Morphology Modification of the Iron Fumarate MIL‐88A Metal–Organic Framework Using Formic Acid and Acetic Acid as Modulators

Bagherzadeh, Elham; Zebarjad, Seyed Mojtaba; Hosseini, Hamid Reza Madaah

doi:10.1002/ejic.201800056

Cited by 48 publications

(16 citation statements)

References 25 publications

(31 reference statements)

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“…35 Using both coordination modulation, the addition of monotopic modulators that mimic the organic ligands, and oxidation modulation, utilising metal starting materials in different oxidation states to those in the product, it is possible to exert kinetic control over self-assembly and select either the non-interpenetrated MIL-88D(Fe) kinetic product or the twofold interpenetrated MIL-126(Fe) polymorph that is the thermodynamic product. 34 Coordination modulation has also been used to control the physical properties of Fe-MOFs, such as particle morphology [36][37][38] and size. 39,40 Herein, we apply coordination and oxidation modulation to the synthesis of Fe-terephthalate MOFs, a much more complex system, allowing mapping of the phase space and simple, reproducible isolation of individual phases.…”

Section: Introductionmentioning

confidence: 99%

Exploring and Expanding the Fe-Terephthalate Metal-Organic Framework Phase Space by Coordination and Oxidation Modulation

Bara

Meekel

Pakamorė

et al. 2021

Preprint

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The synthesis of phase pure metal-organic frameworks (MOFs) – network solids of metal clusters connected by organic linkers – is often complicated by the possibility of forming multiple diverse phases from one metal-ligand combination. For example, there are at least six Fe-terephthalate MOFs reported to date, with many examples of erroneous assignment of phase based on diffraction data alone. Herein, we show that modulated self-assembly can be used to influence the kinetics of self-assembly of Fe-terephthalate MOFs. We comprehensively assess the effect of addition of both coordinating modulators and pH modulators to the outcome of syntheses, as well as probing the influence of the oxidation state of the Fe precursor (oxidation modulation) and the role of the counteranion on the phase(s) formed. In doing so, we shed light on the thermodynamic landscape of this phase system, uncover mechanistics of modulation, provide robust routes to phase pure materials, often as single crystals, and introduce two new Fe-terephthalate MOFs to an already complex system. The results highlight the potential of modulated self-assembly to bring precision control and new structural diversity to systems that have already received significant study.

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Section: Introductionmentioning

confidence: 99%

Exploring and Expanding the Fe-Terephthalate Metal-Organic Framework Phase Space by Coordination and Oxidation Modulation

Bara

Meekel

Pakamorė

et al. 2021

Preprint

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“…For samples without any acidification, rapid clouding and formation of particles in the micrometer range were observed. By adding 100 equivalents formic acid, a monodentate modulator also used for MOF synthesis,24b,28 this immediate aggregation was prevented and the particle formation occurred more slowly (Figure S3, Supporting Information). Additional HCl had a minor influence on size and PDI (Figure S4, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Core‐Shell Functionalized Zirconium‐Pemetrexed Coordination Nanoparticles as Carriers with a High Drug Content

Steinborn

Hirschle

Höhn

et al. 2019

Advanced Therapeutics

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Selected drug molecules with Lewis base functions can be assembled into coordinative nanoparticles (NPs) by linking them with suitable metal ions. Such nanomaterials exhibit a high material economy due to high drug contents and minor amounts of inactive additives. The antifolate pemetrexed (PMX) which is used for the treatment of lung cancers contains two carboxy functions that are able to undergo coordinative binding of metal ions. This study presents the development of a multilayer PMX NP system where each layer serves a distinct purpose. The metal-drug NP core is assembled in a bottom-up approach by coordinative interactions between zirconium (IV) ions and PMX molecules. Since the NP core is generated from drug molecules as essential units, it features a very high drug content of almost 80%. The NP core is stabilized against serum with a shell of a polymerized oligoamine-modified trimethoxysilane derivative (TMSP). As external layer, a polyglutamate-block-polysarcosine-N 3 (pGlu-b-pSar) coating mediates efficient colloidal stabilization and enables introduction of targeting functionalities by click chemistry. Attaching folate or transferrin ligands to the polymer layer enhances NP uptake into target receptor positive KB and L1210 cells. This study illustrates the development and characterization of metal-drug coordination NPs with high drug content and variable external functionalizations.bloodstream and carry cargo molecules are attractive materials for the utilization as drug containers since their pharmacokinetic properties can be tuned without affecting the pharmacodynamics of the drug. NP drug delivery systems are therefore being investigated to overcome the poor selectivity and major side effects frequently associated with chemotherapy. [1] Conventional chemotherapy often suffers from unfavorable pharmacokinetics, limited tumor accumulation, and systemic toxicity. As a consequence, high doses are required for efficient tumor treatment but the severe doselimiting off-target effects determine a narrow therapeutic window and impair patient benefits in the clinical practice. [2] Recent approaches in nanotechnology work toward ameliorating the situation by developing chemotherapeutic NP formulations aimed at increasing drug selectivity toward neoplastic tissues by employing active and passive targeting strategies of single or combination therapies [3] and enhancing therapeutic indices. [4] At present, about 40 nanomedicines, [5] for instance liposomal doxorubicin [6] and iron-oxide NP formulations, [7] are used for a variety of indications. Recently, highly regular coordination polymers such as metal-organic frameworks [8] (MOFs) have emerged as an additional class of nanomaterials. [9] Several MOFs utilize polydentate carboxylic acid linkers and their

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“…35 Using both coordination modulation, the addition of monotopic modulators that mimic the organic ligands, and oxidation modulation, utilising metal starting materials in different oxidation states to those in the product, it is possible to exert kinetic control over self-assembly and select either the non-interpenetrated MIL-88D(Fe) kinetic product or the two-fold interpenetrated MIL-126(Fe) polymorph that is the thermodynamic product. 34 Coordination modulation has also been used to control the physical properties of Fe-MOFs, such as particle morphology [36][37][38] and size. 39,40 Herein, we apply coordination and oxidation modulation to the synthesis of Fe-terephthalate MOFs, a much more complex system, allowing mapping of the phase space and simple, reproducible isolation of individual phases.…”

Section: Introductionmentioning

confidence: 99%

Exploring and Expanding the Fe-Terephthalate Metal-Organic Framework Phase Space by Coordination and Oxidation Modulation

Bara

Meekel

Pakamorė

et al. 2021

Preprint

View full text Add to dashboard Cite

The synthesis of phase pure metal-organic frameworks (MOFs)network solids of metal clusters connected by organic linkersis often complicated by the possibility of forming multiple diverse phases from one metal-ligand combination. For example, there are at least six Fe-terephthalate MOFs reported to date, with many examples of erroneous assignment of phase based on diffraction data alone. Herein, we show that modulated self-assembly can be used to influence the kinetics of self-assembly of Fe-terephthalate MOFs. We comprehensively assess the effect of addition of both coordinating modulators and pH modulators to the outcome of syntheses, as well as probing the influence of the oxidation state of the Fe precursor (oxidation modulation) and the role of the counteranion on the phase(s) formed. In doing so, we shed light on the thermodynamic landscape of this phase system, uncover mechanistics of modulation, provide robust routes to phase pure materials, often as single crystals, and introduce two new Fe-terephthalate MOFs to an already complex system. The results highlight the potential of modulated self-assembly to bring precision control and new structural diversity to systems that have already received significant study.

show abstract

Morphology Modification of the Iron Fumarate MIL‐88A Metal–Organic Framework Using Formic Acid and Acetic Acid as Modulators

Cited by 48 publications

References 25 publications

Exploring and Expanding the Fe-Terephthalate Metal-Organic Framework Phase Space by Coordination and Oxidation Modulation

Exploring and Expanding the Fe-Terephthalate Metal-Organic Framework Phase Space by Coordination and Oxidation Modulation

Core‐Shell Functionalized Zirconium‐Pemetrexed Coordination Nanoparticles as Carriers with a High Drug Content

Exploring and Expanding the Fe-Terephthalate Metal-Organic Framework Phase Space by Coordination and Oxidation Modulation

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