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- ItemCoordination chemistry and photoswitching of dinuclear macrocyclic cadmium-, nickel-, and zinc complexes containing azobenzene carboxylato co-ligands(Frankfurt, Main : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2019) Klose, Jennifer; Severin, Tobias; Hahn, Peter; Jeremies, Alexander; Bergmann, Jens; Fuhrmann, Daniel; Griebel, Jan; Abel, Bernd; Kersting, BertholdThe synthesis of mixed-ligand complexes of the type [M2L(μ-L')]+, where L represents a 24-membered macrocyclic hexaaza-dithiophenolate ligand, L' is an azobenzene carboxylate co-ligand, and M = Cd(II), Ni(II) or Zn(II), is reported. A series of new complexes were synthesized, namely [M2L(μ-L')]+ (L' = azo-H, M = Cd (1), Ni (2); L' = azo-OH, M = Zn (3), Ni (4); L' = azo-NMe2, M = Zn (5), Cd (6), Ni (7); L' = azo-CO2Me, M = Cd (8), Ni (9)), and characterized by elemental analysis, electro-spray ionization mass spectrometry (ESIMS), IR, UV–vis and NMR spectroscopy (for diamagnetic Zn and Cd complexes) and X-ray single crystal structure analysis. The crystal structures of 3' and 5–8 display an isostructural series of compounds with bridging azobenzene carboxylates in the trans form. The paramagnetic Ni complexes 2, 4 and 7 reveal a weak ferromagnetic exchange interaction with magnetic exchange coupling constant values between 21 and 23 cm−1 (H = −2JS1S2). Irradiation of 1 with λ = 365 nm reveals a photoisomerization of the co-ligand from the trans to the cis form. © 2019 Klose et al.
- ItemDual-Zinc Electrode Electrochemical Desalination(Weinheim : Wiley-VCH Verlag, 2020) Dai, J.; Wang, J.; Hou, X.; Ru, Q.; He, Q.; Srimuk, P.; Presser, V.; Chen, F.Continuous and low-energy desalination technologies are in high demand to enable sustainable water remediation. Our work introduces a continuous desalination process based on the redox reaction of a dual-zinc electrode. The system consists of two zinc foils as redox electrodes with flowing ZnCl2 electrolyte, concentrated and diluted salt streams with three anion- and cation-exchange membranes (AEM and CEM) separated configuration (AEM|CEM|AEM). If a constant current is applied, the negative zinc electrode is oxidized, and electrons are released to the external circuit, whereas the positive zinc electrode is reduced, causing salt removal in the dilution stream. The results showed that brackish water can be directly desalted to 380.6 ppm during a continuous batch-mode process. The energy consumption can be as low as 35.30 kJ mol−1 at a current density of 0.25 mA cm−2, which is comparable to reverse osmosis. In addition, the dual-zinc electrode electrochemical desalination demonstrates excellent rate performance, reversibility, and batch cyclability through electrode exchange regeneration. Our research provides a route for continuous low-energy desalination based on metal redox mediators.
- ItemHigh-performance ion removal via zinc–air desalination(Amsterdam : Elsevier, 2020) Srimuk, P.; Wang, L.; Budak, Ö.; Presser, V.Electrochemical processes enable a new generation of energy-efficient desalination technologies. While ion electrosorption via capacitive deionization is only suitable for brackish water with low molar strength, the use of Faradaic materials capable of reversible ion intercalation or conversion reactions allows energy-efficient removal of ions from seawater. However, the limited charge transfer/storage capacity of Faradaic materials indicates an upper limit for their desalination applications. Therefore, a new electrochemical concept must be explored to exceed the current state-of-the-art results and to push the desalination capacity beyond 100–200 mgNaCl/gelectrode. In this proof-of-concept work, we introduce the new concept of using metal–air battery technology for desalination. We do so by presenting performance data for zinc–air desalination (ZAD) in 600 mM NaCl. The ZAD cell provides a desalination capacity of 0.9–1.0 mgNaCl/cm2 (normalized to the membrane area; corresponding to 1300 mgNaCl/gZn) with a charge efficiency of 70% when charging/discharging the cell at 1 mA/cm2. The energy consumption of ZAD is 68–92 kJ/mol.
- ItemGreen-Emissive Zn2+ Complex Supported by a Macrocyclic Schiff-Base/Calix[4]arene-Ligand: Crystallographic and Spectroscopic Characterization(Weinheim : Wiley-VCH, 2021) Ullmann, Steve; Börner, Martin; Kahnt, Axel; Abel, Bernd; Kersting, BertholdThe macrocyclic calix[4]arene ligand H2L comprises two non-fluorescent 2,6-bis-(iminomethyl)phenolate chromophores, which show a chelation-enhanced fluorescence enhancement upon Zn2+ ion complexation. Macrocyclic [ZnL] complexes aggregate in the absence of external coligands via intermolecular Zn−N bonds to give dimeric [ZnL]2 structures comprising two five-coordinated Zn2+ ions. The absorption and emission wavelengths are bathochromically shifted upon going from the liquid (λmax,abs (CH2Cl2)=404 nm, λmax,em (CH2Cl2)=484 nm) to the solid state (λmax,abs=424 nm (4 wt%, BaSO4 pellet), λmax,em=524 nm (neat solid)). Insights into the electronic nature of the UV-vis transitions were obtained with time-dependent density functional theory (TD-DFT) calculations for a truncated model complex.
- ItemBiofunctionalized zinc peroxide (ZnO2) nanoparticles as active oxygen sources and antibacterial agents(London : RSC Publishing, 2017) Bergs, Christian; Brück, Lisa; Rosencrantz, Ruben R.; Conrads, Georg; Elling, Lothar; Pich, AndrijOxygen is one of the most important substances for physiological reactions and metabolisms in biological systems. Through the tailored design of oxygen-releasing materials it might be possible to control different biological processes. In this work we synthesized for the first time zinc peroxide nanoparticles with controlled sizes and biofunctionalized surfaces using a one-step reaction procedure. The zinc peroxide nanoparticles were obtained with tunable sizes (between 4.0 ± 1.2 nm and 9.4 ± 5.2 nm) and were decorated with glucose 1-phosphate (Glc-1P). The specific interaction of the phosphate function of Glc-1P with the nanoparticle surface was monitored by solid state 31P-NMR and zeta-potential measurements. Furthermore, using fluorescence measurements we demonstrated that anchored glucose molecules on the nanoparticle surface are accessible for specific interactions with lectins. It could be shown that these interactions strongly depend on the amount of Glc-1P attached to the nanoparticle surface. Additionally it was demonstrated that the oxygen release from biofunctionalized zinc peroxide nanoparticles could be tuned according to the chemical composition of the nanoparticles and the pH of the aqueous solution. The antibacterial efficiency of the synthesized nanoparticles against Enterococcus faecalis, Aggregatibacter actinomycetemcomitans, Porphyromonas gingivalis and Prevotella intermedia was evaluated by determination of minimal bactericidal concentration (MIC).
- ItemTheoretical mechanistic investigation of zinc(ii) catalyzed oxidation of alcohols to aldehydes and esters(London : RSC Publishing, 2016) Nisa, Riffat Un; Mahmood, Tariq; Ludwig, Ralf; Ayub, KhurshidThe mechanism of the Zn(II) catalyzed oxidation of benzylic alcohol to benzaldehyde and ester by H2O2 oxidant was investigated through density functional theory methods and compared with the similar oxidation mechanisms of other late transition metals. Both inner sphere and intermediate sphere mechanisms have been analyzed in the presence and absence of pyridine-2-carboxylic acid (ligand). An intermediate sphere mechanism involving the transfer of hydrogen from alcohol to H2O2 was found to be preferred over the competitive inner sphere mechanism involving β-hydride elimination. Kinetic barriers associated with the intermediate sphere mechanism are consistent with the experimental observations, suggesting that the intermediate sphere mechanism is a plausible mechanism under these reaction conditions. The oxidation of alcohols to aldehydes (first step) is kinetically more demanding than the oxidation of hemiacetals to esters (second step). Changing the oxidant to tert-butyl hydrogen peroxide (TBHP) increases the activation barrier for the oxidation of alcohol to aldehyde by 0.4 kcal mol−1, but decreases the activation barrier by 3.24 kcal mol−1 for oxidation of hemiacetal to ester. Replacement of zinc bromide with zinc iodide causes the second step to be more demanding than the first step. Pyridine-2-carboxylic acid ligand remarkably decreases the activation barriers for the intermediate sphere pathway, whereas a less pronounced inverse effect is estimated for the inner sphere mechanism.
- ItemThe influence of cadmium stress on the content of mineral nutrients and metal-binding proteins in arabidopsis halleri(Heidelberg : Springer, 2012) Przedpełska-Wąsowicz, Ewa; Polatajko, Aleksandra; Wierzbicka, MałgorzataWe investigated the influence of cadmium stress on zinc hyperaccumulation, mineral nutrient uptake, and the content of metal-binding proteins in Arabidopsis halleri. The experiments were carried out using plants subjected to long-term cadmium exposure (40 days) in the concentrations of 45 and 225 μM Cd2+. Inductively coupled plasma-mass spectrometry, size exclusion chromatography coupled with plasma-mass spectrometry, and laser ablation inductively coupled plasma-mass spectrometry used for ablation of polyacylamide gels were employed to assess the content of investigated elements in plants as well as to identify metal-binding proteins. We found that A. halleri is able to translocate cadmium to the aerial parts in high amounts (translocation index >1). We showed that Zn content in plants decreased significantly with the increase of cadmium content in the growth medium. Different positive and negative correlations between Cd content and mineral nutrients were evidenced by our study. We identified more than ten low-molecular-weight (<100 kDa) Cd-binding proteins in Cd-treated plants. These proteins are unlikely to be phytochelatins or metallothioneins. We hypothesize that low-molecular-weight Cd-binding proteins can be involved in cadmium resistance in A. halleri.