Versatile non-luminescent color palette based on guest exchange dynamics in paramagnetic cavitands.
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ABSTRACT:
SUBMITTER: Goren E
PROVIDER: S-EPMC8144181 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Biomimetic deep-cavity cavitand hosts possess unique recognition and encapsulation properties that make them capable of selectively binding a range of non-polar guests within their hydrophobic pocket. Adamantane based derivatives which snuggly fit within the pocket of octa-acid deep cavity cavitands exhibit some of the strongest host binding. Here we explore the roles of guest size and attractiveness on optimizing guest binding to form 1:1 complexes with octa-acid cavitands in water. Specifically we simulate the water-mediated interactions of the cavitand with adamantane and a range of simple Lennard-Jones guests of varying diameter and attractive well-depth. Initial simulations performed with methane indicate hydrated methanes preferentially reside within the host pocket, although these guests frequently trade places with water and other methanes in bulk solution. The interaction strength of hydrophobic guests increases with increasing size from sizes slightly smaller than methane to Lennard-Jones guests comparable in size to adamantane. Over this guest size range the preferential guest binding location migrates from the bottom of the host pocket upwards. For guests larger than adamantane, however, binding becomes less favorable as the minimum in the potential-of-mean force shifts to the cavitand face around the portal. For a fixed guest diameter, the Lennard-Jones well-depth is found to systematically shift the guest-host potential-of-mean force to lower free energies, however, the optimal guest size is found to be insensitive to increasing well-depth. Ultimately our simulations show that adamantane lies within the optimal range of guest sizes with significant attractive interactions to match the most tightly bound Lennard-Jones guests studied.
| S-EPMC3880382 | biostudies-other
Project description:Paramagnetic metallohost systems can bind guest molecules and find application as biomimetic catalysts. Due to the presence of the paramagnetic metal center, rigorous characterization of these systems by NMR spectroscopy can be very difficult. We report here that metallohost-guest systems can be studied by using the paramagnetic relaxation enhancement (PRE) effect. Manganese(III) porphyrin cage compounds are shown through their PRE to thread and bind viologen guests, including a polymeric one. The binding constants and dethreading activation parameters are lower than those of the metal-free porphyrin cage compounds, which is proposed to be a result of charge repulsion of the trivalent metal center and dicationic viologen guest. The threading rate of the manganese(III) porphyrin cage onto the polymer is more than 10 times faster than that of the non-metallated one, which is ascribed to initial binding of the cage to the polymer chain prior to threading, and to an entron effect.
| S-EPMC8986849 | biostudies-literature
Project description:The Eu(III) complex of (1S,4S,7S,10S)-1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane (S-THP) is studied as a sensor for biologically relevant anions. Anion interactions produce changes in the luminescence emission spectrum of the Eu(III) complex, in the (1)H NMR spectrum, and correspondingly, in the PARACEST spectrum of the complex (PARACEST = paramagnetic chemical exchange saturation transfer). Direct excitation spectroscopy and luminescence lifetime studies of Eu(S-THP) give information about the speciation and nature of anion interactions including carbonate, acetate, lactate, citrate, phosphate, and methylphosphate at pH 7.2. Data is consistent with the formation of both innersphere and outersphere complexes of Eu(S-THP) with acetate, lactate, and carbonate. These anions have weak dissociation constants that range from 19 to 38 mM. Citrate binding to Eu(S-THP) is predominantly innersphere with a dissociation constant of 17 μM. Luminescence emission peak changes upon addition of anion to Eu(S-THP) show that there are two distinct binding events for phosphate and methylphosphate with dissociation constants of 0.3 mM and 3.0 mM for phosphate and 0.6 mM and 9.8 mM for methyl phosphate. Eu(THPC) contains an appended carbostyril derivative as an antenna to sensitize Eu(III) luminescence. Eu(THPC) binds phosphate and citrate with dissociation constants that are 10-fold less than that of the Eu(S-THP) parent, suggesting that functionalization through a pendent group disrupts the anion binding site. Eu(S-THP) functions as an anion responsive PARACEST agent through exchange of the alcohol protons with bulk water. The alcohol proton resonances of Eu(S-THP) shift downfield in the presence of acetate, lactate, citrate, and methylphosphate, giving rise to distinct PARACEST peaks. In contrast, phosphate binds to Eu(S-THP) to suppress the PARACEST alcohol OH peak and carbonate does not markedly change the alcohol peak at 5 mM Eu(S-THP), 15 mM carbonate at pH 6.5 or 7.2. This work shows that the Eu(S-THP) complex has unique selectivity toward binding of biologically relevant anions and that anion binding results in changes in both the luminescence and the PARACEST spectra of the complex.
| S-EPMC3528016 | biostudies-literature
Project description:The ability to mediate the kinetic properties and dissociation activation energies (E a) of bound guests by controlling the characteristics of "supramolecular lids" in host-guest molecular systems is essential for both their design and performance. While the synthesis of such systems is well advanced, the experimental quantification of their kinetic parameters, particularly in systems experiencing fast association and dissociation dynamics, has been very difficult or impossible with the established methods at hand. Here, we demonstrate the utility of the NMR-based guest exchange saturation transfer (GEST) approach for quantifying the dissociation exchange rates (k out) and activation energy (E a,out) in host-guest systems featuring fast dissociation dynamics. Our assessment of the effect of different monovalent cations on the extracted E a,out in cucurbit[7]uril:guest systems with very fast k out highlights their role as "supramolecular lids" in mediating a guest's dissociation E a. We envision that GEST could be further extended to study kinetic parameters in other supramolecular systems characterized by fast kinetic properties and to design novel switchable host-guest assemblies.
| S-EPMC8179218 | biostudies-literature
Project description:We investigated Xe binding in a previously reported paramagnetic metal-organic tetrahedral capsule, [Co4L6]4-, where L2- = 4,4'-bis[(2-pyridinylmethylene)amino][1,1'-biphenyl]-2,2'-disulfonate. The Xe-inclusion complex, [XeCo4L6]4-, was confirmed by 1H NMR spectroscopy to be the dominant species in aqueous solution saturated with Xe gas. The measured Xe dissociation rate in [XeCo4L6]4-, koff = 4.45(5) × 102 s-1, was at least 40 times greater than that in the analogous [XeFe4L6]4- complex, highlighting the capability of metal-ligand interactions to tune the capsule size and guest permeability. The rapid exchange of 129Xe nuclei in [XeCo4L6]4- produced significant hyperpolarized 129Xe chemical exchange saturation transfer (hyper-CEST) NMR signal at 298 K, detected at a concentration of [XeCo4L6]4- as low as 100 pM, with presaturation at -89 ppm, which was referenced to solvated 129Xe in H2O. The saturation offset was highly temperature-dependent with a slope of -0.41(3) ppm/K, which is attributed to hyperfine interactions between the encapsulated 129Xe nucleus and electron spins on the four CoII centers. As such, [XeCo4L6]4- represents the first example of a paramagnetic hyper-CEST (paraHYPERCEST) sensor. Remarkably, the hyper-CEST 129Xe NMR resonance for [XeCo4L6]4- (δ = -89 ppm) was shifted 105 ppm upfield from the diamagnetic analogue [XeFe4L6]4- (δ = +16 ppm). The Xe inclusion complex was further characterized in the crystal structure of (C(NH2)3)4[Xe0.7Co4L6]·75 H2O (1). Hydrogen bonding between capsule-linker sulfonate groups and exogenous guanidinium cations, (C(NH2)3)+, stabilized capsule-capsule interactions in the solid state and also assisted in trapping a Xe atom (∼42 Å3) in the large (135 Å3) cavity of 1. Magnetic susceptibility measurements confirmed the presence of four noninteracting, magnetically anisotropic high-spin CoII centers in 1. Furthermore, [Co4L6]4- was found to be stable toward aggregation and oxidation, and the CEST performance of [XeCo4L6]4- was unaffected by biological macromolecules in H2O. These results recommend metal-organic capsules for fundamental investigations of Xe host-guest chemistry as well as applications with highly sensitive 129Xe-based sensors.
| S-EPMC7672707 | biostudies-literature
Project description:Dynamic and reversible assembly of molecules is ubiquitous in the hierarchical superstructures of living systems and plays a key role in cellular functions. Recent work from the laboratory reported on the reversible formation of such superstructures in systems of peptide amphiphiles conjugated to oligonucleotides and electrostatically complimentary peptide sequences. Here, a supramolecular system is reported upon where exchange dynamics and host-guest interactions between β-cyclodextrin and adamantane on peptide amphiphiles lead to superstructure formation. Superstructure formation with bundled nanoribbons generates a mechanically robust hydrogel with a highly porous architecture that can be 3D printed. Functionalization of the porous superstructured material with a biological signal results in a matrix with significant in vitro bioactivity toward neurons that could be used as a supramolecular model to design novel biomaterials.
| S-EPMC8061421 | biostudies-literature
Project description:In this study, the host-guest behavior of poly(amidoamine) (PAMAM) dendrimers bearing amine, hydroxyl, or carboxylate surface functionalities were investigated by paramagnetic NMR studies. 2,2,6,6-Tetramethylpiperidinyloxy (TEMPO) derivatives were used as paramagnetic guest molecules. The results showed that TEMPO-COOH significantly broaden the ¹H NMR peaks of amine- and hydroxyl-terminated PAMAM dendrimers. In comparison, no paramagnetic relaxation enhancement (PRE) was observed between TEMPO-NH?, TEMPO-OH and the three types of PAMAM dendrimers. The PRE phenomenon observed is correlated with the encapsulation of TEMPO-COOH within dendrimer pockets. Protonation of the tertiary amine groups within PAMAM dendrimers plays an important role during this process. Interestingly, the absence of TEMPO-COOH encapsulation within carboxylate-terminated PAMAM dendrimer is observed due to the repulsion of TEMPO-COO- anion and anionic dendrimer surface. The combination of paramagnetic probes and ¹H NMR linewidth analysis can be used as a powerful tool in the analysis of dendrimer-based host-guest systems.
| S-EPMC3677888 | biostudies-literature
Project description:Living organisms have developed a wide range of appearances from iridescent to matte textures. Interestingly, angular-independent structural colors, where isotropy in the scattering structure is present, only produce coloration in the blue wavelength region of the visible spectrum. One might, therefore, wonder if such observation is a limitation of the architecture of the palette of materials available in nature. Here, by exploiting numerical modeling, we discuss the origin of isotropic structural colors without restriction to a specific light scattering regime. We show that high color purity and color saturation cannot be reached in isotropic short-range order structures for red hues. This conclusion holds even in the case of advanced scatterer morphologies, such as core-shell particles or inverse photonic glasses-explaining recent experimental findings reporting very poor performances of visual appearance for such systems.
| S-EPMC7519302 | biostudies-literature
Project description:We investigate the magnetic resonance properties and exchange kinetics of guest molecules in a series of hetero-bimetallic capsules, [ConFe4-nL6]4- (n = 1-3), where L2- = 4,4'-bis[(2-pyridinylmethylene)amino]-[1,1'-biphenyl]-2,2'-disulfonate. H bond networks between capsule sulfonates and guanidinium cations promote the crystallization of [ConFe4-nL6]4-. The following four isostructural crystals are reported: two guest-free forms, (C(NH2)3)4[Co1.8Fe2.2L6]·69H2O (1) and (C(NH2)3)4[Co2.7Fe1.3L6]·73H2O (2), and two Xe- and CFCl3-encapsulated forms, (C(NH2)3)4[(Xe)0.8Co1.8Fe2.2L6]·69H2O (3) and (C(NH2)3)4[(CFCl3)Co2.0Fe2.0L6]·73H2O (4), respectively. Structural analyses reveal that Xe induces negligible structural changes in 3, while the angles between neighboring phenyl groups expand by ca. 3° to accommodate the much larger guest, CFCl3, in 4. These guest-encapsulated [ConFe4-nL6]4- molecules reveal 129Xe and 19F chemical shift changes of ca. -22 and -10 ppm at 298 K, respectively, per substitution of low-spin FeII by high-spin CoII. Likewise, the temperature dependence of the 129Xe and 19F NMR resonances increases by 0.1 and 0.06 ppm/K, respectively, with each additional paramagnetic CoII center. The optimal temperature for hyperpolarized (hp) 129Xe chemical exchange saturation transfer (hyper-CEST) with [ConFe4-nL6]4- capsules was found to be inversely proportional to the number of CoII centers, n, which is consistent with the Xe chemical exchange accelerating as the portals expand. The systematic study was facilitated by the tunability of the [M4L6]4- capsules, further highlighting these metal-organic systems for developing responsive sensors with highly shifted 129Xe resonances.
| S-EPMC7649716 | biostudies-literature
Project description:SummaryIn the exploratory data analysis of single-cell or spatial genomic data, single-cells or spatial spots are often visualized using a two-dimensional plot where cell clusters or spot clusters are marked with different colors. With tens of clusters, current visualization methods often assign visually similar colors to spatially neighboring clusters, making it hard to identify the distinction between clusters. To address this issue, we developed Palo that optimizes the color palette assignment for single-cell and spatial data in a spatially aware manner. Palo identifies pairs of clusters that are spatially neighboring to each other and assigns visually distinct colors to those neighboring pairs. We demonstrate that Palo leads to improved visualization in real single-cell and spatial genomic datasets.Availability and implementationPalo R package is freely available at Github (https://github.com/Winnie09/Palo) and Zenodo (https://doi.org/10.5281/zenodo.6562505).Supplementary informationSupplementary data are available at Bioinformatics online.
| S-EPMC9272793 | biostudies-literature