Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Methane Storage in Paddlewheel-Based Porous Coordination Cages.

ABSTRACT: Although gas adsorption properties of extended three-dimensional metal-organic materials have been widely studied, they remain relatively unexplored in porous molecular systems. This is particularly the case for porous coordination cages for which surface areas are typically not reported. Herein, we report the synthesis, characterization, activation, and gas adsorption properties of a family of carbazole-based cages. The chromium analog displays a coordination cage record BET (Brunauer-Emmett-Teller) surface area of 1235 m2/g. With precise synthesis and activation procedures, two previously reported cages similarly display high surface areas. The materials exhibit high methane adsorption capacities at 65 bar with the chromium(II) cage displaying CH4 capacities of 194 cm3/g and 148 cm3/cm3. This high uptake is a result of optimal pore design, which was confirmed via powder neutron diffraction experiments.

SUBMITTER: Rowland CA

PROVIDER: S-EPMC6207189 | biostudies-literature | 2018 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Methane Storage in Paddlewheel-Based Porous Coordination Cages.

Rowland Casey A CA Lorzing Gregory R GR Gosselin Aeri J AJ Trump Benjamin A BA Yap Glenn P A GPA Brown Craig M CM Bloch Eric D ED

Journal of the American Chemical Society 20180904 36

Although gas adsorption properties of extended three-dimensional metal-organic materials have been widely studied, they remain relatively unexplored in porous molecular systems. This is particularly the case for porous coordination cages for which surface areas are typically not reported. Herein, we report the synthesis, characterization, activation, and gas adsorption properties of a family of carbazole-based cages. The chromium analog displays a coordination cage record BET (Brunauer-Emmett-Te ...[more]

PMID: 30122041

Similar Datasets

Understanding Gas Storage in Cuboctahedral Porous Coordination Cages.

Project description:Porous molecular solids are promising materials for gas storage and gas separation applications. However, given the relative dearth of structural information concerning these materials, additional studies are vital for further understanding their properties and developing design parameters for their optimization. Here, we examine a series of isostructural cuboctahedral, paddlewheel-based coordination cages, M24(tBu-bdc)24 (M = Cr, Mo, Ru; tBu-bdc2- = 5-tert-butylisophthalate), for high-pressure methane storage. As the decrease in crystallinity upon activation of these porous molecular materials precludes diffraction studies, we turn to a related class of pillared coordination cage-based metal-organic frameworks, M24(Me-bdc)24(dabco)6 (M = Fe, Co; Me-bdc2- = 5-methylisophthalate; dabco = 1,4-diazabicyclo[2.2.2]octane) for neutron diffraction studies. The five porous materials display BET surface areas from 1057-1937 m2/g and total methane uptake capacities of up to 143 cm3(STP)/cm3. Both the porous cages and cage-based frameworks display methane adsorption enthalpies of -15 to -22 kJ/mol. Also supported by molecular modeling, neutron diffraction studies indicate that the triangular windows of the cage are favorable methane adsorption sites with CD4-arene interactions between 3.7 and 4.1 Å. At both low and high loadings, two additional methane adsorption sites on the exterior surface of the cage are apparent for a total of 56 adsorption sites per cage. These results show that M24L24 cages are competent gas storage materials and further adsorption sites may be optimized by judicious ligand functionalization to control extracage pore space.

| S-EPMC6746114 | biostudies-literature

Porous metal-organic alloys based on soluble coordination cages.

Project description:Diverse strategies for the preparation of mixed-metal three-dimensional porous solids abound, although many of them lend themselves only moderate levels of tunability. Herein, we report the design and synthesis of surface functionalized permanently microporous coordination cages and their use in the isolation of mixed metal solids. Judicious alkoxide-based ligand functionalization was utilized to tune the solubility of starting copper(ii)-based cages and their resulting compatibility with the mixed-cage approach described here. We further prepared a family of isostructural molybdenum(ii) cages for a subset of the ligands. The preparation of mixed-metal cage solids proceeds under facile conditions where solutions of parent cages are mixed and product phases isolated. A suite of spectroscopic and characterization tools confirm the starting cages are intact in the amorphous product. Finally, we show that utilization of precise ligand functional groups can be used to prepare mixed cage solids that can be easily and cleanly separated into their constituent components through simple solvent washing or solvent extraction techniques.

| S-EPMC8163318 | biostudies-literature

Investigating Subcellular Compartment Targeting Effect of Porous Coordination Cages for Enhancing Cancer Nanotherapy.

Project description:Understanding the key factors for successful subcellular compartment targeting for cargo delivery systems is of great interest in a variety of fields such as bionanotechnology, cell biology, and nanotherapies. However, the fundamental basis for intracellular transportation with these systems has thus far rarely been discussed. As a cargo vector, porous coordination cages (PCCs) have great potential for use in cancer nanotherapy and to elucidate fundamental insight regarding subcellular compartment targeting. Herein, it is shown that the transportation of PCC cargo vectors though various subcellular barriers of the mammalian cell can be manipulated by tuning the vector's electronic property and surface affinity. It is found that the PCCs become selectively aggregated at the cell membrane, the cytoplasm, or the nucleus, respectively. When a DNA topoisomerase inhibitor is delivered into the nucleus by a neutral and lipophilic PCC, the anticancer efficacy is dramatically improved. The findings shed light to tune the interactions at the "bio-nano" interface. This study provides a key strategy for future work in targeting specific cell organelles for cell imaging, cargo delivery, and therapy. This research also offers key insight into the engineering of nanoscopic materials for furnishing cell organelle-specificity.

| S-EPMC6563816 | biostudies-literature

Coal-Tar Dye-based Coordination Cages and Helicates.

Project description:A strategy to implement four members of the classic coal-tar dye family, Michler's ketone, methylene blue, rhodamine B, and crystal violet, into [Pd2 L4 ] self-assemblies is introduced. Chromophores were incorporated into bis-monodentate ligands using piperazine linkers that allow to retain the auxochromic dialkyl amine functionalities required for intense colors deep in the visible spectrum. Upon palladium coordination, ligands with pyridine donors form lantern-shaped dinuclear cages while quinoline donors lead to strongly twisted [Pd2 L4 ] helicates in solution. In one case, single crystal X-ray diffraction revealed rearrangement to a [Pd3 L6 ] ring structure in the solid state. For nine examined derivatives, showing colors from yellow to deep violet, CD spectroscopy discloses different degrees of chiral induction by an enantiomerically pure guest. Ion mobility mass spectrometry allows to distinguish two binding modes. Self-assemblies based on this new ligand class promise application in chiroptical recognition, photo-redox catalysis and optical materials.

| S-EPMC7986857 | biostudies-literature

Enantiopure Chiral Coordination Polymers Based on Polynuclear Paddlewheel Helices and Arsenyl Tartrate.

Project description:Herein, we report the preparation of chiral, one-dimensional coordination polymers based on trinuclear paddlewheel helices [M₃(dpa)₄]2+ (M = Co(II) and Ni(II); dpa = the anion of 2,2'-dipyridylamine). Enantiomeric resolution of a racemic mixture of [M₃(dpa)₄]2+ complexes was achieved by chiral recognition of the respective enantiomer by [Δ-As₂(tartrate)₂]2- or [Λ-As₂(tartrate)₂]2- in N,N-dimethylformamide (DMF), affording crystalline coordination polymers formed from [(Δ-Co₃(dpa)₄)(Λ-As₂(tartrate)₂)]·3DMF (Δ-1), [(Λ-Co₃(dpa)₄)(Δ-As₂(tartrate)₂)]·3DMF (Λ-1), [(Δ-Ni₃(dpa)₄)(Λ-As₂(tartrate)₂)]·(4 - n)DMF∙nEt₂O (Δ-2) or [(Λ-Ni₃(dpa)₄)(Δ-As₂(tartrate)₂)]·(4 - n)DMF∙nEt₂O (Λ-2) repeating units. UV-visible circular dichroism spectra of the complexes in DMF solutions demonstrate the efficient isolation of optically active species. The helicoidal [M₃(dpa)₄]2+ units that were obtained display high stability towards racemization as shown by the absence of an evolution of the dichroic signals after several days at room temperature and only a small decrease of the signal after 3 h at 80 °C.

| S-EPMC6414907 | biostudies-literature

Chiral Self-Discrimination and Guest Recognition in Helicene-Based Coordination Cages.

Project description:Chiral nanosized confinements play a major role for enantioselective recognition and reaction control in biological systems. Supramolecular self-assembly gives access to artificial mimics with tunable sizes and properties. Herein, a new family of [Pd2 L4 ] coordination cages based on a chiral [6]helicene backbone is introduced. A racemic mixture of the bis-monodentate pyridyl ligand L1 selectively assembles with PdII cations under chiral self-discrimination to an achiral meso cage, cis-[Pd2 L1P 2 L1M 2 ]. Enantiopure L1 forms homochiral cages [Pd2 L1P/M 4 ]. A longer derivative L2 forms chiral cages [Pd2 L2P/M 4 ] with larger cavities, which bind optical isomers of chiral guests with different affinities. Owing to its distinct chiroptical properties, this cage can distinguish non-chiral guests of different lengths, as they were found to squeeze or elongate the cavity under modulation of the helical pitch of the helicenes. The CD spectroscopic results were supported by ion mobility mass spectrometry.

| S-EPMC6563462 | biostudies-literature

Superparamagnetic iron oxide-gold nanoparticles conjugated with porous coordination cages: Towards controlled drug release for non-invasive neuroregeneration.

Project description:This paper reports a smart intracellular nanocarrier for sustainable and controlled drug release in non-invasive neuroregeneration. The nanocarrier is composed by superparamagnetic iron oxide-gold (SPIO-Au) core-shell nanoparticles (NPs) conjugated with porous coordination cages (PCCs) through the thiol-containing molecules as bridges. The negatively charged PCC-2 and positively charged PCC-3 are compared for intracellular targeting. Both types result in intracellular targeting via direct penetration across cellular membranes. However, the pyrene (Py)-PEG-SH bridge enabled functionalization of SPIO-Au NPs with PCC-3 exhibits higher interaction with PC-12 neuron-like cells, compared with the rhodamine B (RhB)-PEG-SH bridge enabled case and the stand-alone SPIO-Au NPs. With neglectable toxicities to PC-12 cells, the proposed SPIO-Au-RhB(Py)-PCC-2(3) nanocarriers exhibit effective drug loading capacity of retinoic acid (RA) at 13.505 μg/mg of RA/NPs within 24 h. A controlled release of RA is achieved by using a low-intensity 525 nm LED light (100% compared to 40% for control group within 96 h).

| S-EPMC8238818 | biostudies-literature

Topological prediction of palladium coordination cages.

Project description:The preparation of functionalized, heteroleptic Pd x L2x coordination cages is desirable for catalytic and optoelectronic applications. Current rational design of these cages uses the angle between metal-binding (∠B) sites of the di(pyridyl)arene linker to predict the topology of homoleptic cages obtained via non-covalent chemistry. However, this model neglects the contributions of steric bulk between the pyridyl residues-a prerequisite for endohedrally functionalized cages, and fails to rationalize heteroleptic cages. We describe a classical mechanics (CM) approach to predict the topological outcomes of Pd x L2x coordination cage formation with arbitrary linker combinations, accounting for the electronic effects of coordination and steric effects of linker structure. Initial validation of our CM method with reported homoleptic Pd12 LFu 24 (LFu = 2,5-bis(pyridyl)furan) assembly suggested the formation of a minor topology Pd15 LFu 30, identified experimentally by mass spectrometry. Application to heteroleptic cage systems employing mixtures of LFu (∠B = 127°) and its thiophene congener LTh (∠B = 149° ∠B exp = 152.4°) enabled prediction of Pd12L24 and Pd24L48 coordination cages formation, reliably emulating experimental data. Finally, the topological outcome for exohedrally (LEx) and endohedrally (LEn) functionalized heteroleptic Pd x L2x coordination cages were predicted to assess the effect of steric bulk on both topological outcomes and coordination cage yields, with comparisons drawn to experimental data.

| S-EPMC8162455 | biostudies-literature

Porous Metal-Organic Polyhedral Frameworks with Optimal Molecular Dynamics and Pore Geometry for Methane Storage.

Project description:Natural gas (methane, CH4) is widely considered as a promising energy carrier for mobile applications. Maximizing the storage capacity is the primary goal for the design of future storage media. Here we report the CH4 storage properties in a family of isostructural (3,24)-connected porous materials, MFM-112a, MFM-115a, and MFM-132a, with different linker backbone functionalization. Both MFM-112a and MFM-115a show excellent CH4 uptakes of 236 and 256 cm3 (STP) cm-3 (v/v) at 80 bar and room temperature, respectively. Significantly, MFM-115a displays an exceptionally high deliverable CH4 capacity of 208 v/v between 5 and 80 bar at room temperature, making it among the best performing metal-organic frameworks for CH4 storage. We also synthesized the partially deuterated versions of the above materials and applied solid-state 2H NMR spectroscopy to show that these three frameworks contain molecular rotors that exhibit motion in fast, medium, and slow regimes, respectively. In situ neutron powder diffraction studies on the binding sites for CD4 within MFM-132a and MFM-115a reveal that the primary binding site is located within the small pocket enclosed by the [(Cu2)3(isophthalate)3] window and three anthracene/phenyl panels. The open Cu(II) sites are the secondary/tertiary adsorption sites in these structures. Thus, we obtained direct experimental evidence showing that a tight cavity can generate a stronger binding affinity to gas molecules than open metal sites. Solid-state 2H NMR spectroscopy and neutron diffraction studies reveal that it is the combination of optimal molecular dynamics, pore geometry and size, and favorable binding sites that leads to the exceptional and different methane uptakes in these materials.

| S-EPMC5620961 | biostudies-literature

Core-Shell Crystals of Porous Organic Cages.

Project description:The first examples of core-shell porous molecular crystals are described. The physical properties of the core-shell crystals, such as surface hydrophobicity, CO2 ?/CH4 selectivity, are controlled by the chemical composition of the shell. This shows that porous core-shell molecular crystals can exhibit synergistic properties that out-perform materials built from the individual, constituent molecules.

| S-EPMC6120484 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data