Hydrophobic Molecule Monolayer Brush-Tethered Zinc Anodes for Aqueous Zinc Batteries
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99 GENERAL AND MISCELLANEOUS↗
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Multi-technique structural analysis of zinc carboxylates (soaps)
A series of medium- and long-chain zinc carboxylates (zinc octanoate, zinc nonanoate, zinc decanoate, zinc undecanoate, zinc dodecanoate, zinc pivalate, zinc stearate, zinc palmitate, zinc oleate, and zinc azelate) was analyzed by ultra-high-field 67 Zn NMR spectroscopy up to 35.2 T, as well as 13 C NMR and FTIR spectroscopy. We also report the single-crystal X-ray diffraction structures of zinc nonanoate, zinc decanoate, and zinc oleate—the first long-chain carboxylate single-crystals to be reported for zinc. The NMR and X-ray diffraction data suggest that the carboxylates exist in three distinct geometric groups, based on structural and spectroscopic parameters. The ssNMR results presented here present a future for dynamic nuclear polarization (DNP)-NMR-based minimally invasive methods for testing artwork for the presence of zinc carboxylates.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Zinc dynamics regulate early ovarian follicle development
Zinc fluctuations regulate key steps in late oocyte and pre-implantation embryo development; however, roles for zinc in preceding stages in early ovarian follicle development, when cooperative interactions exist between the oocyte and somatic cells, are unknown. To understand the roles of zinc during early follicle development, we applied single cell X-ray fluorescence microscopy, a radioactive zinc tracer, and a labile zinc probe to measure zinc in individual mouse oocytes and associated somatic cells within early follicles. Here, we report a significant stage-specific increase and compartmental redistribution in oocyte zinc content upon the initiation of early follicle growth. The increase in zinc correlates with the increased expression of specific zinc transporters, including two that are essential in oocyte maturation. While oocytes in follicles exhibit high tolerance to pronounced changes in zinc availability, somatic survival and proliferation are significantly more sensitive to zinc chelation or supplementation. Finally, transcriptomic, proteomic, and zinc loading analyses reveal enrichment of zinc targets in the ubiquitination pathway. Overall, these results demonstrate that distinct cell type- specific zinc regulations are required for follicle growth and indicate that physiological fluctuation in the localization and availability of this inorganic cofactor has fundamental functions in early gamete development.
59 BASIC BIOLOGICAL SCIENCES↗
Zinc batteries for grid-scale energy storage: Challenges, opportunities, and future directions
The global electricity sector is undergoing rapid transformation, increasing demand for reliable stationary energy storage and intensifying the need for safe, cost-effective, and scalable technologies for grid-scale applications. While lithium-ion batteries currently dominate the market, concerns over cost, safety, and resource availability motivate the exploration of alternative chemistries. Zinc-based batteries have emerged as a promising option due to the abundance, low cost, and wide geographic distribution of zinc, combined with the inherent safety of aqueous electrolytes. This perspective examines the potential of zinc batteries for stationary energy storage, with particular focus on rechargeable zinc-air systems. We discuss the evolution of zinc battery technologies and compare zinc-air, zinc-bromine, nickel-zinc, and aqueous zinc-ion chemistries, highlighting their advantages for grid applications. Key challenges limiting rechargeable zinc battery performance are analyzed, including dendrite formation and corrosion at the zinc anode, electrolyte degradation from carbonation and evaporation, and sluggish oxygen electrocatalysis at the air cathode. Emerging strategies to address these limitations are reviewed, including advanced electrode architectures, electrolyte engineering, catalyst development, and system-level design improvements. Lastly, we outline future research directions and opportunities for developing durable, efficient, and economically viable zinc-based energy storage systems for grid-scale applications.
Aqueous electrolytes↗
A periplasmic zinc capture protein enhances the resistance of Neisseria gonorrhoeae to nutritional immunity
During microbial infection, mammalian hosts reduce the availability of free metals such as zinc in a process known as nutritional immunity. Pathogens counteract nutritional immunity by expressing gene products that enhance growth in metal-limited conditions. One of the most transcriptionally induced genes in zinc-limited Neisseria gonorrhoeae , ngo1049, encodes a DUF4198 family protein we have named Zcp. This family of proteins is widely distributed in Gram-negative bacteria. Here, we provide the first structural, biochemical, and functional characterization of a DUF4198 protein. Zcp is a periplasmic, homodimeric substrate-binding protein (SBP), which binds one zinc ion per subunit with submicromolar affinity. We identified a zinc binding pocket in each subunit, composed of three histidine residues. Zcp enables maximal growth of N. gonorrhoeae in zinc-limited conditions but is dispensable for zinc uptake, in contrast to the cluster A-I SBP ZnuA, which is required for zinc import. The growth defect of zcp mutant N. gonorrhoeae is rescued by zinc supplementation. Zcp associates with proteins with roles in maintaining cell envelope integrity, and N. gonorrhoeae lacking zcp is more sensitive to envelope-targeting antimicrobials. Zcp enables infectivity of human epithelial cells and neutrophils by zinc-limited N. gonorrhoeae . We conclude that N. gonorrhoeae produces Zcp to buffer periplasmic zinc, which enables ZnuA to balance import of different metals and ensures the bioavailability of zinc for extracytoplasmic zinc-requiring proteins, as part of the coordinated response to host-imposed nutritional immunity.
Liyayi, Ian K. [Department of Microbiology, Immuno↗
Zinc against COVID-19? Symptom surveillance and deficiency risk groups
A wide variety of symptoms is associated with Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2) infection, and these symptoms can overlap with other conditions and diseases. Knowing the distribution of symptoms across diseases and individuals can support clinical actions on timelines shorter than those for drug and vaccine development. Here, we focus on zinc deficiency symptoms, symptom overlap with other conditions, as well as zinc effects on immune health and mechanistic zinc deficiency risk groups. There are well-studied beneficial effects of zinc on the immune system including a decreased susceptibility to and improved clinical outcomes for infectious pathogens including multiple viruses. Zinc is also an anti-inflammatory and anti-oxidative stress agent, relevant to some severe Coronavirus Disease 2019 (COVID-19) symptoms. Unfortunately, zinc deficiency is common worldwide and not exclusive to the developing world. Lifestyle choices and preexisting conditions alone can result in zinc deficiency, and we compile zinc risk groups based on a review of the literature. It is also important to distinguish chronic zinc deficiency from deficiency acquired upon viral infection and immune response and their different supplementation strategies. Zinc is being considered as prophylactic or adjunct therapy for COVID-19, with 12 clinical trials underway, highlighting the relevance of this trace element for global pandemics. Using the example of zinc, we show that there is a critical need for a deeper understanding of essential trace elements in human health, and the resulting deficiency symptoms and their overlap with other conditions. This knowledge will directly support human immune health for decreasing susceptibility, shortening illness duration, and preventing progression to severe cases in the current and future pandemics.
59 BASIC BIOLOGICAL SCIENCES↗
The role of zinc in the adaptive evolution of polar phytoplankton
Zinc is an essential trace metal for oceanic primary producers with the highest concentrations in polar oceans. However, its role in the biological functioning and adaptive evolution of polar phytoplankton remains enigmatic. Here, we have applied a combination of evolutionary genomics, quantitative proteomics, co-expression analyses and cellular physiology to suggest that model polar phytoplankton species have a higher demand for zinc because of elevated cellular levels of zinc-binding proteins. We propose that adaptive expansion of regulatory zinc-finger protein families, co-expanded and co-expressed zinc-binding proteins families involved in photosynthesis and growth in these microalgal species and their natural communities were identified to be responsible for the higher zinc demand. The expression of their encoding genes in eukaryotic phytoplankton metatranscriptomes from pole-to-pole was identified to correlate not only with dissolved zinc concentrations in the upper ocean but also with temperature, suggesting that environmental conditions of polar oceans are responsible for an increased demand of zinc. Furthermore, these results suggest that zinc plays an important role in supporting photosynthetic growth in eukaryotic polar phytoplankton and that this has been critical for algal colonization of low-temperature polar oceans.
59 BASIC BIOLOGICAL SCIENCES↗
Performance characteristics of zinc-rich coatings applied to carbon steel
A program was conducted to evaluate the performance of topcoated and untopcoated zinc-rich coatings. Sacrificial coatings of this type are required for protecting carbon steel structures from the aggressive KSC sea coast environment. A total of 59 commercially available zinc-rich coatings and 47 topcoated materials were exposed for an 18-month period. Test panels were placed in special racks placed approximately 30.5 m (100 feet) above the high tide line at the KSC Corrosion Test Site. Laboratory tests to determine the temperature resistance, abrasion resistance, and adhesion of the untopcoated zinc-rich coatings were also performed. It has been concluded that: (1) The inorganic types of zinc-rich coatings are far superior to the organic types in the KSC environment. (2) Organic zinc-rich coatings applied at 0.1 - 0.15 mm (4-6 mils) film thickness provide better corrosion protection than when applied at the manufacturers' recommended nominal film thickness of .08 mm (3 mils). (3) Topcoats are not necessary, or even desirable, when used in conjunction with zinc-rich coatings in the KSC environment. (4) Some types of inorganic zinc-rich coatings require an extended outdoor weathering period in order to obtain adequate mechanical properties. and (5) A properly formulated inorganic zinc-rich coating is not affected by a 24-hour thermal exposure to 400 C (752 F).
Paton, W. J.↗
Zinc and copper balances in healthy adult males during and after 17 wk of bed rest
The effects of long-term bed rest on zinc and copper balances were measured in seven healthy men. Volunteers aged 22-54 y (mean +/- SD, 34 +/- 12 y), 168-185 cm in height (173 +/- 5 cm), and 64-86 kg in weight (74 +/- 9 kg) remained on a metabolic ward for 29 wk. Subjects were ambulatory during weeks 1-5, remained in continuous bed rest for weeks 6-22, and were reambulated during weeks 23-29. Copper and zinc were measured in weekly urine and fecal composites. Dietary intakes provided (mean +/- SD) 19.2 +/- 1.2 mumol Cu (1.22 +/- 0.08 mg), 211 +/- 11 mumol Zn (13.81 +/- 0.72 mg), 25.2 +/- 1.2 mmol Ca (1011 +/- 46 mg), 1086 +/- 46 mmol N (15.21 +/- 0.65 g), and 48.1 +/- 1.4 mmol K (1489 +/- 44 mg)/d. Bed rest increased fecal zinc excretion and decreased zinc balance, whereas copper balance was unchanged. Reambulation decreased fecal zinc excretion and increased both zinc and copper balances. These results suggest that during long-term bed rest or space flight, individuals will lose total body zinc and will retain more zinc and copper when they reambulate.
Non-NASA Center↗
Dynamic zinc fluxes regulate meiotic progression in Caenorhabditis elegans
Abstract Zinc influx and efflux events are essential for meiotic progression in oocytes of several mammalian and amphibian species, but it is less clear whether this evolutionary conservation of zinc signals is also important in late-stage germline development in invertebrates. Using quantitative, single cell elemental mapping methods, we find that Caenorhabditis elegans oocytes undergo significant stage-dependent fluctuations in total zinc content, rising by over sevenfold from Prophase I through the beginning of mitotic divisions in the embryo. Live imaging of the rapid cell cycle progression in C. elegans enables us to follow changes in labile zinc pools across meiosis and mitosis in single embryo. We find a dynamic increase in labile zinc prior to fertilization that then decreases from Anaphase II through pronuclear fusion and relocalizes to the eggshell. Disruption of these zinc fluxes blocks extrusion of the second polar body, leading to a range of mitotic defects. We conclude that spatial temporal zinc fluxes are necessary for meiotic progression in C. elegans and are a conserved feature of germ cell development in a broad cross section of metazoa.
59 BASIC BIOLOGICAL SCIENCES↗
Structure and Function of the Zinc Binding Protein ZrgA from Vibrio cholerae
ATP binding cassette (ABC) transporters are the primary means by which bacteria acquire trace elements from the environment. They rely on solute binding proteins (SBPs) to bind the relevant substrate and deliver it to the integral membrane permease for ATP-powered import into the cytoplasm. SBPs of cluster A-I are known to facilitate the transport of essential metals zinc, manganese, and iron, and many have been characterized to date. A group of ABC transporter operons dubbed zinc-regulated genes (zrg) have recently been shown to transport zinc with putative SBPs (zrgA) bearing no homology to the classical cluster A-I family, and a recent crystal structure of a representative protein from Pseudomonas aeruginosa shows no structural similarity to classical SBPs. Thus, the ZrgA proteins appear to represent a newly discovered family of zinc SBPs widespread among Gram-negative bacteria, including human pathogens. Here, we have determined the crystal structure of ZrgA from Vibrio cholerae and characterized its zinc binding in vitro and function in vivo. We also assessed the role of a histidine-rich sequence that appears to be a hallmark of ZrgA proteins that is particularly long in V. cholerae ZrgA. The results show that the zrgA gene is critical to the function of the operon, consistent with a function as an SBP in this system. Further, the His-rich region is not essential to the function of ZrgA, but it does provide additional zinc binding sites in vitro. The structure and zinc binding data for ZrgA reveal interesting differences between it and its homologue from P. aeruginosa, illustrating diversity within this little-studied protein family.
59 BASIC BIOLOGICAL SCIENCES↗
The corrosion protection of 2219-T87 aluminum by organic and inorganic zinc-rich primers
The behavior of zinc-rich primer-coated 2219-T87 aluminum in a 3.5-percent Na-Cl was investigated using electrochemical techniques. The alternating current (ac) method of electro-chemical impedance spectroscopy (EIS), in the frequency range of 0.001 to 40,000 Hz, and the direct current (dc) method of polarization resistance (PR) were used to evaluate the characteristics of an organic, epoxy zinc-rich primer and an inorganic, ethyl silicate zinc-rich primer. A dc electrochemical galvanic corrosion test was also used to determine the corrosion current of each zinc-rich primer anode coupled to a 2219-T87 aluminum cathode. Duration of the EIS/PR and galvanic testing was 21 days and 24 h, respectively. the galvanic test results demonstrated a very high galvanic current between the aluminum cathode and both zinc-rich primer anodes (37.9 micro A/cm(exp 2) and 23.7 micro A/cm(exp 2) for the organic and inorganic primers, respectively). The PR results demonstrated a much higher corrosion rate of the zinc in the inorganic primer than in the organic primer, due primarily to the higher porosity in the former. Based on this investigation, the inorganic zinc-rich primer appears to provide superior galvanic protection and is recommended for additional study for application in the solid rocket booster aft skirt.
Danford, M. D.↗
The corrosion protection of AISI(TM) 1010 steel by organic and inorganic zinc-rich primers
The behavior of zinc-rich primer-coated AISI 1010 steel in 3.5-percent Na-Cl was investigated using electrochemical techniques. The alternating current (ac) method of electrochemical impedance spectroscopy (EIS), in the frequency range of 0.001 to 40,000 Hz, and the direct current (dc) method of polarization resistance (PR), were used to evaluate the characteristics of an organic, epoxy zinc-rich primer and an inorganic, ethyl silicate zinc-rich primer. A dc electromechanical galvanic corrosion test was also used to determine the corrosion current of each zinc-rich primer anode coupled to a 1010 steel cathode. Duration of the EIS/PR and galvanic testing was 21 days and 24 h, respectively. The galvanic test results demonstrated a very high current between the steel cathode and both zinc-rich primer anodes (38.8 and 135.2 microns A/sq cm for the organic and inorganic primers, respectively). The results of corrosion rate determinations demonstrated a much higher corrosion rate of the zinc in the inorganic primer than in the organic primer, due primarily to the higher porosity in the former. EIS equivalent circuit parameters confirmed this conclusion. Based on this investigation, the inorganic zinc-rich primer appears to provide superior galvanic protection and is recommended for additional study for application on solid rocket booster steel hardware.
Danford, M. D.↗
The Corrosion Protection of 2219-T87 Aluminum by Organic and Inorganic Zinc-Rich Primers
The behavior of zinc-rich primer-coated 2219-T87 aluminum in a 3.5-percent Na-Cl was investigated using electrochemical techniques. The alternating current (ac) method of electrochemical impedance spectroscopy (EIS), in the frequency range of 0.001 to 40,000 Hz, and the direct current (dc) method of polarization resistance (PR) were used to evaluate the characteristics of an organic, epoxy zinc-rich primer and an inorganic, ethyl silicate zinc-rich primer. A dc electrochemical galvanic corrosion test was also used to determine the corrosion current of each zinc-rich primer anode coupled to a 2219-T87 aluminum cathode. Duration of the EIS/PR and galvanic testing was 21 days and 24 h, respectively. The galvanic test results demonstrated a very high galvanic current between the aluminum cathode and both zinc-rich primer anodes (37.9 pA/CM2 and 23.7 pA/CM2 for the organic and inorganic primers, respectively). The PR results demonstrated a much higher corrosion rate of the zinc in the inorganic primer than in the organic primer, due primarily to the higher porosity in the former. Based on this investigation, the inorganic zinc-rich primer appears to provide superior galvanic protection and is recommended for additional study for application in the solid rocket booster aft skirt.
Danford, M. D.↗
PET imaging of zinc transport
A method for producing a solution including a positron emitting zinc cation of 63Zn, and the method comprises bombarding a solution target including 63 Cu with high energy protons to produce a solution including a positron emitting zinc cation. A method for detecting or ruling out Alzheimer's disease in a patient comprises administering to a patient a detectable amount of a compound including a positron emitting zinc cation, wherein the zinc cation is targeted to β-amyloid in the patient, and acquiring an image to detect the presence or absence of β-amyloid in the patient. A method for detecting or ruling out cancer in a patient comprises administering to a patient a detectable amount of a compound including a positron emitting zinc cation, wherein the zinc cation is targeted to tissue in the patient; and acquiring an image using a medical imaging technique to detect zinc distribution in tissue in the patient.
DeGrado, Timothy R.↗
Zinc oxide based sorbent and process for preparing same
Zinc oxide-based sorbents, and processes for preparing and using them are provided, wherein the sorbents are preferably used to remove one or more reduced sulfur species from gas streams. The sorbents contain an active zinc component, optionally in combination with one or more promoter components and/or one or more substantially inert components. The active zinc component is a two-phase material, consisting essentially of a zinc oxide (ZnO) phase and a zinc aluminate (ZnAl 2 O 4 ) phase. Each of the two phases is characterized by a relatively small crystallite size of typically less than about 50 nm (500 Angstroms). Preferably the sorbents are prepared by using an alkali metal base to convert a precursor mixture, containing a precipitated zinc oxide precursor and a precipitated aluminum oxide precursor, to the two-phase, active zinc oxide containing component, with the resulting sorbent having a sodium level within a desired range.
Shen, Jian-Ping↗
Polar algae flaunt their zinc assets
Metal ions have been at the centre of pivotal points in the evolution of extant life. Oxygen-evolving photosynthesis, which irrevocably reshaped the geochemistry and biology of our planet, has an absolute requirement for metal ions to harvest light, split water and transfer electrons. Access to abundant oxygen then led to the propagation of organisms capable of oxidative metabolism, a process that is also dependent on metal ions for electron transfer and reduction of molecular oxygen. Because of the essential links between metal ions and the proteins that require them to function, as well as changes in metal bioavailability through time, metals have shaped the trajectories that evolution can take. Iron typically steals this show, but with access to whole-genome sequences and transcriptomes, the imprint that zinc has made on biology is coming into focus. Writing in Nature Ecology & Evolution, Ye and colleagues present new insights into the complex connections between zinc bioavailability, adaptation of algae to the polar oceans and the evolution of regulatory networks. By combining field and laboratory-based analyses, the authors suggest that expanded families of zinc-binding proteins have enabled the green alga Microglena sp. YARC to flourish in the harsh conditions of the polar Southern Ocean (Fig. 1). As the waters where this alga occurs are known for their enrichment of zinc, the authors further propose that availability of this metal ion was directly responsible for successful microalgal colonization of polar oceans. To test this hypothesis, the authors compare meta-transcriptomes collected from pole-to-pole and find positive correlations between higher copy numbers for transcripts encoding putative zinc-binding proteins, higher latitudes, lower surface temperatures and dissolved zinc.
59 BASIC BIOLOGICAL SCIENCES↗
Long life, rechargeable nickel-zinc battery
A production version of the inorganic separator was evaluated for improving the life of the nickel-zinc system. Nickel-zinc cells (7-10 Ah capacities) of different electrode separator configurations were constructed and tested. The nickel-zinc cells using the inorganic separator encasing the zinc electrode, the nickel electrode, or both electrodes had shorter lives than cells using Visking and cellophane separation. Cells with the inorganic separation all fell below 70% of their theoretical capacity within 30 cycles, but the cells constructed with organic separation required 80 cycles. Failure of the cells using the ceramic separator was irreversible capacity degradation due to zinc loss through cracks developed in the inorganic separator. Zinc loss through the separator was minimized with the use of combinations of the inorganic separator with Visking and cellophane. Cells using the combined separation operated 130 duty cycles before degrading to 70% of their theoretical capacity.
Luksha, E.↗