More Like this

1. The effect of crystal composition and environment on the color Doppler ultrasound twinkling artifact

   https://doi.org/10.1088/1361-6560/acb2ad  

   Rokni, Eric; Simon, Julianna C. (February 2023, Physics in Medicine & Biology)

   Abstract Objective.Pathological mineralizations form throughout the body and can be difficult to detect using conventional imaging methods. Color Doppler ultrasound twinkling highlights ∼60% of kidney stones with a rapid color shift and is theorized to arise from crevice microbubbles as twinkling disappears on kidney stones at elevated pressures and scratched acrylic balls in ethanol. Twinkling also sometimes appears on other pathological mineralizations; however, it is unclear whether the etiology of twinkling is the same as for kidney stones.Approach.In this study, five cholesterol, calcium phosphate, and uric acid crystals were grownin vitroand imaged in Doppler mode with a research ultrasound system and L7-4 transducer in water. To evaluate the influence of pressure on twinkling, the same crystals were imaged in a high-pressure chamber. Then, the effect of surface tension on twinkling was evaluated by imaging crystals in different concentrations of surfactant (1%, 2%, 3%, 4%) and ethanol (10%, 30%, 50%, 70%), artificial urine, bovine blood, and a tissue-mimicking phantom.Main results. Results showed that all crystals twinkled in water, with cholesterol twinkling significantly more than calcium phosphate and uric acid. When the ambient pressure was increased, twinkling disappeared for all tested crystals when pressures reached 7 MPa (absolute) and reappeared when returned to ambient pressure (0.1 MPa). Similarly, twinkling across all crystals decreased with surface tension when imaged in the surfactant and ethanol (statistically significant when surface tension <22 mN m⁻¹) and decreased in blood (surface tension = 52.7 mN m⁻¹) but was unaffected by artificial urine (similar surface tension to water). In the tissue-mimicking phantom, twinkling increased for cholesterol and calcium phosphate crystals with no change observed in uric acid crystals.Significance.Overall, these results support the theory that bubbles are present on crystals and cause twinkling, which could be leveraged to improve twinkling for the detection of other pathological mineralizations. 

   more » « less
2. SPORA, a new silver phosphate precipitation protocol for oxygen isotope analysis of small, organic-rich bioapatite samples

   https://doi.org/10.1016/j.chemgeo.2024.122000  

   Larocca_Conte, Gabriele; Lopes, Lauren E; Mine, Aric H; Trayler, Robin B; Kim, Sora L (April 2024, Chemical Geology)

   Isotopic analysis of phosphate oxygen from bones and teeth (18Op/16Op, δ18Op) is a common tool used to investigate modern and ancient ecosystems and their climate. However, existing methods have expanded to use pretreatments for organic removal, require large sample sizes, or require extended precipitation timing. All together, these factors could affect accuracy and precision of δ18Op measurement by promoting the formation of oxygen-bearing or nitrogen-rich contaminants. However, the nature and occurrence of contamination are not fully explored. Here we sought to develop a method of silver phosphate precipitation that tests the effect of different sample treatments and reduced sample sizes while preserving sample isotopic composition. Our protocol (SPORA) precipitates Ag3PO4 crystals from ∼1.5 mg of starting material while purifying phosphate from contaminants, like nitrogen or carbonate. Isolation and purification of phosphate are achieved with an anion exchange resin, followed by precipitation of silver phosphate using an updated silver ammine solution that targets small amounts of phosphate in solution. We used a variety of phosphate oxygen reference materials and biogenic apatite materials, such as modern and fossil specimens with varying collagen content, to test the SPORA protocol and its effects on the resultant phosphate oxygen isotopic composition. Results were then compared to those from another published silver phosphate precipitation method (i.e., Rapid University of Chicago Dilute, Rapid UC). Overall, δ18Op values of standards and biogenic apatites were similar between protocols (R2 = 0.99, p << 0.05). In addition to isotope composition comparisons, UV–Vis spectroscopy and Fourier Transform Infrared (FTIR) analyses discerned phosphate recovery and material composition of crystals precipitated via different protocols, respectively. We found that the resin i) may retain ∼10% of phosphate with no isotopic effects and ii) the SPORA protocol produces Ag3PO4 with more accurate δ18Op measurements by preventing the formation of contaminant oxygen phases, silver oxide (Ag2O) and silver carbonate (Ag2CO3), that confound the phosphate oxygen isotope composition. The SPORA Ag3PO4 precipitation procedure overcomes analytical limitations such as sample size and collagen contamination, conditions that other procedures for δ18Op analysis cannot address simultaneously. The SPORA protocol can be used on a large array of bioapatite materials for paleoecological, paleoclimatic, and archeological applications, while reducing the required sample size and ensuring pure Ag3PO4 for isotopic analysis. 

   more » « less
3. The impact of nitrogen oxides on electrochemical carbon dioxide reduction

   https://doi.org/10.1038/s41467-020-19731-8  

   Ko, Byung Hee; Hasa, Bjorn; Shin, Haeun; Jeng, Emily; Overa, Sean; Chen, Wilson; Jiao, Feng (November 2020, Nature Communications)

   Abstract The electroreduction of carbon dioxide offers a promising avenue to produce valuable fuels and chemicals using greenhouse gas carbon dioxide as the carbon feedstock. Because industrial carbon dioxide point sources often contain numerous contaminants, such as nitrogen oxides, understanding the potential impact of contaminants on carbon dioxide electrolysis is crucial for practical applications. Herein, we investigate the impact of various nitrogen oxides, including nitric oxide, nitrogen dioxide, and nitrous oxide, on carbon dioxide electroreduction on three model electrocatalysts (i.e., copper, silver, and tin). We demonstrate that the presence of nitrogen oxides (up to 0.83%) in the carbon dioxide feed leads to a considerable Faradaic efficiency loss in carbon dioxide electroreduction, which is caused by the preferential electroreduction of nitrogen oxides over carbon dioxide. The primary products of nitrogen oxides electroreduction include nitrous oxide, nitrogen, hydroxylamine, and ammonia. Despite the loss in Faradaic efficiency, the electrocatalysts exhibit similar carbon dioxide reduction performances once a pure carbon dioxide feed is restored, indicating a negligible long-term impact of nitrogen oxides on the catalytic properties of the model catalysts. 

   more » « less
4. The early Cretaceous was cold but punctuated by warm snaps resulting from episodic volcanism

   https://doi.org/10.1038/s43247-024-01389-5  

   Nordt, Lee; Breecker, Daniel; White, Joseph (December 2024, Communications Earth & Environment)

   Abstract The Cretaceous is characterized as a greenhouse climate from elevated atmospheric carbon dioxide concentrations, transgressive seas, and temperate ecosystems at polar paleolatitudes. Here we test the hypothesis that the early Cretaceous was a cold climate state with a new Aptian atmospheric carbon dioxide record from the C₃plant proxy and early Cretaceous sea level curve from stable oxygen isotopes of belemnites and benthic foraminifera. Results show that carbon dioxide concentrations were persistently below 840 ppm during the Aptian, validating recent General Circulation Model simulations of ice sheets on Antarctica at those concentrations. In addition, sea level was estimated to be within the ice sheet window for much of the early Cretaceous prior to the Albian. This background state appears to have been episodically interrupted by Large Igneous Province volcanism followed by long-term carbon burial from weathering. We hypothesize that the early Cretaceous was largely an icehouse punctuated by warm snaps. 

   more » « less
5. Thermal stability of bivalent cation/phosphoinositide domains in model membranes

   https://doi.org/10.1016/j.chemphyslip.2024.105424  

   Paratore, Trevor A; Schmidt, Greta E; Ross, Alonzo H; Gericke, Arne (October 2024, Chemistry and Physics of Lipids)

   As key mediators in a wide array of signaling events, phosphoinositides (PIPs) orchestrate the recruitment of proteins to specific cellular locations at precise moments. This intricate spatiotemporal regulation of protein activity often necessitates the localized enrichment of the corresponding PIP. We investigate the extent and thermal stabilities of phosphatidylinositol-4-phosphate (PI(4)P), phosphatidylinositol-4,5-bisphosphate (PI(4,5)P2 and phosphatidylinositol-3,4,5-trisphosphate (PI(3,4,5)P3) clusters with calcium and magnesium ions. We observe negligible or minimal clustering of all examined PIPs in the presence of Mg2+ ions. While PI(4)P shows in the presence of Ca2+ no clustering, PI(4,5)P2 forms with Ca2+ strong clusters that exhibit stablity up to at least 80◦C. The extent of cluster formation for the interaction of PI(3,4,5)P3 with Ca2+ is less than what was observed for PI(4,5)P2, yet we still observe some clustering up to 80◦C. Given that cholesterol has been demonstrated to enhance PIP clustering, we examined whether bivalent cations and cholesterol synergistically promote PIP clustering. We found that the interaction of Mg2+ or Ca2+ with PI(4)P remains extraordinarily weak, even in the presence of cholesterol. In contrast, we observe synergistic interaction of cholesterol and Ca2+ with PI(4,5)P2. Also, in the presence of cholesterol, the interaction of Mg2+ with PI(4,5)P2 remains weak. PI(3,4,5)P3 does not show strong clustering with cholesterol for the experimental conditions of our study and the interaction with Ca2+ and Mg2+ was not influenced by the presence of cholesterol. 

   more » « less