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A stimulus-responsive guest-containing spiropyran and viologen unit assembles with a 24-membered crown ether into a stable host-guest complex displaying a partially threaded geometry. Acid addition induces guest transformation to a merocyanine species activating a second recognition site, suitable for the formation of a pseudorotaxane. The simultaneous presence of two recognition sites produces a small-amplitude macrocycle shuttling motion, from the viologen to the merocyanine moiety. Base addition returns the guest to its spiropyran form, and concurrently the translation motion stops.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Ruthenium chemistry and applications in catalytic olefin metathesis based on N-phosphino-functionalized N-heterocyclic carbene ligands (NHCPs) are presented. Alkyl NHCP Ru coordination chemistry is described, and access to several potential synthetic precursors for ruthenium alkylidene complexes is outlined, incorporating both trimethylsilyl and phenyl alkylidenes. The Ru alkylidene complexes are evaluated as potential olefin metathesis catalysts and were shown to behave in a latent fashion. They displayed catalytic activity at elevated temperatures for both ring closing metathesis and ring opening metathesis polymerization.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The genome of the protozoan parasite Plasmodium falciparum, the causative agent of the most lethal type of human malaria, contains a single gene annotated as encoding a carbonic anhydrase (CAs, EC 4.2.1.1) thought to belong to the alpha-class, PfCA. Here we demonstrate the kinetic properties of PfCA for the CO2hydration reaction, as well as an inhibition study of this enzyme with inorganic and complex anions and other molecules known to interact with zinc proteins, including sulfamide, sulfamic acid, and phenylboronic/arsonic acids, detecting several low micromolar inhibitors. A closer examination of the sequence of this and the CAs from other Plasmodium spp., as well as a phylogenetic analysis, revealed that these protozoa encode for a yet undisclosed, new genetic family of CAs termed the eta-CA class. The main features of the eta-CAs are described in this report.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The invention belongs to the field of ionic liquids, which discloses a carbonic acid ester group of ionic liquid […] and its preparation method and application; the ionic liquid has the following structural formula: In the formula, R is 0 the   n? 4 ; Y ? selected from BF 4? , PF 6? , (CF 3 SO 2) 2 N ? or CF 3 SO 3? . The present invention provides carbon acid ester group of ionic liquid […], carbon into the cation in the ester group, the ionic liquid to improve the performance of, on the one hand in the electrolyte of the lithium-containing salt, this kind of carbon acid ester structure of the lithium salts have good solubility reconciliation separating function; on the other hand, the ionic liquid containing carbonate structure can be better generating SEI film, so as to improve electrochemical stability of the ionic liquid electrolyte. (by machine translation)

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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High capacity sodium (Na) metal anodes open up new opportunities for developing next-generation rechargeable batteries with both high power and high energy densities. However, many challenges still plagued their practical application, including low plating/stripping Coulombic efficiency (CE) and dendrite growth after repeated cycle inducing safety issue. Especially, the sodium metal is less stable in organic (i.e. carbonate-based) electrolytes than lithium metal, due to the more unstable organic solid?electrolyte interface (SEI). Herein, we report a facile technology to stabilize sodium metal anode and inhibit the growth of sodium dendrites. The in-situ ultrathin NaI SEI layer successfully endows best-performance Na/I2 metal batteries (>2200 cycles) with high capacity (210 mA h g?1 at 0.5 C) based on the conversion reaction chemistry with higher discharge voltage plateau (> 2.7 V) and lower overpotential (134 mV) due to the fast charge transfer dynamics and interfacial stability compared with pristine Na anode. The detailed theoretical calculations and experimental results elucidate that NaI layer has a much lower diffusion barrier compared to that of NaF (NaF as one the most commonly found inorganic components in Na-based SEI layer), and actually facilitates more uniform sodium deposition. This work provides a new avenue for designing low-cost, high-performance and high-safety sodium metal-iodine batteries and other metal-iodine batteries.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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To investigate the possibility of incorporating the 1,2-bis(pyridinium) ethane24?8 [2]pseudorotaxane motif into dendrimer like macromolecules, a series of branched [n]rotaxanes were prepared employing multiple dibenzo-24-membered crown ether wheels with various aromatic core structures and the 1,2-bis(4,4?dipyridinium)ethane axle. Yields of branched [2]-, [3]- and [4]rotaxanes were dependent on the size of the core and the . relative proximity of the crown ethers arranged around the core unit. The Royal Society of Chemistry 2005.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Energetics of bond dissociation, especially the R-H bond heterolysis free energy (pKa), has played a central role in promoting chemistry to become a rational science. Despite the oceans of acidity studies in the literature, the current knowledge is limited to that in the classical molecular solvents and is unable to be extended to anticipate the acidity changes in ionic media. As the latter is now very popular for replacing volatile organic solvents, it becomes highly desirable to know how the driving force of bond cleavage is varied as the medium composition is switched from neutral molecules to the charged ions. Here we describe a general approach to measure absolute pKa’s in pure ionic liquid (IL). The standard conditions warranting accurate measurement were outlined. The pKa’s of the selected 18 C-H type indicator acids in four ILs were determined and a convenient indicator platform was constructed for easy expansion of acidity scales. These absolute pKa’s make possible, for the first time, direct comparisons of bond energies in IL with those in molecular solvent and in the gas phase and should be able to serve as the standard parameters for calibrating computational methods suitable for the studies in ionic media. The effect of cation and anion in IL in relation to structure was analyzed.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A one-step oxidative fluorination for carbon-fluorine bond formation from well-defined nickel complexes with oxidant and aqueous fluoride is presented, which enables a straightforward and practical 18F late-stage fluorination of complex small molecules with potential for PET imaging.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Ionic liquids (ILs) have proven themselves as a new class of anticancer compounds among the scientific community in the 21st century. With proven efficiency of ionic liquids here an attempt has been made on a legacy anticancer compound noscapine. In this study, a library of novel noscapine (Nos) based ionic liquids were synthesized and characterized using various techniques such as 1H, 13C NMR spectroscopy and Mass spectrometry. These novel Nos-based ionic liquids were studied by in silico assays including molecular docking analysis, which showed the [Pip-Nos]OAc and [Pip-Nos]OTf derivatives of Nos-based ionic liquids have high molecular binding with docking score ?336.19 kJ/mol and ?326.71 kJ/mol, respectively, much higher than the parent compound noscapine (?267.06 kJ/mol). Also, pharmacokinetics and pharmacodynamics properties analyses showed the favorable results with high drug likeliness. The lead compounds were further well validated with in vitro anticancer cytotoxicity assay on HeLa cancer cell line. The in vitro cytotoxicity analysis depicted the high anticancer potency of lead compounds with lower IC50 of acetate and triflate IL derivatives than the parent compound noscapine. In conclusion, the present study paves the way to elucidate the potential anticancer ionic liquids.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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We report regioselective functionalization of pyridones and pyrones via electrophilic bromination (Br2) or radical trifluoromethylation (NaSO2CF3/tBuOOH) at the 3-position. Counter-intuitively, the 3-position EW groups decreased the carbonyl stretching energy by 6?23 cm?1; however, 3,5-dibromination increased the C[dbnd]O frequency by 10?22 cm?1 compared to the 3-Br pyridones. X-ray crystallography revealed pyridone tautomers with contracted C[dbnd]O bond metrics. pKa values and 1H NMR shifts for the series 3-H?Br?CF3 revealed the expected trend of increasing acidity (pKa = 8.85 ? 8.33?6.78, MeOH) and increasing chemical shifts (10.97 ? 11.42?11.71 DMSO-d6). We conclude that the paradoxical decrease in CO stretching frequencies by the 3-positoin EW groups is explained by an ?assistive? electron-withdrawing effect, whereby the 3-position EW group assists the electronegative oxygen atom in recruiting more electron density, and ? as a result ? attaining more oxyanion character (decreased the C[dbnd]O bond strength).

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI