- Paddle Wheel Based Triazolyl Isophthalate MOFs: Impact of Linker Modification on Crystal Structure and Gas Sorption Properties
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Syntheses and comprehensive characterization of two closely related series of isomorphous metal-organic frameworks (MOFs) based on triazolyl isophthalate linkers with the general formula ∞3[M2(R1-R2-trz-ia)2] (M = Cu, Zn) are presented. Using solvothermal synthesis and synthesis of microcrystalline materials on the gram scale by refluxing a solution of the starting materials, 11 MOFs are readily available for a systematic investigation of structure-property relationships. The networks of the two series are assigned to rutile (rtl) (1-4) and α-PbO2 (apo) (5-9) topology, respectively. Due to the orientation of the triazole substituents toward the cavities, both the pore volume and the pore diameter can be adjusted by choice of the alkyl substituents. Compounds 1-9 exhibit pronounced microporosity with calculated porosities of 31-53% and show thermal stability up to 390 °C as confirmed by simultaneous thermal analysis. Systematic investigation of adsorption properties by CO2 (298 K) and N2 (77 K) adsorption studies reveal remarkable network flexibility induced by alkyl substituents on the linker. Fine-tuning of the gate opening pressure and of the hysteresis shape is possible by adjusting the substitution pattern and by choice of the metal ion.
- Kobalz, Merten,Lincke, J?rg,Kobalz, Karolin,Erhart, Oliver,Bergmann, Jens,L?ssig, Daniel,Lange, Marcus,M?llmer, Jens,Gl?ser, Roger,Staudt, Reiner,Krautscheid, Harald
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- Synthesis and Exfoliation of a New Layered Mesoporous Zr-MOF Comprising Hexa- A nd Dodecanuclear Clusters as Well as a Small Organic Linker Molecule
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A new layered mesoporous Zr-MOF of composition [Zr30O20(OH)26(OAc)18L18] was synthesized by employing 5-acetamidoisophthalic acid (H2L) using acetic acid as the solvent. The new MOF, denoted as CAU-45, exhibits a honeycomb structure of stacked layers which comprise both hexa- A nd dodecanucelar zirconium clusters. Its structure was solved from submicrometer-sized crystals by continuous rotation electron diffraction (cRED). Liquid phase exfoliation and size selection were successfully performed on the material.
- Leubner, Sebastian,Bengtsson, Viktor E. G.,Synnatschke, Kevin,Gosch, Jonas,Koch, Alexander,Reinsch, Helge,Xu, Hongyi,Backes, Claudia,Zou, Xiaodong,Stock, Norbert
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- Solvent-Dependent Structural Variation of Zinc(II) Coordination Polymers and Their Catalytic Activity in the Knoevenagel Condensation Reaction
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The novel self-assembled zinc(II) coordination polymers [Zn(L)(H2O)2]n (1), [Zn(L)(H2O)2]n·n(formamide) (2), [Zn(L)(H2O)2]n·n(N-methylformamide) (3), [Zn(L)
- Karmakar, Anirban,Rúbio, Guilherme M. D. M.,Guedes Da Silva, M. Fátima C.,Hazra, Susanta,Pombeiro, Armando J. L.
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- Isoreticular Chemistry of Group 13 Metal-Organic Framework Compounds Based on V-Shaped Linker Molecules: Exceptions to the Rule?
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Following the concept of isoreticular chemistry, we carried out a systematic study on Ga-containing metal-organic frameworks (MOFs) using six V-shaped linker molecules of differing sizes, geometries, and additional functional groups. The linkers included three isophthalic acid derivatives (m-H2BDC-R, R = CH3, OCH3, NHCOCH3), thiophene-2,5-dicarboxylic acid (H2TDC), and two 4,4′-sulfonyldibenzoic acid derivatives (H2SDBA, DPSTA). The crystal structures of seven compounds were elucidated by a combination of model building, single-crystal X-ray diffraction (SCXRD), three-dimensional electron diffraction (3D ED), and Rietveld refinements against powder X-ray diffraction (PXRD) data. Four new Ga-MOFs that are isoreticular with their aluminum counterparts, i.e. Ga-CAU-10-R (Ga(OH)(m-BDC-R); R = OCH3, NHCOCH3), Ga-CAU-11 (Ga(OH)(SDBA)), and Ga-CAU-11-COOH (Ga(OH)(H2DPSTC)), were obtained. For the first time large single crystals of a MOF crystallizing in the CAU-10 structure type could be isolated, i.e. Ga-CAU-10-OCH3, which permitted a detailed structural characterization. In addition, the use of 5-methylisophthalic acid and thiophene-2,5-dicarboxylic acid resulted in two new Ga-MOFs denoted Ga-CAU-49 and Ga-CAU-51, respectively, which are not isostructural with any known Al-MOF. The crystal structure of Ga-CAU-49 ([Ga4(m-HBDC-CH3)2(m-BDC-CH3)3(OH)4(H2O)]) contains an unprecedented rod-shaped inorganic building unit (IBU) of the formula ∞1{Ga16(OH)18O60}, composed of corner-sharing GaO5 and GaO6 polyhedra. In Ga-CAU-51 ([Ga(OH)(C5H2O2S)]) chains of alternating cis and trans corner-sharing GaO6 polyhedra form the IBU. A detailed characterization of the title compounds was carried out, including nitrogen gas and water vapor sorption measurements. Ga-CAU-11 was the only compound exhibiting porosity toward nitrogen with a type I isotherm, a specific surface area of aS,BET = 210 m2/g, and a micropore volume of Vmic = 0.09 cm3/g. The new MOF Ga-CAU-51 exhibits exceptional water sorption properties with a reversible S-shaped isotherm and a high uptake around p/p0 = 0.38 of mads = 370 mg/g.
- Grape, Erik Svensson,Inge, A. Ken,Lieb, Alexandra,Rabe, Timo,Reinsch, Helge,Rohr, Hauke,Stock, Norbert,W?hlbrandt, Stephan
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- Thioacids mediated selective and mild N-acylation of amines
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N-Acylated amines are ubiquitous in nature. Selective N-acylation at neutral conditions remains a key area of interest. Here we are reporting the copper sulfate-mediated highly selective, mild, and rapid N-acylation of various aliphatic and aromatic amines using thioacids in methanol at neutral conditions. All N-acylated products of primary and secondary amines were isolated in good to excellent yields. This method is found to be highly selective for the amines and not sensitive to other functional groups such as phenols, alcohols, and thiols. The simple workup, high yields, and high selectivity of this reaction can be an attractive alternative to those of the existing acyl halide- and acid anhydride-mediated N-acylation reactions.
- Mali, Sachitanand M.,Bhaisare, Rupal D.,Gopi, Hosahudya N.
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p. 5550 - 5555
(2013/07/25)
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- Synthesis and evaluation of fully (5-amidoisophthalic acid)-functionalised polyacrylamides as selective inhibitors of the beta crystal polymorph of L-glutamic acid
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Poly-N-5-acrylamidoisophthalic acid (4), poly-N-(5-(N-(3,5-dicarboxyphenyl) carbamoyl)pentyl)acryl-amide (10a) and poly-N-(11-(N-(3,5-dicarboxyphenyl) carbamoyl)undecyl)acrylamide (10b) were prepared and assessed as polymorph-selective crystallization inhibitors of the stable b form of L-glutamic acid.Polymerization was carried out as the final step in the preparation of 10a and 10b to ensure the preparation of fully functionalized polymers.Polymers 4, 10a and 10b were effective as complete inhibitors of the stable b form of L-glutamic acid in quantities of 0.5% w/w or greater, whereas the corresponding 'monomeric' additives 2 and 11 required quantities of 3% or greater to completely inhibit the b form, demonstrating a cooperative binding effect by the polymeric additives.Within the series of polymers 4, 10a and 10b, polymer 10a, which features a short tethering chain, was the most effective.
- Kelly, Dawn M.,Moynihan, Humphrey A.
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experimental part
p. 5459 - 5466
(2010/08/13)
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- Naaladase inhibitors for treating retinal disorders and glaucoma
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The present invention relates to pharmaceutical compositions and methods for treating a retinal disorder or glaucoma using NAALADase inhibitors.
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- Naaladase inhibitors for treating amyotrophic lateral sclerosis
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The present invention relates to pharmaceutical compositions and methods for treating amyotrophic lateral sclerosis using NAALADase inhibitors.
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- Benzenedicarboxylic acid derivatives
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New benzenedicarboxylic acid derivative compounds; pharmaceutical compositions, diagnostic methods, and diagnstic kits that include those compounds; and methods of using those compounds for inhibiting NAALADase enzyme activity, detecting diseases where NAALADase levels are altered, effecting neuronal activity, effecting TGF-β activity, inhibiting angiogenesis, and treating glutamate abnormalities, neutopathy, pain, compulsive disorders, prostate diseases, cancers, and glaucoma.
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- THE INHIBITION OF GLUTAMATE DEHYDROGENASE BY DERIVATIVES OF ISOPHTHALIC ACID
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A range of compounds, structurally related to glutamate, have been tested as inhibitors of pea leaf glutamate dehydrogenase assayed in either direction.Only 5-N-substituted derivatives of aminoisophthalic acid completely inhibited the enzyme when tested at concentrations equal to either those of 2-oxoglutarate or glutamate.A minimum of three carbon atoms attached linearly to the amino group was required for maximum inhibition, inhibition was removed if there was any substitution on the first carbon.The 5-N-substituted derivatives also inhibited yeast (to a greater extent) and bovine liver (to a lesser extent) glutamate dehydrogenases.Key Word Index - Pisum sativum; Leguminoseae; yeast; bovine; glutamate dehydrogenase inhibition; isophthalic acid derivatives.
- Cunliffe, Denise,Leason, Mark,Parkin, Donald,Lea, Peter J.
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p. 1357 - 1360
(2007/10/02)
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