- Functionalization in flexible porous solids: Effects on the pore opening and the host-guest interactions
-
The synthesis on the gram scale and characterization of a series of flexible functionalized iron terephthalate MIL-53(Fe) type solids are reported. Chemical groups of various polarities, hydrophilicities, and acidities (-Cl, -Br, -CF3, -CH3, -NH2, -OH, -CO2H) were introduced through the aromatic linker, to systematically modify the pore surface. X-ray powder diffraction (XRPD), molecular simulations, thermogravimetric analyses, and in situ IR and 57Fe Moessbauer spectrometries indicate some similarities with the pristine MIL-53(Fe) solid, with the adoption of the narrow pore form for all solids in both the hydrated and dry forms. Combined XRPD and computational structure determinations allow concluding that the geometry of the pore opening is predominantly correlated with the intraframework interactions rather than the steric hindrance of the substituent. Only (MIL-53(Fe)-(CF3)2) exhibits a nitrogen accessible porosity (SBET ≈ 100 m2 g-1). The adsorption of some liquids leads to pore openings showing some very specific behaviors depending on the guest-MIL-53(Fe) framework interactions, which can be related to the energy difference between the narrow and large pore forms evaluated by molecular simulation.
- Devic, Thomas,Horcajada, Patricia,Serre, Christian,Salles, Fabrice,Maurin, Guillaume,Moulin, Beatrice,Heurtaux, Daniela,Clet, Guillaume,Vimont, Alexandre,Greneche, Jean-Marc,Le Ouay, Benjamin,Moreau, Florian,Magnier, Emmanuel,Filinchuk, Yaroslav,Marrot, Jerome,Lavalley, Jean-Claude,Daturi, Marco,Ferey, Gerard
-
-
Read Online
- Microwave-assisted solvothermal synthesis and optical properties of tagged MIL-140A metal-organic frameworks
-
A series of tagged MIL-140A-R frameworks have been synthesized using a microwave-assisted solvothermal method. Compared with their UiO-66-R polymorphs, the absorption energies in the MIL-140A-R series (R = NH2, NO 2, Br, Cl, and F) are extended toward the visible region because of the spatial arrangement of the linkers.
- Liang, Weibin,Babarao, Ravichandar,D'Alessandro, Deanna M.
-
-
Read Online
- Preparation method of aromatic dicarboxylic acid derivative
-
The invention provides a preparation method of an aromatic dicarboxylic acid derivative, wherein the preparation method comprises the following steps: step 1, carrying out a coupling reaction on dihalogenated aromatic hydrocarbon and metal cyanide at a temperature of 40-200 DEG C under metal catalysis in a solvent, and carrying out extraction layering concentration to obtain a dicyano compound after the reaction is finished; and step 2, carrying out a hydrolysis reaction on the obtained dicyanogen compound at the temperature of 60-200 DEG C under an acidic condition, and carrying out post-treatment to obtain the final product. According to the preparation method of the aromatic dicarboxylic acid derivative, dihalogenated aromatic hydrocarbon reacts with metal cyanide and then is hydrolyzedunder the acidic condition to obtain aromatic acid or the derivative thereof, and the preparation method has the remarkable advantages that the raw materials are cheap and easy to obtain, operation is easy and convenient, the yield is high, three wastes are easy to dispose, the product quality is high, and the substrate tolerance is good.
- -
-
Paragraph 0025; 0049-0052
(2021/03/11)
-
- BIS-BENZIMIDAZOLE COMPOUNDS AND METHODS OF USING SAME
-
Provided herein are compounds and methods for modulating abnormal repeat expansions of gene sequences. More particularly, provided are inhibitors of RNA and the uses of such inhibitors in regulating nucleotide repeat expansions, e.g., to treat Myotonic Dystrophy Type 1 (DM1 ), Myotonic Dystrophy Type 2 (DM2), Fuchs dystrophy, Huntington Disease, Amyotrophic Lateral Sclerosis, or Frontotemporal Dementia.
- -
-
Paragraph 00922-00924
(2019/06/05)
-
- Halogen bonding in UiO-66 frameworks promotes superior chemical warfare agent simulant degradation
-
Herein, a series of halogenated UiO-66 derivatives was synthesized and analyzed for the breakdown of the chemical warfare agent simulant dimethyl-4-nitrophenyl phosphate (DMNP) to analyze ligand effects. UiO-66-I degrades DMNP at a rate four times faster than the most active previously reported MOFs. MOF defects were quantified and ruled out as a cause for increased activity. Theoretical calculations suggest the enhanced activity of UiO-66-I originates from halogen bonding of the iodine atom to the phosphoester linkage allowing for more rapid hydrolysis of the P-O bond.
- Kalaj, Mark,Momeni, Mohammad R.,Bentz, Kyle C.,Barcus, Kyle S.,Palomba, Joseph M.,Paesani, Francesco,Cohen, Seth M.
-
supporting information
p. 3481 - 3484
(2019/03/26)
-
- Cerium-based metal organic frameworks with UiO-66 architecture: Synthesis, properties and redox catalytic activity
-
A series of nine Ce(IV)-based metal organic frameworks with the UiO-66 structure containing linker molecules of different sizes and functionalities were obtained under mild synthesis conditions and short reaction times. Thermal and chemical stabilities were determined and a Ce-UiO-66-BDC/TEMPO system was successfully employed for the aerobic oxidation of benzyl alcohol.
- Lammert, Martin,Wharmby, Michael T.,Smolders, Simon,Bueken, Bart,Lieb, Alexandra,Lomachenko, Kirill A.,De Vos, Dirk,Stock, Norbert
-
supporting information
p. 12578 - 12581
(2015/08/06)
-
- Tuning the hydrogenation activity of Pd NPs on Al-MIL-53 by linker modification
-
The hydrogenation activity of 3 wt.% Pd nanoparticles supported on various mono-group (H, OCH3, NH2, Cl, and NO2) substituted Al-MIL-53 materials has been investigated. Substituents enhanced the dispersion of palladium nanoparticles on Al-MIL-53, leading to a narrow particle size distribution in the range of 2 to 4 nm. Pd nanoparticles on fresh catalysts were present as a mixture of Pd(ii) and Pd(0) with different ratios. These Pd species readily became metallic in a hydrogen flow even at room temperature. Their activities in hydrogenation of phenol and phenylacetylene are linked to the substituents on the aromatic ring of the framework. Catalysts with electron-donating groups (OCH3 and NH2) show much higher activity than those containing electron-withdrawing groups (Cl and NO2). This behavior might be explained by the hydrogen dissociation abilities of metallic Pd nanoparticles affected by the organic linkers.
- Zhang, Damin,Guan, Yejun,Hensen, Emiel J. M.,Xue, Teng,Wang, Yimeng
-
p. 795 - 802
(2014/03/21)
-
- Single- and mixed-linker Cr-MIL-101 derivatives: A high-throughput investigation
-
New single- and mixed-linker Cr-MIL-101 derivatives bearing different functional groups have been synthesized. The influence of the reaction parameters, such as metal source (CrO3, CrCl3, and Cr(NO3)3·9H2O) or linker composition, on product formation have been investigated using high-throughput methods. Highly crystalline Cr-MIL-101 materials were obtained with CrCl3 as the metal source with either 2-bromoterephthalic (TA-Br) or 2-nitroterephthalic (TA-NO2) acid as one of the mixed-linker components. On the basis of these results, numerous new mixed-linker Cr-MIL-101 derivatives containing -NH2, -NO2, -H, -SO3H, -Br, -OH, -CH 3, and -COOH have been synthesized. The use of TA-NH2 and TA-OH were shown, under the same reaction conditions, to lead to decarboxylation and the formation of 3-amino- and 3-hydroxybenzoic acid, respectively. Furthermore, we were also able to directly synthesize single-linker Cr-MIL-101-X derivatives with X = F, Cl, Br, CH3. Postsynthetic modification was used to selectively reduce the mixed-linker compound Cr-MIL-101-Br-NO 2 to Cr-MIL-101-Br-NH2. To establish the successful incorporation of the linker molecules and possible decomposition of certain starting materials, 1H NMR spectra of dissolved reaction products were recorded.
- Lammert, Martin,Bernt, Stephan,Vermoortele, Frederik,De Vos, Dirk E.,Stock, Norbert
-
supporting information
p. 8521 - 8528
(2013/09/02)
-
- USE OF A POROUS CRYSTALLINE HYBRID SOLID AS A NITROGEN OXIDE REDUCTION CATALYST AND DEVICES
-
The present invention relates to the use of solids consisting of a metal-organic framework (MOF) and having the units of the following formula (I): MmOkXILp as a nitrogen-oxide catalyst. The present invention also relates to devices for enabling the implementation of said use. The nitrogen oxides in question are nitrogen monoxide and nitrogen dioxide, collectively referred to as NOx. The MOF solids of the present invention are advantageously capable of removing nitrogen oxides from a liquid or gaseous effluent, for example from water, from the exhaust gases of a vehicle, factory, workshop, laboratory, stored products, urban air vents, etc., without any reducing agent and at a low temperature. The DeNOx catalysis is a major issue for our societies. The invention can be used for reducing or even avoiding the consequences for public health of the toxic NOx gases resulting from human activity.
- -
-
-
- POROUS CRYSTALLINE HYBRID SOLID FOR ADSORBING AND RELEASING GAS OF BIOLOGICAL INTEREST
-
The invention relates to solids made of a porous crystalline metal-organic framework (MOF) loaded with at least one gas of biological interest, and to a method for preparing the same. The MOF solids of the present invention are capable of adsorbing and releasing in a controlled manner gases having a biological interest. They can be used in the pharmaceutical field and/or for applications in the cosmetic field. They can also be used in the food industry.
- -
-
-
- REDUCIBLE POROUS CRYSTALLINE HYBRID SOLID FOR THE SEPARATION OF MIXTURES OF MOLECULES HAVING DIFFERENT DEGREES AND/OR A DIFFERENT NUMBER OF UNSATURATIONS
-
The present invention relates to reducible porous crystalline solids, constituted of a metal-organic framework (MOF), for the separation of mixtures of molecules having different unsaturation degrees and/or a different number of unsaturations with a selectivity that can be adjusted by controlling the reduction of the MOF. The MOF solids of the present invention, after reduction, have a strong affinity for molecules containing at least one unsaturation. They can be used in various separation processes, especially those relating to hydrocarbons.
- -
-
Page/Page column 25
(2011/08/03)
-
- SOLID INORGANIC/ORGANIC HYBRID WITH MODIFIED SURFACE
-
The invention relates to solid organometallic hybrids with modified surface. Said solid may be used for example for the encapsulation and vectoring of molecules of interest such as active pharmaceutical agents, compounds of interest in cosmetics and markers, for example, contrast agents. Said solids show good results in terms of loading capacity in medicament agents and in biocompatibility.
- -
-
-
- PROLYL HYDROXYLASE INHIBITORS
-
The invention described herein relates to certain 2,4-dioxo-l,2,3,4-tetrahydro-7- quinazolinecarboxamide derivatives of formula (I) which are antagonists of HIF prolyl hydroxylases and are useful for treating diseases benefiting from the inhibition of this enzyme, anemia being one example.
- -
-
Page/Page column 25
(2010/07/10)
-
- ORGANIC/INORGANIC HYBRID NANOPARTICULATES MADE FROM IRON CARBOXYLATES
-
The invention relates to nanoparticles made from organometallic hybrid materials made from iron carboxylates, used for example as contrast agents. The particles can also be used for the encapsulation and vectoring of molecules of interest such as active3 pharmaceutical agents, cosmetically interesting compounds and markers. Apart from the intrinsic properties thereof for imaging, said nanoparticles give good results in terms of capacity for loading with medicaments and in biocompatibility.
- -
-
Page/Page column 21
(2010/08/22)
-
- PYRIDYL INHIBITORS OF HEDGEHOG SIGNALLING
-
The invention provides novel inhibitors of hedgehog signaling that are useful as s therapeutic agent for treating malignancies where the compounds have the general formula (I): where A, X, Y R1, R2, R3, R4, m and n are as described herein.
- -
-
Page/Page column 119-120
(2009/11/29)
-
- PROCESS FOR THE SYNTHESIS OF HALOGENATED AROMATIC DIACIDS
-
The production of high-purity halogenated aromatic diacids from halogenated dimethylbenzene by oxidation with an oxygen-containing gas is conducted using a four-component catalyst system and a two-stage temperature process.
- -
-
Page/Page column 17
(2008/12/07)
-
- Pyridyl inhibitors of hedgehog signalling
-
The invention provides novel inhibitors of hedgehog signaling that are useful as a therapeutic agents for treating malignancies where the compounds have the general formula I: wherein A, X, Y R1, R2, R3, R4, m and n are as described herein.
- -
-
Page/Page column 88-89
(2010/10/20)
-
- COBALT CARBONYL CATALYZED POLYCARBONYLATION OF POLYHALOGENATED AROMATICS UNDER PHOTOSTIMULATION
-
Cobalt carbonyl catalyzed polycarbonylation of much less reactive polychlorobenzenes could be easily achieved under photostimulation in aqueous sodium hydroxide.All these reactions could be performed without any organic solvent(in some cases, ethanol was used as a co-solvent) and any phase transfer catalyst.
- Kashimura, Tsugunori,Kudo, Kiyoshi,Mori, Sadayuki,Sugita, Nobuyuki
-
p. 299 - 302
(2007/10/02)
-
