Article
Environmental Sciences
John T. Sullivan, Ryan M. Stauffer, Anne M. Thompson, Maria A. Tzortziou, Christopher P. Loughner, Carolyn E. Jordan, Joseph A. Santanello
Summary: Coastal areas are densely populated and economically important regions. Protecting the health of humans and ecosystems in these areas and understanding the impacts of environmental stressors like air pollution is crucial.
Article
Geosciences, Multidisciplinary
Brian Zambri, Douglas E. Kinnison, Susan Solomon
Summary: Heterogeneous halogen chemistry plays a dominant role in driving changes in polar chemical composition and ozone depletion. This study compared NO2 measurements from the Stratospheric Aerosol and Gas Experiment III (SAGE3m) with simulations from a coupled climate-chemistry model to characterize and quantify subpolar heterogeneous halogen chemistry. Results showed that heterogeneous chemistry significantly influences the chemical composition of the subpolar lower stratosphere in the Southern Hemisphere spring, highlighting the importance of analyzing distribution functions in understanding chemical processes.
GEOPHYSICAL RESEARCH LETTERS
(2021)
Article
Geosciences, Multidisciplinary
Qi Tang, Michael J. Prather, Juno Hsu, Daniel J. Ruiz, Philip J. Cameron-Smith, Shaocheng Xie, Jean-Christophe Golaz
Summary: The new ozone chemistry module O3v2 implemented in E3SMv1 improves simulation performance in terms of stratospheric column ozone, although not as good as the UCI CTM. It enables a more accurate representation of ozone in the lowermost stratosphere and provides key diagnostics for stratosphere-troposphere exchange flux.
GEOSCIENTIFIC MODEL DEVELOPMENT
(2021)
Article
Chemistry, Inorganic & Nuclear
Chunyang Li, Anne-Doriane Manick, Jian Yang, David Givaudan, Bohdan Biletskyi, Sabine Michaud-Chevalier, Jean-Pierre Dutasta, Damien Herault, Xavier Bugaut, Bastien Chatelet, Alexandre Martinez
Summary: Chloroazaphosphatranes have been identified as a new class of halogen bond donors with modulable synthesis, showing comparable binding abilities to conventional iodine-based monodentate XB receptors and a relationship with the basicity of Verkade superbases. The strength of the XB interaction was revealed by the Delta delta(P-31) NMR shift observed in CD2Cl2 solution in the presence of triethylphosphine oxide (TEPO), expanding the repertory of XB motifs based on C-Ar-I bonds.
INORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Colleen B. Baublitz, Arlene M. Fiore, Sarah M. Ludwig, Julie M. Nicely, Glenn M. Wolfe, Roisin Commane, Michael J. Prather, Daniel C. Anderson, Gustavo Correa, Bryan N. Duncan, Melanie Follette- Cook, Daniel M. Westervelt, Ilann Bourgeois, William H. Brune, T. Paul Bui, Joshua P. Digangi, Glenn S. Diskin, Samuel R. Hall, Kathryn Mckain, David O. Miller, Jeff Peischl, Alexander B. Thames, Chelsea R. Thompson, Kirk Ullmann, Steven C. Wofsy
Summary: ProxyOH is developed as an observation-based proxy for spatial variations in hydroxyl radical (OH) in the remote marine troposphere. It scales linearly with in situ [OH] spatial variations and can be used to map OH variations over a large area.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2023)
Article
Chemistry, Multidisciplinary
Lu Liu, Seyfeddine Rahali, Remi Maurice, Cecilia Gomez Pech, Gilles Montavon, Jean-Yves Le Questel, Jerome Graton, Julie Champion, Nicolas Galland
Summary: Halogen bonding is recognized as a valuable non-covalent interaction in various fields for intermolecular recognition control. The pK(BAtI) basicity scale quantifies the halogen bonding strength of astatine as the most potent halogen-bond donor element, with sulphur bases showing the highest AtI basicity. The scale can be used to enhance binding of carrier agents for targeted radionuclide therapy using At-211.
Article
Environmental Sciences
Julian Villamayor, Fernando Iglesias-Suarez, Carlos A. Cuevas, Rafael P. Fernandez, Qinyi Li, Marta Abalos, Ryan Hossaini, Martyn P. Chipperfield, Douglas E. Kinnison, Simone Tilmes, Jean-Francois Lamarque, Alfonso Saiz-Lopez
Summary: In contrast to the overall recovery of stratospheric ozone, recent observations show ongoing net ozone depletion in the tropical lower stratosphere. This depletion is thought to be driven by dynamical transport accelerated by global warming, while chemical processes have been considered unimportant. However, using a chemistry-climate model, researchers demonstrate that halogenated ozone-depleting very short-lived substances (VSLS) chemistry may account for a significant portion of this observed ozone loss. They predict that the contribution of VSLS to ozone depletion will persist throughout the twenty-first century in the tropical lower stratosphere, emphasizing the need for mitigation strategies to preserve the ozone layer in low latitudes.
NATURE CLIMATE CHANGE
(2023)
Article
Chemistry, Organic
Christoph J. Vonnemann, David Bulfield, Elric Engelage, Stefan M. Huber
Summary: A tweezer-like halogen bonding receptor capable of binding a neutral molecule (DABCO) from both sides is introduced. The coordination of DABCO and chloride ions is investigated in the solid state and in solution, and DFT calculations are used to explain the findings. This is the first molecular tweezer based solely on halogen bonding, which coordinates bifunctional substrates in a pincer-like fashion.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Jonas Matern, Nils Baeumer, Gustavo Fernandez
Summary: Halogens play a crucial role in natural processes and synthetic materials due to their unique physicochemical properties. Recent research has focused on the influence of chlorine ligands on molecular packing and complex pathway phenomena of metal complexes. The study reveals different supramolecular polymerization pathways influenced by halogen nature, with chlorine, bromine, and iodine exhibiting distinct behaviors in nonpolar media.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Meteorology & Atmospheric Sciences
David O. Miller, William H. Brune
Summary: Understanding the chemistry of OH and HO2 in the atmosphere is crucial for studying the impact of human activity on atmospheric composition and climate. Comparing observed and modeled data from the Penn State Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS), it was found that the oxidation chemistry in most of the free troposphere is well understood, but specific environments such as cities, forests, and pollution plumes can be influenced by the model's chemical mechanism and data set size.
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES
(2022)
Review
Chemistry, Multidisciplinary
Binoy K. Saha, Ragima V. P. Veluthaparambath, Vibha G. Krishna
Summary: Halogen interaction is a controversial and important topic in crystal engineering and supramolecular chemistry, involving F, Cl, Br, and I. Lighter and heavier halogens behave differently, and the nature of the interaction depends on the atom covalently bonded to the halogens. This review discusses different types of homo-halogen, hetero-halogen, and halogen-halide interactions, their natures, preferred geometries, as well as various motifs and interchangeability with other functional groups. The review also mentions important applications of halogen interactions.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Irina S. Aliyarova, Elena Yu. Tupikina, Natalia S. Soldatova, Daniil M. Ivanov, Pavel S. Postnikov, Mekhman Yusubov, Vadim Yu. Kukushkin
Summary: This study investigated the halogen bonding interactions in diaryliodonium tetrachloroaurates and found that gold(III) atoms exhibit nucleophilicity in these interactions, despite their substantial positive charge.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Shilin Yu, Jas S. Ward, Khai-Nghi Truong, Kari Rissanen
Summary: Neutral halogen-bonded O-I-N complexes were prepared using carbonyl hypoiodites and aromatic organic bases. Modulating the Lewis basicity led to halogen-bonded complexes where the O-I...N bond transforms more into an asymmetric ion pair. X-ray analyses and NMR studies confirmed the geometries of the complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Adam N. Barrett, Callum R. Woof, Christopher A. Goult, Danila Gasperini, Mary F. Mahon, Ruth L. Webster
Summary: The hydrogen/halogen exchange of phosphines has been utilized to establish a method for the synthesis of cyclopolyphosphines. The use of catalytic quantities of iron(III) acetylacetonate significantly improves conversion and selectivity for specific ring sizes. Investigation into the reactivity of Fe(acac)(3) suggests that the iron species acts as a sink for the hydrochloric acid byproduct of the reaction.
INORGANIC CHEMISTRY
(2021)
Article
Crystallography
Dmitriy F. Mertsalov, Rosa M. Gomila, Vladimir P. Zaytsev, Mikhail S. Grigoriev, Eugeniya Nikitina, Fedor Zubkov, Antonio Frontera
Summary: This paper reports the synthesis and X-ray characterization of two derivatives containing the four most abundant halogen atoms, aiming to study Ha···Ha halogen bonding interactions. The heavier halogen atoms exhibit anisotropy of electron density, leading to the formation of multiple Ha···Ha contacts in the solid state. The halogen bonding assemblies in both compounds were analyzed using various methods such as DFT calculations, MEP surfaces, QTAIM, NCIplot, and ELF.
Article
Multidisciplinary Sciences
Carlos A. Cuevas, Rafael P. Fernandez, Douglas E. Kinnison, Qinyi Li, Jean-Francois Lamarque, Tarek Trabelsi, Joseph S. Francisco, Susan Solomon, Alfonso Saiz-Lopez
Summary: This study found that the injection of iodine into the Antarctic stratosphere has a significant impact on the formation and development of the Antarctic ozone hole, especially in spring. The inclusion of iodine can advance the formation of the ozone hole and delay its closure, increasing the area and mass deficit of the hole.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Editorial Material
Chemistry, Physical
Ibon Alkorta, John M. C. Plane, Jose Elguero, Juan Z. Davalos, A. Ulises Acuna, Alfonso Saiz-Lopez
Summary: In this study, the authors address the argument raised in a previous comment regarding the energy of the NO3 radical and its impact on the reaction profiles of the NO3 radical with various compounds. They used 49 DFT functionals to obtain the optimized geometry of the NO3 radical and compared the results from different functionals. The thermodynamic values of three reactions were calculated using the functionals with smaller errors and compared with experimental data. The authors also recalculated the barriers of the reactions using these functionals and observed a difference of 10.5 kJ mol(-1) compared to the results obtained with the M08HX functional.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Environmental Sciences
Ernesto Pino-Cortes, Katherine Gomez, Fernando Gonzalez Taboada, Joshua S. Fu, Alfonso Saiz-Lopez, Juan Hofer
Summary: This study describes a method to adapt the CAMS-GLOB-OCE dataset for use in the preprocessor software SMOKE. The method involves updating file attributes and bilinear interpolation of compound emission fields. Testing the method with halocarbon and DMS emissions fields around Antarctica showed its potential for including marine emissions in air quality studies.
AIR QUALITY ATMOSPHERE AND HEALTH
(2023)
Article
Multidisciplinary Sciences
Charel Wohl, Qinyi Li, Carlos A. Cuevas, Rafael P. Fernandez, Mingxi Yang, Alfonso Saiz-Lopez, Rafel Simo
Summary: Measurements of benzene and toluene in the remote Southern Ocean and the Arctic marginal ice zone suggest a marine biogenic source. Calculated emission fluxes for benzene and toluene in the Southern Ocean were 0.023 +/- 0.030 and 0.039 +/- 0.036 μmol m-2 day-1, while in the Arctic, they were 0.023 +/- 0.028 and 0.034 +/- 0.041 μmol m-2 day-1, respectively. These emissions, previously overlooked, have a significant impact on secondary organic aerosol mass concentrations, particularly over the Southern Ocean.
Article
Geosciences, Multidisciplinary
Wuhu Feng, John M. C. Plane, Martyn P. P. Chipperfield, Alfonso Saiz-Lopez, Jean-Paul Booth
Summary: We used a 3-D Whole Atmospheric Community Climate Model to examine the effects of small satellite launches with an iodine propulsion system on stratospheric ozone depletion. The model suggests that the emissions from these satellites can reach the troposphere within a 4-year timescale. In the base case scenario of 40,000 small satellite launches per year, the impact on global stratospheric ozone is negligible, while a 100-fold increase in launch rate could lead to significant ozone depletion over the polar regions.
GEOPHYSICAL RESEARCH LETTERS
(2023)
Article
Geosciences, Multidisciplinary
Delia Segato, Alfonso Saiz-Lopez, Anoop Sharad Mahajan, Feiyue Wang, Juan Pablo Corella, Carlos Alberto Cuevas, Tobias Erhardt, Camilla Marie Jensen, Chantal Zeppenfeld, Helle Astrid Kjaer, Clara Turetta, Warren Raymond Lee Cairns, Carlo Barbante, Andrea Spolaor
Summary: According to ice-core data and atmospheric chemistry modeling, deposition of mercury onto the Greenland Ice Sheet increased during the transition from the Last Glacial Termination to the early Holocene epoch. This increase was associated with regional climate warming and the retreat of sea ice, driven by oceanic mercury evaporation and atmospheric bromine. The findings suggest that climate change may contribute to higher mercury levels in Arctic ecosystems.
Article
Meteorology & Atmospheric Sciences
Javier A. Barrera, Douglas E. Kinnison, Rafael P. Fernandez, Jean-Francois Lamarque, Carlos A. Cuevas, Simone Tilmes, Alfonso Saiz-Lopez
Summary: This study investigates the impact of anthropogenically amplified natural emissions of halogenated species on tropospheric ozone under pre-industrial and present-day atmospheric conditions using the CAM-Chem model. The results show that natural halogens have a slightly greater effect on tropospheric ozone depletion in pre-industrial conditions, with bromine playing a more significant role in this period.
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES
(2023)
Article
Multidisciplinary Sciences
Alfonso Saiz-Lopez, Rafael P. P. Fernandez, Qinyi Li, Carlos A. A. Cuevas, Xiao Fu, Douglas E. E. Kinnison, Simone Tilmes, Anoop S. S. Mahajan, Juan Carlos Gomez Martin, Fernando Iglesias-Suarez, Ryan Hossaini, John M. C. Plane, Gunnar Myhre, Jean-Francois Lamarque
Summary: Observational evidence suggests that ocean-emitted short-lived halogens have a widespread presence in the global atmosphere. These compounds, both naturally emitted and anthropogenically amplified, have a significant cooling effect on Earth's radiative balance. This effect has increased since pre-industrial times and is projected to change further in the future.
Article
Geosciences, Multidisciplinary
Chao Yan, Yee Jun Tham, Wei Nie, Men Xia, Haichao Wang, Yishuo Guo, Wei Ma, Junlei Zhan, Chenjie Hua, Yuanyuan Li, Chenjuan Deng, Yiran Li, Feixue Zheng, Xin Chen, Qinyi Li, Gen Zhang, Anoop S. Mahajan, Carlos A. Cuevas, Dan Dan Huang, Zhe Wang, Yele Sun, Alfonso Saiz-Lopez, Federico Bianchi, Veli-Matti Kerminen, Douglas R. Worsnop, Neil M. Donahue, Jingkun Jiang, Yongchun Liu, Aijun Ding, Markku Kulmala
Summary: This study reveals that the activation of nocturnal nitrogen chemistry during severe haze pollution contributes to the formation of fine particulate matter despite the reduction in nitrogen oxides (NOx) emissions. The heterogeneous reactions of dinitrogen pentoxide (N2O5) dominate the formation of particulate nitrate (pNO(3)(-)) and provide a source of chlorine radicals, leading to the oxidation of volatile organic compounds and the formation of oxygenated organic molecules and secondary organic aerosol.
Article
Geosciences, Multidisciplinary
Cyril Caram, Sophie Szopa, Anne Cozic, Slimane Bekki, Carlos A. Cuevas, Alfonso Saiz-Lopez
Summary: The atmospheric chemistry of halogenated species plays a significant role in the global chemical sink of tropospheric ozone and affects the oxidising capacity of the troposphere, notably by influencing the atmospheric lifetime of methane. This study implemented tropospheric sources and chemistry of halogens in the LMDZ-INCA model and evaluated their effects on the tropospheric ozone budget. The results showed that the model satisfactorily simulated the impact of halogens on the photo-oxidising system, with a significant decrease in ozone burden, OH, and NOx when tropospheric halogens were considered.
GEOSCIENTIFIC MODEL DEVELOPMENT
(2023)
Article
Geography, Physical
Francois Burgay, Rafael Pedro Fernandez, Delia Segato, Clara Turetta, Christopher S. Blaszczak-Boxe, Rachael H. Rhodes, Claudio Scarchilli, Virginia Ciardini, Carlo Barbante, Alfonso Saiz-Lopez, Andrea Spolaor
Summary: Based on a 210-year bromine record, this study finds that the bromine signal in ice at Dome C in East Antarctica is preserved and not influenced by variations in ultraviolet radiation. However, due to limited satellite measurements and low sea-ice variability in the past 30 years, the effectiveness of bromine enrichment as a proxy for past sea-ice reconstructions at Dome C is still uncertain.
Review
Environmental Sciences
Liselotte Tinel, Jonathan Abbatt, Eric Saltzman, Anja Engel, Rafael Fernandez, Qinyi Li, Anoop S. Mahajan, Melinda Nicewonger, Gordon Novak, Alfonso Saiz-Lopez, Stephanie Schneider, Shanshan Wang
Summary: Ocean biogeochemistry plays a crucial role in atmospheric chemistry by producing and consuming organic compounds and trace gases. Researchers have made progress in understanding the impact of ocean biogeochemistry on gas-phase atmospheric chemistry, but there are still unresolved issues and future research directions.
ELEMENTA-SCIENCE OF THE ANTHROPOCENE
(2023)
Article
Chemistry, Physical
Juan Carlos Gomez Martin, Thomas R. Lewis, Kevin M. Douglas, Mark A. Blitz, Alfonso Saiz-Lopez, John M. C. Plane
Summary: The rate constants of many reactions in atmospheric chemistry of mercury are still unknown. This study conducted the first experimental determination of the rate constant of the gas-phase reaction between the HgBr radical and ozone, as well as the rate constants of two reduction side reactions. The results support the notion that the main atmospheric fate of HgBr is reaction with ozone to form BrHgO.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Environmental Sciences
Hisahiro Takashima, Yugo Kanaya, Saki Kato, Martina M. Friedrich, Michel Van Roozendael, Fumikazu Taketani, Takuma Miyakawa, Yuichi Komazaki, Carlos A. Cuevas, Alfonso Saiz-Lopez, Takashi Sekiya
Summary: Iodine compounds can destroy ozone and form aerosols, affecting the global radiative balance. This study reports measurements of iodine monoxide concentrations from the Arctic to the Southern Hemisphere, with the highest concentrations observed over the Western Pacific warm pool. A negative correlation was found between ozone and iodine monoxide, suggesting that there are O-3-independent pathways that contribute to ozone loss. The daily ozone loss rate related to iodine in the Western Pacific warm pool is as high as approximately 2 ppbv, indicating a potential impact of climate change on marine atmospheric chemistry.
ATMOSPHERIC CHEMISTRY AND PHYSICS
(2022)
Article
Environmental Sciences
Zhiyuan Gao, Nicolas-Xavier Geilfus, Alfonso Saiz-Lopez, Feiyue Wang
Summary: The episodic buildup of reactive bromine species over sea ice and snowpack in the springtime Arctic leads to concurrent depletion of ozone and gaseous elemental mercury. However, there are significant knowledge gaps regarding the cryo-photochemical processes and meteorological conditions causing these events. A mesocosm study in Canada successfully reproduced ozone and mercury depletion events, providing new insight into these processes and their sensitivities to climate change.
ATMOSPHERIC CHEMISTRY AND PHYSICS
(2022)
Review
Chemistry, Multidisciplinary
Yikuan Liu, Xiaona Liu, An Su, Chengtao Gong, Shenwei Chen, Liwei Xia, Chengwei Zhang, Xiaohuan Tao, Yue Li, Yonghe Li, Tulai Sun, Mengru Bu, Wei Shao, Jia Zhao, Xiaonian Li, Yongwu Peng, Peng Guo, Yu Han, Yihan Zhu
Summary: Covalent organic frameworks are crystalline porous materials with designable structures and functions, which can acquire multifunctionalities and have versatile applications in gas separation/storage, catalysis, and optoelectronic devices.
CHEMICAL SOCIETY REVIEWS
(2024)
Review
Chemistry, Multidisciplinary
Heyang Zhang, Jo Vandesompele, Kevin Braeckmans, Stefaan C. De Smedt, Katrien Remaut
Summary: Gene therapy has the potential to revolutionize the treatment of inherited and acquired diseases, but its success rate is currently limited. This review focuses on the obstacles faced by gene therapies in the human body, such as nucleic acid degradation by abundant nucleases, and discusses strategies to reduce degradation and methods to assess nucleic acid integrity.
CHEMICAL SOCIETY REVIEWS
(2024)
Review
Chemistry, Multidisciplinary
Chenxi Duan, Chunming Cui
Summary: Low valent group 14 compounds with diazaborolyl substituents exhibit unique structures and reactivity due to the combination of sigma-electron donation and steric hindrance. The modulation of the HOMO-LUMO gap by the diazaborolyl substituents results in novel reaction patterns in the activation of small molecules and inert chemical bonds.
CHEMICAL SOCIETY REVIEWS
(2024)
Review
Chemistry, Multidisciplinary
David E. Salazar Marcano, Nada D. Savic, Kilian Declerck, Shorok A. M. Abdelhameed, Tatjana N. Parac-Vogt
Summary: Metal-oxo clusters have great potential in various fields and can react with biomolecules, making them promising for applications in disease treatment and energy development. They can also be used in the development of inorganic drugs and bioanalytical tools.
CHEMICAL SOCIETY REVIEWS
(2024)
Review
Chemistry, Multidisciplinary
Lana K. Moree, Logan A. V. Faulkner, James D. Crowley
Summary: In this tutorial review, the general methods for synthesizing heterometallic metallosupramolecular architectures (MSAs), specifically heterometallic cages, are examined. The intrinsic properties and potential applications of these cages as host-guest systems and reaction catalysts are discussed.
CHEMICAL SOCIETY REVIEWS
(2024)