuously cast round billets

Archimedes’ principle was applied to strand lengths of up to 14 m of round 177 mm diameter billets to determine cavity volume V (in cm³/m) for a series of tubemaking steels. Under steady state casting conditions, V depends primarily on the chemical composition and solidification behaviour of the steels. Averages ranged up to in an extreme case (bearing steel; v_C = 2.0 m/min). Stopping the strand and abrupt lowering of withdrawal speed made it possible to artificially induce individual shrinkage cavities with peak values of V = 45 cm³/m. In the round mould, subsequent necking of the liquid crater is initiated in this process. Whisker-like and icicle-like dendrites can be observed in horizontally formed macroscopic shrinkage cavities. The liquid crater is broken off by periodic bridging (the mini-lingot model). As permeability decreases, the bridges deflect downward in a U-shape under the ferrostatic load. The residual inter-dendritic melt is squeezed out in this plastic deformation process. Some bridges ultimately break. This interpretation is based on comprehensive CMA studies and concentration maps. Cores taken from the centre of a strand of bearing steel were submitted to various heat treatments between 1100 and 1350°C. Homogenization occurs below solidus (T < 1225°C). Carbides dissolve and sulfides become globular. Spatial segregation, on the other hand, increases, above solidus. In the extreme case at 1350°C/30 h, the residual melt at the grain boundaries migrates practically completely from the surface zone to the centre of the cylindrical sample (40 mm diameter). The propellent forces for this macro-heterogenization are provided by the activity gradient from the cylindrical surface to the centre and minimization of interface energy γ/I.     

Control of the chromium-oxygen reaction in pure iron melts

Oxygen activities in Fe-O-Cr melts, equilibrated with chromium oxide, were determined as a function of chromium content by EMF measurements using ZrO₂(CaO) plug-type sensors with a Cr-Cr₂O₃ reference. Plug-type sensors with or without Cr₂O₃ saturator were used in the experiments. From the experimental results values for the activity coefficient f_O and the interaction parameters and were evaluated. Raoultian chromium activity features a slight positive deviation from ideal solution behaviour in the temperature range from 1550 to 1650°C. Taking into account the calculated interaction parameters, the equilibrium constant K_Cr-O was redetermined at 1550 to 1650°C. In comparison with previous studies a better agreement was obtained with existing thermochemical data.