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991.
Laura Machin Martin Piontek Sara Todhe Katrin Staniek Lianet Monzote Werner Fudickar Torsten Linker Lars Gille 《Molecules (Basel, Switzerland)》2022,27(20)
Leishmaniasis is a vector-borne disease caused by protozoal Leishmania parasites. Previous studies have shown that endoperoxides (EP) can selectively kill Leishmania in host cells. Therefore, we studied in this work a set of new anthracene-derived EP (AcEP) together with their non-endoperoxidic analogs in model systems of Leishmania tarentolae promastigotes (LtP) and J774 macrophages for their antileishmanial activity and selectivity. The mechanism of effective compounds was explored by studying their reaction with iron (II) in chemical systems and in Leishmania. The correlation of structural parameters with activity demonstrated that in this compound set, active compounds had a LogPOW larger than 3.5 and a polar surface area smaller than 100 Å2. The most effective compounds (IC50 in LtP < 2 µM) with the highest selectivity (SI > 30) were pyridyl-/tert-butyl-substituted AcEP. Interestingly, also their analogs demonstrated activity and selectivity. In mechanistic studies, it was shown that EP were activated by iron in chemical systems and in LtP due to their EP group. However, the molecular structure beyond the EP group significantly contributed to their differential mitochondrial inhibition in Leishmania. The identified compound pairs are a good starting point for subsequent experiments in pathogenic Leishmania in vitro and in animal models. 相似文献
992.
Iron is the most abundant mineral in the human body and plays essential roles in sustaining life, such as the transport of oxygen to systemic organs. The Fenton reaction is the reaction between iron and hydrogen peroxide, generating hydroxyl radical, which is highly reactive and highly toxic to living cells. “Ferroptosis”, a programmed cell death in which the Fenton reaction is closely involved, has recently received much attention. Furthermore, various applications of the Fenton reaction have been reported in the medical and nutritional fields, such as cancer treatment or sterilization. Here, this review summarizes the recent growing interest in the usefulness of iron and its biological relevance through basic and practical information of the Fenton reaction and recent reports. 相似文献
993.
Dr. Peter G. N. Neate Dr. Mark D. Greenhalgh Dr. William W. Brennessel Dr. Stephen P. Thomas Prof. Dr. Michael L. Neidig 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17218-17224
N,N,N′,N′-Tetramethylethylenediamine (TMEDA) has been one of the most prevalent and successful additives used in iron catalysis, finding application in reactions as diverse as cross-coupling, C−H activation, and borylation. However, the role that TMEDA plays in these reactions remains largely undefined. Herein, studying the iron-catalyzed hydromagnesiation of styrene derivatives using TMEDA has provided molecular-level insight into the role of TMEDA in achieving effective catalysis. The key is the initial formation of TMEDA–iron(II)–alkyl species which undergo a controlled reduction to selectively form catalytically active styrene-stabilized iron(0)–alkyl complexes. While TMEDA is not bound to the catalytically active species, these active iron(0) complexes cannot be accessed in the absence of TMEDA. This mode of action, allowing for controlled reduction and access to iron(0) species, represents a new paradigm for the role of this important reaction additive in iron catalysis. 相似文献
994.
Jakob Steube Dipl.-Chem. Lukas Burkhardt Ayla Päpcke Johannes Moll Dr. Peter Zimmer Dr. Roland Schoch Dr. Christoph Wölper Prof. Dr. Katja Heinze Prof. Dr. Stefan Lochbrunner Prof. Dr. Matthias Bauer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(51):11826-11830
The complex class [Fe(N^N^C)(N^N^N)]+ with an Earth-abundant metal ion has been repeatedly suggested as a chromophore and potential photosensitizer on the basis of quantum chemical calculations. Synthesis and photophysical properties of the parent complex [Fe(pbpy)(tpy)]+ (Hpbpy=6-phenyl-2,2′-bipyridine and tpy=2,2′:6′,2′′-terpyridine) of this new chromophore class are now reported. Ground-state characterization by X-ray diffraction, electrochemistry, spectroelectrochemistry, UV/Vis, and X-ray spectroscopy in combination with DFT calculations proves the high impact of the cyclometalating ligand on the electronic structure. The photophysical properties are significantly improved compared to the prototypical [Fe(tpy)2]2+ complex. In particular, the metal-to-ligand absorption extends into the near-IR and the 3MLCT lifetime increases by 5.5, whereas the metal-centered excited triplet state is very short-lived. 相似文献
995.
An efficient and robust water oxidation catalyst based on abundant and cheap materials is the key to converting solar energy into fuels through artificial photosynthesis for the future of humans. The development of molecular water oxidation catalysts (MWOCs) is a smart way to achieve promising catalytic activity, thanks to the clear structures and catalytic mechanisms of molecular catalysts. Efficient MWOCs based on noble‐metal complexes, for example, ruthenium and iridium, have been well developed over the last 30 years; however, the development of earth‐abundant metal‐based MWOCs is very limited and still challenging. Herein, the promising prospect of iron‐based MWOCs is highlighted, with a comprehensive summary of previously reported studies and future research focus in this area. 相似文献
996.
Dr. David Kuter Dr. Liliana Suárez Dr. Erin L. Dodd Dr. Bruce C. Noll Prof. Dr. Peter W. Stephens Prof. Dr. D. Scott Bohle 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(17):4373-4378
Treating deuterohemin, chloro(deuteroporphyrinato)iron(III), with a non-coordinating base in DMSO/methanol allows for the isolation of [(deuteroporphyrinato)iron(III)]2, deuterohematin anhydride (DHA), an analogue of malaria pigment, the natural product of heme detoxification by malaria. The structure of DHA obtained from this solvent system has been solved by X-ray powder diffraction analysis and displays many similarities, yet important structural differences, to malaria pigment. Most notably, a water molecule of solvation occupies a notch created by the propionate side chains and stabilizes a markedly bent propionate ligand coordinated with a long Fe−O bond, and a carboxylate cluster associated with water molecules is generated. Together, these features account for its increased solubility and more open structure, with an increased porphyrin–porphyrin separation. The IR spectroscopic signature associated with this structure also accounts for the strong IR band at 1587 cm−1 seen for many amorphous preparations of synthetic malaria pigment, and it is proposed that stabilizing these structures may be a new objective for antimalarial drugs. The important role of the vinyl substituents in this biochemistry is further demonstrated by the structure of deuterohemin obtained by single-crystal X-ray diffraction analysis. 相似文献
997.
Dr. Ian M. Riddlestone Philippe Weis Dr. Arthur Martens Marcel Schorpp Dr. Harald Scherer Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(45):10546-10551
Upon coordinating P4 to electron poor cyclopentadienyl-iron cations, the average P−P bond distances shrink and the respective P4 breathing mode in the Raman spectra (600 cm−1, P4, free) is blueshifted by >40 cm−1 in [CpFe(CO)(L)(η1-P4)]+ cations (L=CO or PPh3). Analysis suggests that this corresponds to an umpolung of the bonding from more phosphidic in the known, electron-rich systems to more phosphonium-like in the reported electron-poor versions. This may open new functionalization pathways for white phosphorus P4. 相似文献
998.
999.
《Mendeleev Communications》2022,32(3):323-326
Nanoparticles of ε-Fe2O3 were obtained by template synthesis in the pores of opal-like matrices. The maximum content of ε-Fe2O3 is achieved upon calcination at 1000 °C for 2–4 h. The content of ε-Fe2O3 in a mixture of modifications of iron oxides reaches 80–90%, which is confirmed by the data of X-ray diffraction analysis, Mössbauer spectroscopy and magnetometry experiments. 相似文献
1000.
Stefan Lülf Luxuan Guo Dr. Tobias Parchomyk Prof. Dr. Jeremy N. Harvey Prof. Dr. Konrad Koszinowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(65):e202202030
Despite its practical importance, organoiron chemistry remains poorly understood due to its mechanistic complexity. Here, we focus on the oxidative addition of organyl halides to phenylferrate anions in the gas phase. By mass-selecting individual phenylferrate anions, we can determine the effect of the oxidation state, the ligation, and the nuclearity of the iron complex on its reactions with a series of organyl halides RX. We find that Ph2Fe(I)− and other low-valent ferrates are more reactive than Ph3Fe(II)−; Ph4Fe(III)− is inert. The coordination of a PPh3 ligand or the presence of a second iron center lower the reactivity. Besides direct cross-coupling reactions resulting in the formation of RPh, we also observe the abstraction of halogen atoms. This reaction channel shows the readiness of organoiron species to undergo radical-type processes. Complementary DFT calculations afford further insight and rationalize the high reactivity of the Ph2Fe(I)− complex by the exothermicity of the oxidative addition and the low barriers associated with this reaction step. At the same time, they point to the importance of changes of the spin state in the reactions of Ph3Fe(II)−. 相似文献