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131.
Checkers R. Marshall Emma E. Timmel Sara A. Staudhammer Carl K. Brozek 《Chemical science》2020,11(42):11539
Nanoparticles of metal–organic frameworks (nanoMOFs) boast superior properties compared to their bulk analogs, yet little is known about how common synthetic parameters dictate particle sizes. Here, we provide experimental evidence for the “seesaw” model of nanoMOF growth. Solution acidity, ligand excess, and reactant concentrations are decoupled and shown to form the key independent determinants of nanoMOF sizes, thereby validating the proposal that nanoMOFs arise from coupled equilibria involving ligand deprotonation and metal–ligand complexation. By achieving the first demonstration of a seesaw relationship between nanoMOF sizes and ligand excess, these results provide further proof of the model, as they required deliberate manipulation of relationships outlined by the model. Exploring the relative impacts of these parameters reveals that ligand excess has the greatest ability to decrease sizes, although low acidity and high concentrations can exhibit similar effects. As a complement to existing models of polymer formation and crystal growth, the seesaw model therefore offers a powerful tool for reliable control over nanoMOF sizes.Nanoparticles of metal–organic frameworks (nanoMOFs) boast superior properties compared to their bulk analogs, yet little is known about how common synthetic parameters dictate particle sizes. 相似文献
132.
Sara Chumillas Carlos Busó-Rogero José Solla-Gullón Francisco J. Vidal-Iglesias Enrique Herrero Juan M. Feliu 《Electrochemistry communications》2011,13(11):1194-1197
Formic acid and ethanol oxidations on spherical platinum nanoparticles dispersed on carbon with different loadings have been studied. The increasing loading of the catalyst leads to a lower diffusion flux of reactants in the internal parts of the catalyst layer, resulting in a lower apparent activity. In some cases, as in ethanol oxidation, it may also affect the diffusion of the products. As a practical consequence, the structure of the supporting layer and the catalyst loading should be optimized so that the maximum catalyst utilization is obtained. Finally, these diffusion effects may mask some important catalytic activity increase of the nanoparticles. In the case of formic acid, a significant increase in the activity is obtained for very small nanoparticles. 相似文献
133.
Stevens K Claeys DD Catak S Figaroli S Hocek M Tromp JM Schürch S Van Speybroeck V Madder A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(25):6940-6953
Oligodeoxynucleotides incorporating a reactive functionality can cause irreversible cross-linking to the target sequence and have been widely studied for their potential in inhibition of gene expression or development of diagnostic probes for gene analysis. Reactive oligonucleotides further show potential in a supramolecular context for the construction of nanometer-sized DNA-based objects. Inspired by the cytochrome P450 catalyzed transformation of furan into a reactive enal species, we recently introduced a furan-oxidation-based methodology for cross-linking of nucleic acids. Previous experiments using a simple acyclic building block equipped with a furan moiety for incorporation into oligodeoxynucleotides have shown that cross-linking occurs in a very fast and efficient way and that substantial amounts of stable, site-selectively cross-linked species can be isolated. Given the destabilization of duplexes observed upon introduction of the initially designed furan-modified building block into DNA duplexes, we explore here the potential benefits of two new building blocks featuring an extended aromatic system and a restored cyclic backbone. Thorough experimental analysis of cross-linking reactions in a series of contexts, combined with theoretical calculations, permit structural characterization of the formed species and allow assessment of the origin of the enhanced cross-link selectivity. Our experiments clearly show that the modular nature of the furan-modified building blocks used in the current cross-linking strategy allow for fine tuning of both yield and selectivity of the interstrand cross-linking reaction. 相似文献
134.
Aerts A Follens LR Biermans E Bals S Van Tendeloo G Loppinet B Kirschhock CE Martens JA 《Physical chemistry chemical physics : PCCP》2011,13(10):4318-4325
Synchrotron small angle X-ray scattering (SAXS) was used to characterize silicalite-1 zeolite crystallization from TEOS/TPAOH/water clear sol. SAXS patterns were recorded over a broad range of length scales, enabling the simultaneous monitoring of nanoparticles and crystals occurring at various stages of the synthesis. A simple two-population model accurately described the patterns. Nanoparticles were modeled by polydisperse core-shell spheres and crystals by monodisperse oblate ellipsoids. These models were consistent with TEM images. The SAXS results, in conjunction with in situ light scattering, showed that nucleation of crystals occurred in a short period of time. Crystals were uniform in size and shape and became increasingly anisotropic during growth. In the presence of nanoparticles, crystal growth was fast. During crystal growth, the number of nanoparticles decreased gradually but their size was constant. These observations suggested that the nanoparticles were growth units in an aggregative crystal growth mechanism. Crystals grown in the presence of nanoparticles developed a faceted habit and intergrowths. In the final stages of growth, nanoparticles were depleted. Concurrently, the crystal growth rate decreased significantly. 相似文献
135.
Kyle Clagg Sara Hold Archana Kumar Stefan G. Koenig Remy Angelaud 《Tetrahedron letters》2019,60(1):5-7
The direct application of Knochel-Hauser derivative arylmagnesium halides in Kumada-Corriu couplings is described. By utilizing the in situ-generated Grignard reagents, the transmetalation with stoichiometric zinc salts to known Negishi coupling conditions is avoided, thereby streamlining the transformation. Several aromatic hetereocycles participate in the deprotonation and couple with a variety of phenyl iodides and bromides in isolated yields up to 81%. The parent system is demonstrated on 6?g scale with 79% yield, and monitored via ReactIR to show the stability of the Grignard and progression of the deprotonation/CC coupling reaction. 相似文献
136.
Dr. Mahnaz Najafi Dr. Sara Abednatanzi Abbas Yousefi Prof. Mehrorang Ghaedi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):17999-18014
Photocatalysis has been known as one of the promising technologies due to its eco-friendly nature. However, the potential application of many photocatalysts is limited owing to their large bandgaps and inefficient use of the solar spectrum. One strategy to overcome this problem is to combine the advantages of heteroatom-containing supports with active metal centers to accurately adjust the structural parameters. Metal nanoparticles (MNPs) and single atom catalysts (SACs) are excellent candidates due to their distinctive coordination environment which enhances photocatalytic activity. Metal-organic frameworks (MOFs), covalent organic frameworks (COFs) and carbon nitride (g-C3N4) have shown great potential as catalyst support for SACs and MNPs. The numerous combinations of organic linkers with various heteroatoms and metal ions provide unique structural characteristics to achieve advanced materials. This review describes the recent advancement of the modified MOFs, COFs and g-C3N4 with SACs and NPs for enhanced photocatalytic applications with emphasis on environmental remediation. 相似文献
137.
138.
Kittaka A Kurihara M Peleg S Suhara Y Takayama H 《Chemical & pharmaceutical bulletin》2003,51(3):357-358
Hereditary vitamin D-resistant rickets (HVDRR) is a genetic disorder caused by mutations in the vitamin D receptor, which lead to resistance to 1alpha,25-dihydroxyvitamin D(3) [1alpha,25(OH)(2)D(3)]. We found that the A ring-modified analogues, 2alpha-(3-hydroxypropyl)- and 2alpha-(3-hydroxypropoxy)-1alpha,25(OH)(2)D(3), (O1C3 and O2C3) can bind better than the natural hormone to the mutant VDR (R274A), which similar to the HVDRR mutant, R274L, had lost the hydrogen bond to the 1alpha-hydroxyl group of 1alpha,25(OH)(2)D(3). 相似文献
139.
Samskog J Bergström SK Jönsson M Klett O Wetterhall M Markides KE 《Electrophoresis》2003,24(11):1723-1729
A method for coupling an electrophoretic driven separation to a liquid flow, using conventional fused-silica capillaries and a soft polymeric interface is presented. A novel design of the electrode providing high voltage to the electrophoretic separation was also developed. The electrode consisted of a conductive polyimide/graphite imbedded coating immobilized onto the capillary electrophoresis (CE) column inlet. This integrated electrode gave the same separation performance as a commonly used platinum electrode. The on-column electrode also showed good electrochemical stability in chronoamperometric experiments. In addition, with this electrode design, the electrode position relative to the inlet end of the CE column will always be constant and well defined. The on-line flow injection analysis (FIA)-CE system was used with electrospray ionization (ESI)-time of flight (TOF)-mass spectrometry detection. The preparation of the PDMS (poly(dimethylsiloxane)) interface for FIA-CE is described in detail and used for initial tests of the on-column polymer-imbedded graphite inlet electrode. In this interface, a pressure-driven liquid flow, a make up CE electrolyte and a CE column inlet meet in a two-level cross (95 microm ID) in the PDMS structure, enabling independent flow characterization. 相似文献
140.
A designed 12-residue beta-hairpin peptide with a diagonal tryptophan (Trp) pair was shown to bind ATP in water through a combination of aromatic and electrostatic interactions. The affinity for ATP was 5800 M-1 (DeltaG approximately -5.0 kcal/mol), a remarkable affinity for a short, structured peptide in water, consisting of entirely natural amino acid residues. Proton NMR measurements indicate that the adenine ring of the nucleotide is intercalated between the diagonal tryptophans in the bound state. Delineation of the contributions to ATP binding to the hairpin suggest that aromatic interactions contribute approximately -1.8 kcal/mol, while individual electrostatic interactions involving the ATP phosphates and positively charged side chains of the hairpin contribute approximately -1 kcal/mol each. The designed beta-hairpin receptor presents a novel minimalist system to investigate the energetic contributions to protein-nucleic acid recognition through the surface of a beta-sheet. 相似文献