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The use of a laser to cut or drill ice has been proposed and demonstrated multiple times in previous decades as a novel, but never adopted, machining tool in glaciology and paleoclimate studies. However, with the rapid development of high power fiber-laser technology over the past few decades, it is timely to perform further studies using this new tool. An investigation is made herein on the cutting of ice using a Yb-doped fiber laser emitting at a wavelength of 1070 nm, the most extensively developed and highest power fiber laser technology, in pulsed and continuous-wave operation. Visible-light observations of clear tap water ice samples, moving at a constant velocity relative to a pulsed laser beam, demonstrate a linear relationship between the duration of a millisecond-range laser pulse and the depth of the meltwater-free cut formed in response. Thermal imaging of the irradiated face shows that peripheral heating trends linearly for pulse lengths greater than 5 ms. A comparison of pulse trains with a constant time-averaged power suggests that shorter pulses are advantageous in slot-cutting efficiency and in minimizing visible alterations in the surrounding ice. These results demonstrate the viability of powerful fiber-compatible lasers as a tool for ice sample retrieval and processing. 

A new supramolecular tecton is designed that has the unique potential of assembling well-ordered supramolecular complexes by forming five directional hydrogen bonds at a time. It ensures an ordered distribution of inorganic halometallate anions. 

Deferasirox (Def), an orally administered iron‐chelating drug, has drawn significant interest in repurposing for anticancer application due to the elevated Fe demand by cancer cells. But there are also concerns about its severe off target health effects. Herein Cu(II) binding is studied as a potential off target interaction. The aqueous solution stability and speciation of the ternary complex Cu(Def)(pyridine) was studied by UV‐Vis and EPR spectroscopy, ESI‐mass spectrometry, and cyclic voltammetry under physiologically relevant conditions. The complex is observed to be a redox active, mononuclear Cu(II) complex in square planar geometry. UV‐Vis spectroscopy demonstrates that at pH 7.4 the complex is quite stable (ϵ337nm =10,820 M^−1cm^−1) with a log K=16.65±0.1. Cu scavenging from the Cu transporters ceruloplasmin and albumin was also studied. Def does not inhibit ceruloplasmin activity but forms a ternary Cu(II) complex at the bovine serum albumin ATCUN site. Cu(Def)(py) displays potent but nonselective cytotoxicity against A549 cancer and MRC‐5 noncancer lung cells but the potency of the ternary protein complex was more moderate. This work elucidates potential Def toxicity from Cu complexation in the body but also cytotoxic synergy between the metal and chelator that informs on new drug design directions. 

ABSTRACT Everywhere, pests and pathogens evolve resistance to our control efforts, impairing human health and welfare. Developing sustainable solutions to this problem requires working with evolved immune and ecological systems, rather than against these evolutionary forces. We advocate a transdisciplinary approach to resistance based on an evolutionary foundation informed by the concepts of integrated pest management and One Health. Diverse, multimodal management approaches create a more challenging environment for the evolution of resistance. Given our permanent evolutionary and ecological relationships with pests and pathogens, responses to most biological threats to health and agriculture should seek sustainable harm reduction rather than eradication. 

Biopyrrin pigments, which result from the degradation of heme in biological settings, feature three or two pyrrole rings and characteristic pyrrolin-2-one termini. These scaffolds serve as redox-active ligands and electron reservoirs in coordination compounds. Tripyrrin-1,14-dione coordinates divalent transition metals as a dianionic ligand hosting a delocalized radical. Herein, we report the synthesis and characterization of palladium(II) and platinum(II) tripyrrindione complexes featuring a primary amine (i.e., aniline, tert-butylamine, 1,2-ethylenediamine) at the fourth coordination site within square planar geometries. Interligand hydrogen-bonding interactions are observed between the coordinated amine and the carbonyl groups on the tripyrrindione scaffold. Notably, 1,2-ethylenediamine is employed to link two Pt(II) tripyrrindione complexes. As revealed by optical absorption and electron paramagnetic resonance (EPR) spectroscopy, all resulting complexes present ligand-based radicals that are stable at room temperature and when exposed to air. Spin pairing through multicenter interactions leads to [Formula: see text]-dimerization of the tripyrrindione radicals and a decrease in the EPR signal at low temperatures. Electrochemical measurements indicate that the ligand system undergoes quasi-reversible one-electron oxidation and reduction, thus confirming the ability of tripyrrindione to form square planar complexes in three different redox states. 

The tripyrrin-1,14-dione biopyrrin, which shares the scaffold of several naturally occurring heme metabolites, is a redox-active platform for metal coordination. We report the synthesis of square planar platinum( ii ) tripyrrindiones, in which the biopyrrin binds as a tridentate radical and the fourth coordination position is occupied by either aqua or tert -butyl isocyanide ligands. These complexes are stable through chromatographic purification and exposure to air. Electron paramagnetic resonance (EPR) data and density functional theory (DFT) analysis confirm that the spin density is located predominantly on the tripyrrindione ligand. Pancake bonding in solution between the Pt( ii ) tripyrrindione radicals leads to the formation of diamagnetic π dimers at low temperatures. The identity of the monodentate ligand ( i.e. , aqua vs . isocyanide) affects both the thermodynamic parameters of dimerization and the tripyrrindione-based redox processes in these complexes. Isolation and structural characterization of the oxidized complexes revealed stacking of the diamagnetic tripyrrindiones in the solid state as well as a metallophilic Pt( ii )−Pt( ii ) contact in the case of the aqua complex. Overall, the properties of Pt( ii ) tripyrrindiones, including redox potentials and intermolecular interactions in solution and in the solid state, are modulated through easily accessible changes in the redox state of the biopyrrin ligand or the nature of the monodentate ligand.