Cation-Modulated Rotary Speed in a Light-Driven Crown Ether Functionalized Molecular Motor.
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ABSTRACT:
SUBMITTER: Dorel R
PROVIDER: S-EPMC6038094 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:UV resonance Raman (UVRR) spectroscopy is used to probe changes in vibrational structure associated with cation-? interactions for the most prevalent amino acid ? -donor, tryptophan. The model compound studied here is a diaza crown ether with two indole substituents. In the presence of sodium or potassium sequestered in the crown ether, or a protonated diaza group on the compound, the indole moieties participate in a cation-? interaction in which the pyrrolo group acts as the primary ?-donor. Systematic shifts in relative intensity in the 760-780 cm-1 region are observed upon formation of this cation-? interaction; we propose that these modifications reflect shifts of the delocalized, ring-breathing W18 and hydrogen-out-of-plane (HOOP) vibrational modes in this spectral region. The observed changes are attributed to perturbations of the ?-electron density as well as of normal modes that involve large displacement of the hydrogen atom on the C2 position of the pyrrole ring. Modest variations in the UVRR spectra for the three complexes studied here are correlated to differences in cation-? strength. Specifically, the UVRR spectrum of the sodium-bound complex differs from those of the potassium-bound or protonated-diaza complexes, and may reflect the observation that the C2 hydrogen atom in the sodium-bound complex exhibits the greatest perturbation relative to the other species. Normal modes sensitive to hydrogen-bonding, such as the tryptophan W10, W9, and W8 modes, also undergo shifts in the presence of the salts. These shifts reflect the strength of interaction of the indole N-H group with the iodide or hexafluorophosphate counteranion. The current observation that the W18 and HOOP normal mode regions of the indole crown ether compound are sensitive to cation-pyrrolo ? interactions suggests that this region may provide reliable spectroscopic evidence of these important interactions in proteins.
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Project description:The rotational speed of an overcrowded alkene-based molecular rotary motor, having an integrated 4,5-diazafluorenyl coordination motif, can be regulated allosterically via the binding of metal ions. DFT calculations have been used to predict the relative speed of rotation of three different (i.e., zinc, palladium, and platinum) metal dichloride complexes. The photochemical and thermal isomerization behavior of these complexes has been studied in detail using UV-vis and 1H NMR spectroscopy. Our results confirm that metal coordination induces a contraction of the diazafluorenyl lower half, resulting in a reduction of the steric hindrance in the "fjord" region of the molecule, which causes an increase of the rotational speed. Importantly, metal complexation can be accomplished in situ and is found to be reversible upon the addition of a competing ligand. Consequently, the rotational behavior of these molecular motors can be dynamically controlled with chemical additives.
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Project description:The working mechanism of conventional light-driven molecular rotary motors, especially Feringa-type motors, contains two photoisomerization steps and two thermal helix inversion steps. Due to the existence of a thermal helix inversion step, both the ability to work at lower temperatures and the rotation speed are limited. In this work, a two-stroke light-driven molecular rotary motor, 2-(1,5-dimethyl-4,5-dihydrocyclopenta[b]pyrrol-6(1H)-ylidene)-1,2-dihydro-3H-pyrrol-3-one (DDPY), is proposed, which is capable of performing unidirectional and repetitive rotation by only two photoisomerization (EP→ZP and ZP→EP) steps. With trajectory surface-hopping simulation at the semi-empirical OM2/MRCI level, the EP→ZP and ZP→EP nonadiabatic dynamics of DDPY were systematically studied at different temperatures. Both EP→ZP and ZP→EP photoisomerizations are on an ultrafast timescale (ca. 200-300 fs). The decay mode of EP→ZP photoisomerization is approximately bi-exponential, while that of ZP→EP photoisomerization is found to be periodic. For EP and ZP isomers of DDPY, after the S0→S1 excitation, the dynamical processes of nonadiabatic decay are both followed by twisting about the central C=C double bond and the pyramidalization of the C atom at the stator-axle linkage. The effect of temperature on the nonadiabatic dynamics of EP→ZP and ZP→EP photoisomerizations of DDPY has been systematically investigated. The average lifetimes of the S1 excited state and quantum yields for both EP→ZP and ZP→EP photoisomerization are almost temperature-independent, while the corresponding unidirectionality of rotation is significantly increased (e.g., 74% for EP→ZP and 72% for ZP→EP at 300 K vs 100% for EP→ZP and 94% for ZP→EP at 50 K) with lowering the temperature.
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Project description:Regulation of the sodium cations level in the case of renal failure diseases is a very challenging task for clinicians, and new pollutant extractors based on nanomaterials are emerging as potential treatments. In this work, we report different strategies for the chemical functionalization of biocompatible large pore mesoporous silica, denoted stellate mesoporous silica (STMS), with chelating ligands able to selectively capture sodium. We address efficient methods to covalently graft highly chelating macrocycles onto STMS NPs such as crown ethers (CE) and cryptands (C221) through complementary carbodiimidation reactions. Regarding sodium capture in water, C221 cryptand-grafted STMS showed better capture efficiency than CE-STMS due to higher sodium atom chelation in the cryptand cage (Na+ coverage of 15.5% vs. 3.7%). The sodium selectivity was hence tested with C221 cryptand-grafted STMS in a multi-element aqueous solution (metallic cations with the same concentration) and in a solution mimicking peritoneal dialysis solution. Results obtained indicate that C221 cryptand-grafted STMS are relevant nanomaterials to extract sodium cations in such media and allow us to regulate their levels.
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Project description:Due to the increased demand for palladium, as well due to its reduced availability in nature, its recovery from diluted waste solutions becomes a necessity, and perhaps an emergency. As a result of economic and technological development, new materials with improved adsorbent properties that are more efficient for metallic ions' recovery were synthesized and introduced to market. The goal of this study was to obtain a new adsorbent material by functionalizing through impregnation a commercial polymeric support that was both inexpensive and environmentally friendly (Amberlite XAD7) with crown ether (di-benzo-18-crown-6-DB18C6). Crown ethers are known for their ability to form complexes within metallic ions, by including them inside of the ring, regardless of its atomic size. Adsorbent material was prepared by impregnation using the solvent-impregnated resin method (SIR). To highlight the presence of crown ether on the resin surface, a new synthesized material was characterized by scanning electron microscopy (SEM), elemental analysis X-ray energy dispersive spectroscopy (EDX) and Fourier transform infrared spectroscopy (FT-IR). The specific surface of the adsorbent material was also determined by the Brunauer-Emmett-Teller (BET) method. Adsorbent performances of the prepared material were highlighted by kinetic, thermodynamic and equilibrium studies and a possible mechanism was also proposed. The influence of specific parameters for the adsorption process (contact time, temperature, Pd(II) initial concentration) on the maximum adsorption capacity was pursued.
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Project description:The concentration of sodium and potassium ions in biological fluids, such as blood, urine and sweat, is indicative of several basic body function conditions. Therefore, the development of simple methods able to detect these alkaline ions is of outmost importance. In this study, we explored the electrochemical and optical properties of graphene quantum dots (GQDs) combined with the selective chelating ability of the crown ethers 15-crown-5 and 18-crown-6, with the final aim to propose novel composites for the effective detection of these ions. The results obtained comparing the performances of the single GQDs and crown ethers with those of the GQDs-15-crown-5 and GQDs-18-crown-6 composites, have demonstrated the superior properties of these latter. Electrochemical investigation showed that the GQDs based composites can be exploited for the potentiometric detection of Na+ and K+ ions, but selectivity still remains a concern. The nanocomposites showed the characteristic fluorescence emissions of GQDs and crown ethers. The GQDs-18-crown-6 composite exhibited ratiometric fluorescence emission behavior with the variation of K+ concentration, demonstrating its promising properties for the development of a selective fluorescent method for potassium determination.
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