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The increasing concerns on uranium and rare earth metal ion pollution in the environment require sustainable strategies to remove them from wastewater. The present study reports an eco-friendly approach to convert a kind of protein-rich biomass, brewer's spent grain (BSG), into effective biosorbents for uranyl and rare earth metal ions. The employed method reduces the energy consumption by performing the hydrothermal treatment at a significantly lower temperature (150 °C) than conventional hydrothermal carbonization. In addition, with the aid of the Maillard reaction between carbohydrates and proteins forming melanoidins, further activation processes are not required. Treatment at 150 °C for 16 h results in an altered biosorbent (ABSG) with increased content of carboxyl groups (1.46 mmol g

The complexation of the trivalent lanthanides Nd(III) and Eu(III) and of the actinide Am(III) with malate was studied using a multi−method approach. The combination of structural and thermodynamic studies was required for the interpretation of the stoichiometry and thermodynamic data (logβ0, ΔrH0m,2, ΔrS0m, ΔrG0m) of the lanthanide/actinide malate complexes leading to a profound molecular understanding of the system. The structure-sensitive methods vibrational spectroscopy and extended X–ray absorption fine structure spectroscopy complemented with quantum-mechanical ab–initio molecular dynamics calculations revealed a tridentate ring structure of the respective metal complexes. The metal is coordinated by two carboxylate groups and a hydroxyl group. UV–Vis, laser fluorescence and calorimetric studies consistently yielded two complex species having a 1:1 and a 1:2 (metal:malate) stoichiometry. Parallel factor analysis and iterative transformation factor analysis were applied to decompose experimental spectra into their single components and to determine stability constants. The 1:1 and 1:2 Nd(III) malate complexation constants determined by isothermal titration calorimetry were extrapolated to zero ionic strength using the specific ion interaction theory, yielding logβ10 and logβ20 of about 6 and 9, respectively. The respective complexation enthalpies ΔrH0m,1 and ΔrH0m,2 showed average values of 5 kJ·mol−1 which are typical for small organic molecules. The comparison of Nd(III) and Am(III) malate complexes showed that the malate binding motif, the speciation and the thermodynamics can be transferred from lanthanides(III) to actinides(III) supporting the 4f–/ 5f–element homology.

Reaction of equimolar amounts of Cu(OAc)2·H2O and bis[4-(3-ethoxysalicylideneamino)phenyl]methane (H2L1) or bis[4-(3-ethoxysalicylideneamino)phenyl]sulfide (H2L2) in a 1:1 THF/MeOH mixture leads to the formation of structure-analogous CuII helicates of the composition [{Cu2L2}(H2O)2}]·4H2O. The helicates form left- and right-handed hydrogen bonded strands using the bound water molecules as glue. Finally, a compact 3D arrangement of the molecules is achieved by weak π···π and CH···π interactions. The CuII ions possess a strongly distorted tetrahedral arrangement with a N2O2 donor set of the involved diimines. In addition, the molecular structure of the ligand H2L2 was determined and solution studies of the complex formation using UV/Vis and ESI-MS were performed.

The formation equilibria of salicylatoborate, lactatoborate and 3-hydroxybutyratoborate were studied by means of (11)B NMR spectroscopy. The smaller the pKa of the respective organic acid, the higher is the formation constant of the organoborate. The complexation of Eu(III) with salicylatoborate and lactatoborate was investigated by means of TRLFS (time-resolved laser-induced fluorescence spectroscopy) and (11)B NMR spectroscopy, yielding complexation constants lg β₁₁⁰ = 2.6-3.2. A Eu(III)-3-hydroxybutyrate complex was characterized by TRLFS and (1)H NMR spectroscopy (lg β₁₁⁰ = 2.89). DFT calculations of the investigated Eu(III)-organoborates and inorganic Eu(III)-(poly)borates provided information about the Eu(III) coordination (most likely chelate). They support the hypothesis that the complexation of Eu(III) with organic as well as inorganic borate structures containing the binding site "B(OR)4(-)" (R = H, threefold coordinated boron center(s), organic moiety) is comparable.

Thermodynamic parameters for the complex formation of Am(iii) and Eu(iii) with lactate were determined with UV-vis and time-resolved laser-induced fluorescence spectroscopy (TRLFS) in a temperature range between 25 and 70 °C. The reaction enthalpy decreased with increasing ionic strength. ATR FT-IR and NMR spectroscopy in combination with density functional theory (DFT) calculations revealed structural details of the Eu(iii) lactate 1 : 1 complex: a chelating coordination mode of the lactate with a monodentate binding carboxylate group and the hydroxyl group being deprotonated.

The complex formation of europium(III) with salicylic acid was investigated with time-resolved laser-induced fluorescence spectroscopy (TRLFS) in aqueous solution at elevated temperatures. Three complexes with metal-to-ligand stoichiometries of 1:1, 1:2 and 1:3 could be identified. Stability constants have been calculated for these complexes at various temperatures between 25 and 60 °C and at ionic strengths of 0.1 and 1 mol kg −1 . The constants were extrapolated to infinite dilution applying SIT. Using the van’t Hoff equation, thermodynamic data (reaction enthalpy Δ r H , reaction entropy Δ r S and reaction energy Δ r G ) could be determined. The formation of the 1:1 complex with Δ r H 0 = 4.3 ± 3.6 kJ mol −1 is nearly temperature independent, whereas the formation of the 1:2 and 1:3 complexes with standard reaction enthalpies of 17.8 ± 3.8 and 33.4 ± 5.8 kJ mol −1 , respectively, is clearly endothermic.

The influence of temperature up to 50 ºC and small organic ligands (citrate, tartrate) on the sorption of Eu(III) on the natural clay rock Opalinus Clay (OPA) under aerobic (p CO2 = 10−3.5 atm) synthetic OPA pore water conditions (pH 7.6, I = 0.4 mol L−1) was investigated. Batch sorption experiments and time-resolved laser-induced fluorescence spectroscopy (TRLFS) were used to study these influencing factors on the Eu(III) sorption. Sorption isotherms and distribution coefficients R d (15 ºC: log R d = 4.50 ± 0.05...50 ºC: log R d = 5.54 ± 0.06) at 2 × 10−9 mol L−1 Eu(III) as a function of the solid-to-liquid ratio (up to 3 g L−1) and temperature were determined. A significant temperature dependency of the Eu(III) sorption was observed. With rising temperature the Eu(III) sorption increases. The surface reaction is endothermic (Δ H sorb ∼ 50 kJ mol−1). Using TRLFS, a surface species with a luminescence emission lifetime of 201 ± 9 μs was identified. In the presence of tartrate or citrate the Eu(III) sorption decreases with increasing ligand concentration due to a complex formation of Eu(III) in solution, with citrate having a more pronounced influence on the sorption than tartrate. With the batch sorption experiments it can be shown that at a citrate concentration larger than 10−5 mol L−1 and at a tartrate concentration larger than 10−4 mol L−1 an increasing Eu(III) desorption occurs. This result is supported by TRLFS measurements, which show the correlation between the complexation of Eu(III) by citrate or tartrate in solution and the Eu(III) desorption process. Possible Eu(III) citrate or Eu(III) tartrate surface species on OPA could not be detected using TRLFS.

Periodic convective instability has been observed in a biphasic system during the complexation reaction of alkali picrate and dicyclohexano-18-crown-6 which undergoes mass transfer from the hexane phase into the aqueous phase. The convection was visualized by means of precipitated crystals that are formed in both phases by the complexation reaction. The fluid motion was observed with an optical microscope and further analyzed with the particle image velocimetry (PIV) technique. The partition at the extraction of cesium into the organic phase was followed by means of the radioactive isotope (137)Cs. The type of the hydrodynamic instability is governed by the alkali metal expressed via its stability constants for the complex formed. More stable complexes trigger a higher precipitation, thereby favoring a Raleigh-Taylor instability. Complexes with a lower stability constant induce Marangoni cells which show a pulsating character in a cubic container. Depending on the confinement of the experiment cell the fluid motion can also follow a back-and-forth movement. Possible mechanisms for the occurring oscillations are discussed.

We study the chemohydrodynamic pattern formation during interfacial mass transfer accompanied by a neutralization reaction. The system, which is placed in a Hele-Shaw cell, is a configuration of two immiscible liquid phases in contact along a plane interface. In the upper, organic layer a carboxylic acid is dissolved, the concentration of which is far beyond the equilibrium partition ratio. Interfacial acid transfer initiates the neutralization with an organic base dissolved in the lower, aqueous layer. Focus is on the exploration of a novel instability consisting of a regular cellular structure penetrating into the aqueous bulk solution. By several complementary experimental methods, including shadowgraph visualization with different magnifications, particle image velocimetry, differential interferometry, and detailed measurements of relevant material properties, the driving mechanism of the instability is identified. Synthesis of the experimental results suggests that lateral differences in buoyancy are responsible for the convection.

A dedicated spectrofluorimeter using ultrashort laser pulses as an excitation source was developed to measure the fluorescence properties of organic ligands for metal ion complexation with organic ligands. The laser system consists of an oscillator system for generation of femtosecond laser pulses, an amplifier system to increase the pulse energy of the generated pulses to about 2 mJ and an optical parametrical amplifier system to provide tunable laser pulses over a wide wavelength range (280 nm-10 microm). The laser pulses were applied to the sample and the emitted fluorescence was detected using a fast-gating intensified CCD camera-based spectrometer. To verify the performance of the laser, the well-known protonation constant [Pure Appl. Chem. 69 (1997) 329] of 2,3-dihydroxybenzoic acid was determined. The fluorescence lifetime of the excited species was determined as 375+/-32 ps in the pH range from 1.0 to 6.0, having a fluorescence emission maximum at 438 nm. The first protonation constant was determined from fluorescence data as log K(3)=3.17+/-0.05 at an ionic strength of 0.1 M and at 294 K exploiting the Stern-Volmer mechanism. The agreement of the protonation constant with literature data (log K(3)=3.10+/-0.20, I=0.1 M, T=298 K [Bull. Soc. Jpn. 44 (1971) 3459]) demonstrates the excellent performance of our system. Furthermore, we determined the complex formation constant log K(1)=-3.11+/-0.16 by measuring the fluorescence properties of the ligand for the 1:1 uranyldihydroxobenzoate complex in the pH range from 3.0 to 4.5 at ionic strength of 0.1 M and at 294 K. We also determined the complex formation constant via the fluorescence emission of the metal ion uranium(VI). The fluorescence of the uranyl ion is influenced by dynamic quenching of the non-dissociated ligand and by static quenching due to the complex formation. After correction of these effects using the determined fluorescence lifetime, the complex formation constant was calculated to be log K(1)=-3.99+/-0.44. A 1:1 metal:ligand stoichiometry was determined with both measurement methods. However, the difference of the obtained formation constants and the derived standard deviations indicate a superimposition of effects with the excited-state reactions of the ligand.

In the presence of polyborates (detected by B-11-NMR) the formation of a weak Eu(III) borate complex (lg beta(11) similar to 2, estimated) was observed by time-resolved laser-induced fluorescence spectroscopy (TRLFS). This complex is a precursor for the formation of a solid Eu(III) borate species. The formation of this solid in solution was investigated by TRLFS as a function of the total boron concentration: the lower the total boron concentration, the slower is the solid formation. The solid Eu(III) borate was characterized by IR spectroscopy, powder XRD and solid-state TRLFS. The determination of the europium to boron ratio portends the existence of pentaborate units in the amorphous solid.

A combined study devoted to chemo-Marangoni convection and the underlying kinetics is presented for a biphasic system in which surfactants are produced in situ by an interfacial reaction. The pattern formation studied in a Hele-Shaw cell in both microgravity and terrestrial environments initially shows an ensemble of chemo-Marangoni cells along a nearly planar interface. Soon, a crossover occurs to periodic large-scale interfacial deformations which coexist with the Marangoni cells. This crossover can be correlated with the autocatalytic nature of the interfacial reaction identified in the kinetic studies. The drastic increase in the product concentration is associated with an enhanced aggregate-assisted transfer after the critical micellar concentration is approached. In this context, it was possible to conclusively explain the changes in the periodicity of the interfacial deformations depending on the reactant concentration ratio.

Thermodynamic parameters for the complexation of Eu(3+) with pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid, BTC) as a model system for polymerizable metal-complexing humic acids were determined using temperature-dependent time-resolved laser-induced fluorescence spectroscopy (TRLFS) and isothermal titration calorimetry (ITC). At low metal and ligand concentrations (50 μM Eu(3+),1 mM BTC), a 1:1 monomeric Eu-BTC complex was identified in the range of 25-60 °C. At elevated concentrations (500 μM Eu(3+) and BTC) a temperature-dependent polymerization was observed, where BTC monomers are linked via coordinating shared Eu(3+) ions. The two methods lead to comparable thermodynamic data (ΔH = 18.5 ± 1.5/16.5 ± 0.1 kJ mol(-1); ΔS = 152 ± 5/130 ± 5 J mol(-1) K(-1); TRLFS/ITC) in the absence of polymerization. With the onset of polymerization, TRLFS reveals the water coordination number of the lanthanide, whereas calorimetry is superior in determining the thermodynamic data in this regime. Evaluating the heat uptake kinetics, the monomer and polymer formation steps could be separated by "time-resolved" ITC, revealing almost identical binding enthalpies for the sequential reactions. Structural features of the complexes were studied by Fourier-transform infrared (FTIR) spectroscopy in combination with density functional theory (DFT) calculations showing predominantly chelating coordination with two carboxylate groups in the monomeric complex and monodentate binding of a single carboxylate group in the polymeric complex of the polycarboxylate with Eu(3+). The data show that pyromellitic acid is a suitable model for the study of metal-mediated polymerization as a crucial factor in determining the effect of humic acids on the mobility of heavy metals in the environment.

For the first time Am(III) complexation with a small organic ligand could be identified and characterized with time-resolved laser-induced fluorescence spectroscopy (TRLFS) at room temperature and trace metal concentration. With pyromellitic acid (1,2,4,5-benzene-tetracarboxylic acid, BTC) as ligand spectroscopic characteristics for the Am BTC complex system as well as for the Am3+(aq) ion were determined at pH 5.0, an ionic strength of 0.1 M (NaClO4) and room temperature. The fluorescence lifetimes were determined to be 20.8 ± 3.4 ns for Am3+(aq) and 27.3 ± 2.3 ns for the Am BTC 1 : 1 complex; the emission maximum for the 5D1 7F1 transition is 691 nm for both species. The complex stability constant for the Am BTC 1 : 1 complex was calculated to be log β110 = 5.42 ± 0.09.