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A series of isostructural 3D coordination polymers (3)∞[M(tdc)(bpy)] (M(2+) = Zn(2+), Cd(2+), Co(2+), Fe(2+); tdc(2-) = 2,5-thiophenedicarboxylate; bpy = 4,4'-bipyridine) was synthesized and characterized by X-ray diffraction, thermal analysis, and gas adsorption measurements. The materials show high thermal stability up to approximately 400 °C and a solvent induced phase transition. Single crystal X-ray structure determination was successfully performed for all compounds after the phase transition. In the zinc-based coordination polymer, various amounts of a second type of metal ions such as Co(2+) or Fe(2+) could be incorporated. Furthermore, the catalytic behavior of the homo- and heteronuclear 3D coordination polymers in an oxidation model reaction was investigated.
Adsorption of N2 and CO2 on Activated Carbon, AlO(OH) Nanoparticles, and AlO(OH) Hollow Spheres
(2015)
Phosphate-based inorganic–organic hybrid nanoparticles (IOH-NPs) with the general composition [M]2+[Rfunction(O)PO3]2– (M = ZrO, Mg2O; R = functional organic group) show multipurpose and multifunctional properties. If [Rfunction(O)PO3]2– is a fluorescent dye anion ([RdyeOPO3]2–), the IOH-NPs show blue, green, red, and near-infrared fluorescence. This is shown for [ZrO]2+[PUP]2–, [ZrO]2+[MFP]2–, [ZrO]2+[RRP]2–, and [ZrO]2+[DUT]2– (PUP = phenylumbelliferon phosphate, MFP = methylfluorescein phosphate, RRP = resorufin phosphate, DUT = Dyomics-647 uridine triphosphate). With pharmaceutical agents as functional anions ([RdrugOPO3]2–), drug transport and release of anti-inflammatory ([ZrO]2+[BMP]2–) and antitumor agents ([ZrO]2+[FdUMP]2–) with an up to 80% load of active drug is possible (BMP = betamethason phosphate, FdUMP = 5′-fluoro-2′-deoxyuridine 5′-monophosphate). A combination of fluorescent dye and drug anions is possible as well and shown for [ZrO]2+[BMP]2–0.996[DUT]2–0.004. Merging of functional anions, in general, results in [ZrO]2+([RdrugOPO3]1–x[RdyeOPO3]x)2– nanoparticles and is highly relevant for theranostics. Amine-based functional anions in [MgO]2+[RaminePO3]2– IOH-NPs, finally, show CO2 sorption (up to 180 mg g–1) and can be used for CO2/N2 separation (selectivity up to α = 23). This includes aminomethyl phosphonate [AMP]2–, 1-aminoethyl phosphonate [1AEP]2–, 2-aminoethyl phosphonate [2AEP]2–, aminopropyl phosphonate [APP]2–, and aminobutyl phosphonate [ABP]2–. All [M]2+[Rfunction(O)PO3]2– IOH-NPs are prepared via noncomplex synthesis in water, which facilitates practical handling and which is optimal for biomedical application. In sum, all IOH-NPs have very similar chemical compositions but can address a variety of different functions, including fluorescence, drug delivery, and CO2 sorption.
Eine neue Prozessidee zur Auftrennung racemischer Wirkstoffe unter Verwendung nanoskaliger AlO(OH)‐Hohlkugeln als Adsorbens und überkritischen Kohlenstoffdioxides (sc‐CO2) als Lösungsmittel wird vorgestellt. Zur Auslegung des Prozesses werden Untersuchungen zur Abscheidung der racemischen Wirkstoffe (RS)‐Flurbiprofen, (RS)‐Ibuprofen, (RS)‐Ketoprofen und den reinen Enantiomeren (R)‐Flurbiprofen, (S)‐Ibuprofen und (S)‐Ketoprofen an AlO(OH)‐Hohlkugeln präsentiert und bewertet. Zudem werden Adsorptionsdaten von gasförmigem CO2 an den Hohlkugeln und kommerziellen AlO(OH)‐Partikeln, die mit einer Magnetschwebewaage ermittelt wurden, verglichen. Abschließend werden erste Ergebnisse von orientierenden Versuchen zur Adsorption von racemischem Flurbiprofen aus sc‐CO2 an den Hohlkugeln vorgestellt.