Persistent interactions between hydroxylated nanoballs and atactic poly(2-hydroxyethyl methacrylate)(PHEMA)

Mohomed, K.; Abourahma, Heba; Zaworotko, Michael J.; Harmon, Julie P.

doi:10.1039/b503028e

Cited by 18 publications

(13 citation statements)

References 8 publications

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“…6 Earlier characterization of the solid state structure of the OC 12 -NB revealed that crystallizing solvents with increased polarity forced the pendant OC 12 chains into the interior of the structure. 58 This is in contrast to the hydroxylnanoball composites we studied earlier, 55,56 where glass transition temperature increased smoothly with increasing concentration when the hydroxyl-NBs were dissolved in HEMA and polymerized. This was attributed to the polymer chains threading into the hydroxyl-nanoballs during polymerization.…”

Section: Glass Transition Temperature and Microhardnessmentioning

confidence: 60%

“…In fact, the relation between T g and hardness (H) is almost linear in ideal systems (2). 84 Indeed, our earlier hydroxyl NB studies 55,56 exhibited hardness data that tracked along with the glass transition data. That is, both hardness and glass transition temperature increased with NB concentration in the PHEMA but decreased in the PMMA composites.…”

Section: Glass Transition Temperature and Microhardnessmentioning

confidence: 63%

“…NBs resemble rhombihexahedra with the formula [L 2 Cu 2 (5-R-bdc) 2 ] 12 (L ¼ solvent or substituted pyridine, 5-R-bdc ¼ 5-substituted-benzene-1,3-dicarboxylate). 54 For initial studies, 55,56 we chose a nanoball with hydroxyl functionality: [(DMSO)(MeOH)Cu 2 (5-OH-benzene-1,3-dicarboxylate) 2 ] 12 . This nanoball, referred to as the hydroxyl-NB, has -OH groups on the surface and an internal volume of $1 nm 3 .…”

Section: Introductionmentioning

confidence: 99%

“…58,59 This nanoball attracted our interest because the nonpolar dodecyloxy chains offer a hydrophobic environment for interactions with PMMA and PHEMA, in contrast to the hydroxyl-NB mentioned above. 55,56 OC 12 -NB self-assembles, and the solid structure is [L 2 Cu 2 (OC 12 -bdc) 2 ] 12 [(OC 12 -bdc) 2 ¼ 5-(dodecyloxy)-1,3-benzenedicarboxylate; L ¼ solvent]. In the solid state, the crystal packing is such that each OC 12 -NB is surrounded by four others in a distorted tetrahedral arrangement (Fig.…”

Section: Introductionmentioning

confidence: 99%

“…Results from this study are compared to our earlier results using OH-nanoballs, wherein we found that variation of basic nanocomposite properties directly correlated with nanoball concentration. 55,56 In designing this experiment, we were particularly interested in documenting the effect of the OC 12 chain on how properties varied with NB loading. Herein, we characterize glass transition temperatures, microhardness, and dielectric properties.…”

Section: Introductionmentioning

confidence: 99%

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Zero-periodic metal–organic material, organic polymer composites: tuning properties of methacrylate polymers via dispersion of dodecyloxy-decorated Cu-BDC nanoballs

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Section: Glass Transition Temperature and Microhardnessmentioning

confidence: 60%

Section: Glass Transition Temperature and Microhardnessmentioning

confidence: 63%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Zero-periodic metal–organic material, organic polymer composites: tuning properties of methacrylate polymers via dispersion of dodecyloxy-decorated Cu-BDC nanoballs

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Polymeric Nanoparticles

Vasilakes¹,

Dziubla²,

Wattamwar³

2013

Engineering Polymer Systems for Improved Drug Delivery

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Surface Functionalization of Porous Coordination Nanocages Via Click Chemistry and Their Application in Drug Delivery

et al. 2010

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The discrete coordination-driven self assemblies have received continuous attention due to their molecular architecture esthetics and applications in recognition, catalysis, storage, etc. [ 1 ] Among these self assemblies, one species that has emerged recently is the porous coordination nanocages formed between carboxylate ligands and metal clusters, which are also known as metal-organic polyhedra (MOP). [ 2 ] Due to the robust porous structure and versatile functionality, they have found applications as plasticizer, gas sponge, ion channel, coatings, and building units. [ 3 ] Presumably, the porous shell and uniform yet tunable cavity make them good candidates for drug delivery purpose. However, almost all the coordination nanocages reported so far are hydrophobic, which greatly limits their applications in aqueous condition. We hypothesize this problem can be circumvented by turning these nanocages into colloids through surface functionalization with hydrophilic polymers. In this Communication, we report a porous coordination nanocage covered with alkyne groups and its surface functionalization by grafting with azide-terminated polyethylene glycol (PEG) through "click chemistry". In addition, its drug load and release capacity has been evaluated using an anticancer drug 5-fl uorouracil as a model.The metal-organic cuboctahedron was chosen as the prototype of nanocage in this study. [ 2a , 2c ] It is composed of 12 dicopper paddlewheel clusters and 24 isophthalate moieties, with 8 triangular and 6 square windows that are roughly 8 and 12 Å across, respectively. The internal cavity has a diameter of around 15 Å. The 5-position of isophthalate moieties would be the reaction site for surface functionalization. The Cu(I)-catalyzed Huisgen cycloaddition between azide and alkyne, a so-called "click reaction", was chosen as the synthetic tool in this study due to its high yield, mild reaction condition, and easy operation. [ 4 ] Based on the retrosynthetic analysis and the convenience of implementation, alkyne-covered nanocage and azide-terminated PEG are two prerequisites. The synthesis and characterization of alkyne-covered metal-organic cuboctahedron is not as straightforward as it seems to be. Since NMR signal would be elusive due to the presence of paramagnetic Cu(II) in these nanocages, [ 5 ] single crystal X-ray diffraction might be the only characterization tool available. Therefore, obtaining a single crystal of the nanocage would be of paramount importance for characterization. Figure 1a illustrates all the ligand precursors we've tried in synthesizing this "clickable" nanocage, which comprise isophthalate moiety capable of forming metalorganic cuboctahedron and alkyne group suitable for click reaction. Solvothermal reaction, a process involving heating the ligand/metal mixture solution within sealed environment at high temperature, is often used in synthesizing these coordination nanocages. [ 2a ] The solvothermal reaction between 5-ethynylisophthalic acid (H 2 ei) and copper salt ended up with a coordin...

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Persistent interactions between hydroxylated nanoballs and atactic poly(2-hydroxyethyl methacrylate)(PHEMA)

Cited by 18 publications

References 8 publications

Zero-periodic metal–organic material, organic polymer composites: tuning properties of methacrylate polymers via dispersion of dodecyloxy-decorated Cu-BDC nanoballs

Zero-periodic metal–organic material, organic polymer composites: tuning properties of methacrylate polymers via dispersion of dodecyloxy-decorated Cu-BDC nanoballs

Polymeric Nanoparticles

Surface Functionalization of Porous Coordination Nanocages Via Click Chemistry and Their Application in Drug Delivery

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