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1. Low-molecular-mass labile metal pools in Escherichia coli: advances using chromatography and mass spectrometry

   https://doi.org/10.1007/s00775-021-01864-w  

   Brawley, Hayley N. ; Lindahl, Paul A. ( June 2021 , JBIC Journal of Biological Inorganic Chemistry)

   Abstract Labile low-molecular-mass (LMM) transition metal complexes play essential roles in metal ion trafficking, regulation, and signalling in biological systems, yet their chemical identities remain largely unknown due to their rapid ligand-exchange rates and weak M–L bonds. Here, an Escherichia coli cytosol isolation procedure was developed that was devoid of detergents, strongly coordinating buffers, and EDTA. The interaction of the metal ions from these complexes with a SEC column was minimized by pre-loading the column with 67 ZnSO 4 and then monitoring 66 Zn and other metals by inductively coupled plasma mass spectrometry (ICP-MS) when investigating cytosolic ultrafiltration flow-through-solutions (FTSs). Endogenous cytosolic salts suppressed ESI-MS signals, making the detection of metal complexes difficult. FTSs contained ca. 80 µM Fe, 15 µM Ni, 13 µM Zn, 10 µM Cu, and 1.4 µM Mn (after correcting for dilution during cytosol isolation). FTSs exhibited 2–5 Fe, at least 2 Ni, 2–5 Zn, 2–4 Cu, and at least 2 Mn species with apparent masses between 300 and 5000 Da. Fe(ATP), Fe(GSH), and Zn(GSH) standards were passed through the column to assess their presence in FTS. Major LMM sulfur- and phosphorus-containing species were identified. These included reduced and oxidized glutathione, methionine, cysteine, orthophosphate, and common mono- and di-nucleotides such as ATP,more »ADP, AMP, and NADH. FTSs from cells grown in media supplemented with one of these metal salts exhibited increased peak intensity for the supplemented metal indicating that the size of the labile metal pools in E. coli is sensitive to the concentration of nutrient metals.« less
2. Multipurpose made colorimetric materials for amines, pH change and metal ion detection

   https://doi.org/10.1039/d1ra07811a  

   Bao, Lihong ; Jones, Leighton O. ; Garrote Cañas, Ana M. ; Yan, Yunhan ; Pask, Christopher M. ; Hardie, Michaele J. ; Mosquera, Martin A. ; Schatz, George C. ; Sergeeva, Natalia N. ( January 2022 , RSC Advances)

   Sensors are routinely developed for specific applications, but multipurpose sensors are challenging, due to stability and poor functional design. We report organic materials that operate in solution and gas phase. They show a strong response behaviour to at least three types of environmental changes: pH, amine and metal ion binding/detection. We have confirmed and validated our findings using various analytical and computational methods. We found that the changes in polarity of the solvent and pH not only red shift the tail of the absorption spectra, but also extend the peak optical absorption of these structures by up to 100 nm, with consequential effects on the optical gap and colour changes of the materials. Acid–base response has been studied by spectrophotometric titrations with trifluoroacetic acid (TFA) and triethyl amine (TEA). The experiments show excellent reversibility with greater sensitivity to base than acid for all compounds. Analysis into metal sensing using Zn( ii ) and Cu( ii ) ions as analytes show that the materials can successfully bind the cations forming stable complexes. Moreover, a strong suppression of signal with copper gives an operative modality to detect the copper ion as low as 2.5 × 10 −6 M. The formation of themore »metal complexes was also confirmed by growing crystals using a slow diffusion method; subsequent single crystal X-ray analysis reveals the ratio of ligand to metal to be 2 to 1. To test sensitivity towards various amine vapours, paper-based sensors have been fabricated. The sensors show a detection capability at 1 ppm of amine concentration. We have employed CIE L * a * b * colour space as the evaluation method, this provides numeric comparison of the samples from different series and allows comparison of small colour differences, which are generally undetectable by the human-eye. It shows that the CIE L * a * b * method can assess both sensitivity to a particular class of analytes and a specificity response to individual amines in this subclass offering an inexpensive and versatile methodology.« less
3. Multivariate effects of pH, salt, and Zn2+ ions on Aβ40 fibrillation

   https://doi.org/10.1038/s42004-022-00786-1  

   Wang, Hongzhi ; Wu, Jinming ; Sternke-Hoffmann, Rebecca ; Zheng, Wenwei ; Mörman, Cecilia ; Luo, Jinghui ( December 2022 , Communications Chemistry)

   Abstract Amyloid-β (Aβ) peptide aggregation plays a central role in the progress of Alzheimer’s disease (AD), of which Aβ-deposited extracellular amyloid plaques are a major hallmark. The brain micro-environmental variation in AD patients, like local acidification, increased ionic strength, or changed metal ion levels, cooperatively modulates the aggregation of the Aβ peptides. Here, we investigate the multivariate effects of varied pH, ionic strength and Zn 2+ on Aβ 40 fibrillation kinetics. Our results reveal that Aβ fibrillation kinetics are strongly affected by pH and ionic strength suggesting the importance of electrostatic interactions in regulating Aβ 40 fibrillation. More interestingly, the presence of Zn 2+ ions can further alter or even reserve the role of pH and ionic strength on the amyloid fibril kinetics, suggesting the importance of amino acids like Histidine that can interact with Zn 2+ ions. Both pH and ionic strength regulate the secondary nucleation processes, however regardless of pH and Zn 2+ ions, ionic strength can also modulate the morphology of Aβ 40 aggregates. These multivariate effects in bulk solution provide insights into the correlation of pH-, ionic strength- or Zn 2+ ions changes with amyloid deposits in AD brain and will deepen our understanding of the molecular pathologymore »in the local brain microenvironment.« less
4. Metal binding and interdomain thermodynamics of mammalian metallothionein-3: enthalpically favoured Cu ⁺ supplants entropically favoured Zn ²⁺ to form Cu ₄ ⁺ clusters under physiological conditions

   https://doi.org/10.1039/d2sc00676f  

   Mehlenbacher, Matthew R. ; Elsiesy, Rahma ; Lakha, Rabina ; Villones, Rhiza Lyne ; Orman, Marina ; Vizcarra, Christina L. ; Meloni, Gabriele ; Wilcox, Dean E. ; Austin, Rachel N. ( January 2022 , Chemical Science)

   Metallothioneins (MTs) are a ubiquitous class of small metal-binding proteins involved in metal homeostasis and detoxification. While known for their high affinity for d 10 metal ions, there is a surprising dearth of thermodynamic data on metals binding to MTs. In this study, Zn 2+ and Cu + binding to mammalian metallothionein-3 (MT-3) were quantified at pH 7.4 by isothermal titration calorimetry (ITC). Zn 2+ binding was measured by chelation titrations of Zn 7 MT-3, while Cu + binding was measured by Zn 2+ displacement from Zn 7 MT-3 with competition from glutathione (GSH). Titrations in multiple buffers enabled a detailed analysis that yielded condition-independent values for the association constant ( K ) and the change in enthalpy (Δ H ) and entropy (Δ S ) for these metal ions binding to MT-3. Zn 2+ was also chelated from the individual α and β domains of MT-3 to quantify the thermodynamics of inter-domain interactions in metal binding. Comparative titrations of Zn 7 MT-2 with Cu + revealed that both MT isoforms have similar Cu + affinities and binding thermodynamics, indicating that Δ H and Δ S are determined primarily by the conserved Cys residues. Inductively coupled plasma mass spectrometry (ICP-MS)more »analysis and low temperature luminescence measurements of Cu-replete samples showed that both proteins form two Cu 4 + –thiolate clusters when Cu + displaces Zn 2+ under physiological conditions. Comparison of the Zn 2+ and Cu + binding thermodynamics reveal that enthalpically-favoured Cu + , which forms Cu 4 + –thiolate clusters, displaces the entropically-favoured Zn 2+ . These results provide a detailed thermodynamic analysis of d 10 metal binding to these thiolate-rich proteins and quantitative support for, as well as molecular insight into, the role that MT-3 plays in the neuronal chemistry of copper.« less
5. Photoresponsive Zn ²⁺ -specific metallohydrogels coassembled from imidazole containing phenylalanine and arylazopyrazole derivatives

   https://doi.org/10.1039/d0dt01809k  

   Sallee, Ashanti ; Ghebreyessus, Kesete ( August 2020 , Dalton Transactions)

   Stimuli-responsive supramolecular gels and metallogels have been widely explored in the past decade, but the fabrication of metallogels with reversible photoresponsive properties remains largely unexplored. In this study, we report the construction of photoresponsive hybrid zinc-based metallohydrogel systems coassembled from an imidazole functionalized phenylalanine derivative gelator (ImF) and carboxylic acid functionalized arylazopyrazole (AzoPz) molecular photoswitches in the presence of Zn 2+ ions. Unlike traditional covalent conjugation, noncovalent introduction of small molecular switches into the gel matrix provides a convenient route to generate photoresponsive functional materials with tunable properties and expands the scope of optically controlled molecular self-assemblies. It has been found that the carboxylic acid functionalized AzoPz derivatives alone or mixed with the ImF moiety could not self-assemble to form any gels. However, in the presence of Zn 2+ ions they readily formed the coassembled hybrid metallogels in an alkaline aqueous solution with various morphologies. These results suggest that the gelation process was triggered by the Zn 2+ ions. In addition, the ImF gelator shows specific response to Zn 2+ ions only. The presence of the AzoPz moiety in the gel matrix makes the metallogel coassemblies photoresponsive and the reversible gel-to-sol phase transition was studied by UV-vis spectroscopy. The gelsmore »showed a slow reversible light-induced gel-to-sol phase transition under UV ( λ = 365 nm) and then sol-to-gel transition by green light ( λ = 530) irradiation resulting in the reformation of the original gel state. The morphology and viscoelastic properties of the fibrillar opaque metallogels have been characterized by transmission electron microscopy (TEM) and rheological measurement, respectively.« less