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Herein we present the preparation of two novel cyclam-based macrocycles (te1pyp and cb-te1pyp), bearing phosphonate-appended pyridine side arms for the coordination of copper(II) ions in the context of 64Cu PET imaging. The two ligands have been prepared through conventional protection-alkylation sequences on cyclam, and their coordination properties have been thoroughly investigated. The corresponding copper complexes have been fully characterized in the solid state (X-ray diffraction analysis) and in solution (EPR and UV-vis spectroscopies). Potentiometric studies combined with spectrometry have also allowed us to determine their thermodynamic stability constants, confirming their high affinity for copper(II) cations. The kinetic inertness of the complexes has been verified by acid-assisted dissociation experiments, enabling their use in 64Cu-PET imaging in mice for the first time. Indeed, the two ligands could be quantitatively radiolabeled under mild conditions, and the resulting 64Cu complexes have demonstrated excellent stability in serum. PET imaging demonstrated a set of features emerging from the combination of picolinates and phosphonate units high stability in vivo, fast clearance from the body via renal elimination, and most interestingly, very low fixation in the liver. This is in contrast with what was observed for monopicolinate cyclam (te1pa), which had a non-negligible accumulation in the liver, owing probably to its different charge and lipophilicity. These results thus pave the way for the use of such phosphonated pyridine chelators for in vivo64Cu-PET imaging.Because H2O2 is thermally unstable, it seems to be difficult to synthesize peroxides at elevated temperatures. We describe here the in situ generation of peroxide that is incorporated in a new uranyl peroxo complex, HT-UPO1, through the hydrothermal treatment of uranyl nitrate at 150 °C in the presence of organic ligands. In this novel process, a highly conjugated aromatic carboxylate linker, (E)-4-[2-(pyridin-4-yl)vinyl]benzoic acid (HPyVB), plays a crucial role by inducing the reduction of oxygen in air to form peroxide in situ and coordinating with uranyl to promote the preferred formation of thermally stable HT-UPO1. This work expands our knowledge on the speciation and chemistry of uranyl peroxide compounds and also sheds light on the possibility of their synthesis under more harsh conditions.Dynamical properties of proteins play an essential role in their function exertion. The elastic network model (ENM) is an effective and efficient tool in characterizing the intrinsic dynamical properties encoded in biomacromolecule structures. The Gaussian network model (GNM) and anisotropic network model (ANM) are the two often-used ENM models. Here, we introduce an equally weighted multiscale ENM (equally weighted mENM) based on the original mENM (denoted as mENM), in which fitting weights of Kirchhoff/Hessian matrixes in mENM are removed since they neglect the details of pairwise interactions. https://www.selleckchem.com/JAK.html Then, we perform its comparison with the mENM, traditional ENM, and parameter-free ENM (pfENM) in reproducing dynamical properties for the six representative proteins whose molecular dynamics (MD) trajectories are available in http//mmb.pcb.ub.es/MoDEL/. In the results, for B-factor prediction, mENM performs best, while the equally weighted mENM performs also well, better than the traditional ENM and pfENM models. As to the dynamical cross-correlation map calculation, mENM performs worst, while the results produced from the equally weighted mENM and pfENM models are close to those from MD trajectories with the latter a little better than the former. Furthermore, encouragingly, the equally weighted mANM displays the best performance in capturing the functional motional modes, followed by pfANM and traditional ANM models, while the mANM fails in all the cases. This work is helpful for strengthening the understanding of the elastic network model and provides a valuable guide for researchers to utilize the model to explore protein dynamics.Active species were introduced into MOFs to prepare multifunctional fluorescent probes by a stepwise postsynthetic modulation strategy. First, two-dimensional HPU-16 (HPU = Henan Polytechnic University; HPU-16 = Zn(L)2(H2O); HL = 2-(5-pyridin-4-yl-5H-[1,2,4]triazol-3-yl)-pyrazine) was transformed into three-dimensional HPU-17 (Zn3(L)2(btc)2(H2O) n ) through a crystal dissolution-recrystallization process. Second, linker replacement was used to introduce -NH2 into the HPU-17 to generate functional NH 2 -HPU-17 via a single-crystal to single-crystal transformation. The functional amino groups caused NH 2 -HPU-17 to show a significant response to ClO-. Because of the interaction of amino groups and ClO-, the fluorescence of NH 2 -HPU-17 gradually changed from blue to yellow-green. More interestingly, NH 2 -HPU-17 could encapsulate Tb3+ and sensitize the visible-emitting characteristic fluorescence of Tb3+ in aqueous solution. Then, newly generated Tb 3+ @NH 2 -HPU-17 could serve as an effective probe for the determination of DPA. This work paves a new way for the design and modulation of ratiometric fluorescence probes for the selective and sensitive detection of special molecules.Deficits in insect-mediated pollination service undermine ecosystem biodiversity and function, human nutrition, and economic welfare. Global pollinator supply continues to decline, while production of pollination-dependent crops increases. Using publicly available price and production data and existing pollination field studies, we quantify economic dependence of United States crops on insect-mediated pollination service at the county level and update existing coefficients of insect dependence of sample crops when possible. Economic value dependent on pollination service totals 34.0 billion USD in 2012. Twenty percent of US counties produce 80% of total economic value attributable to insect pollinators. We compile county-level data and consider the spatial relationship between economic value dependent on insect-mediated pollination, region-specific forage suitability, and crop-specific agricultural areas within US landscapes. We identify vulnerable, highly dependent areas where habitat for wild pollinators has been reduced.
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