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:A supramolecular lithium cation assemblies of crown ether, [Li 12-crown-4](+), has been used to replace conventional tetraalkylammonium counterion in thiolate/disulfide (ET(-)/BET) mediated dye-sensitized solar cells (DSCs), which exhibit high stability and efficiency of 6.61% under 100 mW·cm(-2) simulated sunlight illumination.
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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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Project description:Mycoplasma mobile exhibits a smooth gliding movement as does its membrane-permeabilized ghost model. Ghost experiments revealed that the energy source for M. mobile motility is adenosine triphosphate (ATP) and that the gliding comprises repetitions of 70?nm steps. Here we show a new motility mode, in which the ghost model prepared with 0.013% Triton X-100 exhibits directed rotational motions with an average speed of approximately 2.1?Hz when ATP concentration is greater than 3.0?×?10-1?mM. We found that rotary ghosts treated with sialyllactose, the binding target for leg proteins, were stopped. Although the origin of the rotation has not been conclusively determined, this result suggested that biomolecules embedded on the cell membrane nonspecifically attach to the glass and work as a fluid pivot point and that the linear motion of the leg is a driving force for the rotary motion. This simple geometry exemplifies the new motility mode, by which the movement of a linear motor is efficiently converted to a constant rotation of the object on a micrometer scale.
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Project description:Convenient macrocyclization synthetic routes for the preparation of different-sized monoaza anthracylmethyl crown ether chemsensors (15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8 and 27-crown-9) are described. Evaluation of these crowns as chemosensors for saxitoxin revealed that the larger crowns have moderately higher binding constants, with the 27-crown-9 chemosensor having the largest binding constant: 2.29×10(5) M(-1). Fluorescence enhancements of 100% were observed at saxitoxin concentrations of 5 ?M, which is close to the detection limit in mouse bioassay.
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Project description:Highly toxic bacterial ionophores are commonly used in veterinary medicine, but their therapeutic index is too narrow for human usage. With the goal of developing ionophores with a broader therapeutic index, we constructed highly derivatized synthetic ionophores. The toxicities of crown ether host-rotaxanes (CEHR's) against the SKOV-3 cell line were measured. The effect of Mg2+ or Ca2+ on toxicity was explored because changes in the intracellular concentration of these cations can cause cell death through apoptosis. We found Boc-CEHR is highly toxic and Arg-CEHR is slightly less toxic with IC50 values of 0.5 ?M and 6 ?M, respectively, in standard growth medium. Increasing the concentration of Ca2+ resulted in greater toxicity of the CEHRs, whereas increasing the concentration of Mg2+ was less effective on reducing IC50. Cell death occurs mainly through apoptosis. Although preliminary, these results suggest that the CEHRs deliver Ca2+ and perhaps Mg2+ into cells inducing apoptosis.
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Project description:F1-ATPase is a rotary motor protein driven by ATP hydrolysis. The rotary motion of F1-ATPase is tightly coupled to catalysis, in which the catalytic sites strictly obey the reaction sequences at the resolution of elementary reaction steps. This fine coordination of the reaction scheme is thought to be important to achieve extremely high chemomechanical coupling efficiency and reversibility, which is the prominent feature of F1-ATPase among molecular motor proteins. In this study, we intentionally change the reaction scheme by using single-molecule manipulation, and we examine the resulting effect on the rotary motion of F1-ATPase. When the sequence of the products released, that is, ADP and inorganic phosphate, is switched, we find that F1 frequently stops rotating for a long time, which corresponds to inactivation of catalysis. This inactive state presents MgADP inhibition, and thus, we find that an improper reaction sequence of F1-ATPase catalysis induces MgADP inhibition.
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Project description:Two new light-driven molecular rotary motors based on the N-alkylated indanylidene benzopyrrole frameworks are proposed and studied using quantum chemical calculations and nonadiabatic molecular dynamics simulations. These new motors perform pure axial rotation, and the photochemical steps of the rotary cycle are dominated by the fast bond-length-alternation motion that enables ultrafast access to the S1/S0 intersection. The new motors are predicted to display a quantum efficiency higher than that of the currently available synthetic all-hydrocarbon motors. Remarkably, the quantum efficiency is not governed by the topography (peaked versus sloped) of the minimum-energy conical intersection, whereas the S1 decay time depends on the topography as well as on the energy of the intersection relative to the S1 minimum. It is the axial chirality (helicity), rather than the point chirality, that controls the sense of rotation of the motor.
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