| 1. |
- Amombo Noa, Francoise Mystere, 1988, et al.
(författare)
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Metal-Organic Frameworks with Hexakis(4-carboxyphenyl)benzene: Extensions to Reticular Chemistry and Introducing Foldable Nets
- 2020
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 142:20, s. 9471-9481
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Tidskriftsartikel (refereegranskat)abstract
- Nine metal-organic frameworks have been prepared with the hexagon-shaped linker 1,2,3,4,5,6-hexakis(4-carboxyphenyl)-benzene (H(6)cpb) by solvothermal reactions in dimethylformamide (dmf) or dimethylacetamide (dmac) with acetic acid or formic acid as modulators: [Bi-2(cpb)(acetato)(2)(dmf)(2)]center dot 2dmf CTH-6 forms a rtl-net; 2(H2NMe2)[Cu-2(cpb)] CTH-7 forms a kgd-net; [Fe-4(cpb)-(acetato)(2)(dmf)(4)] CTH-8 and [Co-4(cpb)(acetato)(2)(dmf)(4)] CTH-9 are isostructural and form yav-nets; 2(HNEt3)[Fe-2(cpb)] CTH-10 and the two polymorphs of 2(H2NMe2)[Zn-2(cpb)]center dot 1.5dmac, Zn-MOF-888 and CTH-11, show kgd-nets; [Cu-2(cpb)-(acetato)(2)(dmf)(2)]center dot 2dmf, CTH-12, forms a mixed coordination and hydrogen-bonded sql-net; and 2(H2NMe2)[Zn-2(cpb)] CTH-13, a similarly mixed yav-net. Surface area values (Brunauer-Emmett-Teller, BET) range from 34 m(2) g(-1) for CTH-12 to 303 m(2) g(-1) for CTH-9 for samples activated at 120 degrees C in dynamic vacuum. All compounds show normal (10-fold higher) molar CO2 versus N-2 uptake at 298 K, except the 19-fold CO2 uptake for CTH-12 containing Cu(II) dinuclear paddle-wheels. We also show how perfect hexagons and triangles can combine to a new 3D topology laf, a model of which gave us the idea of foldable network topologies, as the laf-net can fold into a 2D form while retaining the local geometry around each vertex. Other foldable nets identified are cds, cds-a, ths, sqc163, clh, jem, and tfc covering the basic polygons and their combinations. The impact of this concept on "breathing" MOFs is discussed. I-2 sorption, both from gas phase and from MeOH solution, into CTH-7 were studied by time of flight secondary ion mass spectrometry (ToF-SIMS) on dried crystals. I-2 was shown to have penetrated the crystals, as layers were consecutively peeled off by the ion beam. We suggest ToF-SIMS to be a method for studying sorption depth profiles of MOFs.
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| 2. |
- Brülls, Steffen, 1991, et al.
(författare)
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Bonding between π-Conjugated Polycations and Monolayer Graphene: Decisive Role of Anions
- 2023
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 127:4, s. 1917-28
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Tidskriftsartikel (refereegranskat)abstract
- Functionalization and precise modulation of the electronic properties of graphene are key processes in the development of new applications of this promising material. This study examines the potential of using organic polycations as p-dopants and/or anchoring motifs for non-covalent functionalization. A library of hybrid materials was prepared through wet-chemical non-covalent functionalization. Both chemical vapor deposition graphene and reduced graphene oxide were functionalized with a series of neutral and polycationic benzimidazole-based systems. We report on how both the number of anions and the size, shape, and magnitude of the positive charge of the benzimidazole-based systems cooperatively affect the redox properties as well as the affinity for and the nature of bonding to graphene. The redox properties of the benzimidazole-based systems were studied by cyclic voltammetry. The functionalized graphene materials were characterized by Raman spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry. Density functional theory calculations were performed to make contact between the experimental results obtained for molecular samples and hybrid materials. No universal dependence of the binding affinity on a single parameter, such as the amount of positive charge or the size of the system, was found. Instead, the cooperative effect of the three-dimensional structure of the benzimidazole-based systems and the number of anions was found to play a pivotal role. Together, these parameters determine the degree of partial electron sharing and magnitude of dispersion forces involved in the binding of members of this family of benzimidazole-based systems to graphene.
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| 3. |
- Brülls, Steffen, 1991, et al.
(författare)
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Evidence for Electron Transfer between Graphene and Non-Covalently Bound pi-Systems
- 2020
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Ingår i: Chemistry - A European Journal. - : Wiley. - 1521-3765 .- 0947-6539. ; 26:29, s. 6694-6702
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Tidskriftsartikel (refereegranskat)abstract
- Hybridizing graphene and molecules possess a high potential for developing materials for new applications. However, new methods to characterize such hybrids must be developed. Herein, the wet-chemical non-covalent functionalization of graphene with cationic pi-systems is presented and the interaction between graphene and the molecules is characterized in detail. A series of tricationic benzimidazolium salts with various steric demand and counterions was synthesized, characterized and used for the fabrication of graphene hybrids. Subsequently, the doping effects were studied. The molecules are adsorbed onto graphene and studied by Raman spectroscopy, XPS as well as ToF-SIMS. The charged pi-systems show a p-doping effect on the underlying graphene. Consequently, the tricationic molecules are reduced through a partial electron transfer process from graphene, a process which is accompanied by the loss of counterions. DFT calculations support this hypothesis and the strong p-doping could be confirmed in fabricated monolayer graphene/hybrid FET devices. The results are the basis to develop sensor applications, which are based on analyte/molecule interactions and effects on doping.
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| 4. |
- Brülls, Steffen, 1991
(författare)
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Non-covalent Modification of Graphene and MoS2 Synthesis and Characterization of Charged Molecules and Two-Dimensional Materials
- 2020
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Graphene is a material of superlatives. It has unique properties, which are explored in various areas of interdisciplinary research. Graphene can improve the properties of other materials or even give them new functions and is therefore a suitable candidate for different sensor applications. While covalent functionalization of graphene comprises the outstanding properties of graphene, non-covalent modification of graphene does not affect the outstanding properties of graphene. Next to graphene there are other two-dimensional materials such as molybdenum disulfide in the focus of research, which increases the scope of applications for two-dimensional materials. This thesis presents the synthesis of a series of neutral and charged π-conjugated systems with a different amount of either benzimidazole or pyridine moieties. The molecules differ in the size of their π-conjugated system, the amount of charges, and the counter ions. Selected molecules were used to non-covalently functionalize either graphene or molybdenum disulfide. The new two-dimensional materials were characterized by Raman spectroscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, atomic force microscopy and Time-of-Flight secondary ion mass spectrometry. Both, neutral and charged molecules can interact with graphene/ molybdenum disulfide via intermolecular forces. Computational studies support experimental observations and helped to gain more insight about the intermolecular attraction between the π-conjugated systems and graphene. Lastly, the non-covalently functionalized graphene was used to fabricate FET-devices, which showed strong p-doping of the underlying graphene by the π-conjugated systems. To summarize, we showed the non-covalent functionalization of graphene and molybdenum disulfide with π-conjugated molecules and the influence of structural and electrochemical parameters on the interaction with graphene or molybdenum disulfide. The results presented in this thesis can be the basis of novel sensors on the nanoscale such as a pH-meter or a humidity sensors.
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| 5. |
- Kaya, Ibrahim, et al.
(författare)
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On-Tissue Chemical Derivatization of Catecholamines Using 4-(N-Methyl)pyridinium Boronic Acid for ToF-SIMS and LDI-ToF Mass Spectrometry Imaging
- 2018
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Ingår i: Analytical Chemistry. - : American Chemical Society (ACS). - 0003-2700 .- 1520-6882. ; 90:22, s. 13580-13590
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Tidskriftsartikel (refereegranskat)abstract
- The analysis of small polar compounds with ToF-SIMS and MALDI-ToF-MS have been generally hindered by low detection sensitivity, poor ionization efficiency, ion suppression, analyte in-source fragmentation, and background spectral interferences from either a MALDI matrix and/or endogenous tissue components. Chemical derivatization has been a well-established strategy for improved mass spectrometric detection of many small molecular weight endogenous compounds in tissues. Here, we present a devised strategy to selectively derivatize and sensitively detect catecholamines with both secondary ion ejection and laser desorption ionization strategies, which are used in many imaging mass spectrometry (IMS) experiments. Chemical derivatization of catecholamines was performed by a reaction with a synthesized permanent pyridinium-cation-containing boronic acid molecule, 4-(N-methyl)pyridinium boronic acid, through boronate ester formation (boronic acid-diol reaction). The derivatization facilitates their sensitive detection with ToF-SIMS and LDI-ToF mass spectrometric techniques. 4-(N-Methyl)pyridinium boronic acid worked as a reactive matrix for catecholamines with LDI and improved the sensitivity of detection for both SIMS and LDI, while the isotopic abundances of the boron atom reflect a unique isotopic pattern for derivatized catecholamines in MS analysis. Finally, the devised strategy was applied, as a proof of concept, for on-tissue chemical derivatization and GCIB-ToF-SIMS (down to 3 μm per pixel spatial resolution) and LDI-ToF mass spectrometry imaging of dopamine, epinephrine, and norepinephrine in porcine adrenal gland tissue sections. MS/MS using collision-induced dissociation (CID)-ToF-ToF-SIMS was subsequently employed on the same tissue sections after SIMS and LDI mass spectrometry imaging experiments, which provided tandem MS information for the validation of the derivatized catecholamines in situ. This methodology can be a powerful approach for the selective and sensitive ionization/detection and spatial localization of diol-containing molecules such as aminols, vic-diols, saccharides, and glycans along with catecholamines in tissue sections with both SIMS and LDI/MALDI-MS techniques. © 2018 American Chemical Society.
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| 6. |
- Rietsch, Philipp, et al.
(författare)
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Fluorescence of a chiral pentaphene derivative derived from the hexabenzocoronene Motif
- 2019
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Ingår i: Chemical Communications. - : Royal Society of Chemistry (RSC). - 1364-548X .- 1359-7345. ; 55:71, s. 10515-10518
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Tidskriftsartikel (refereegranskat)abstract
- A new fluorescent pentaphene derivative is presented that differs from hexabenzocoronene (HBC) by one carbon atom in the basal plane skeleton. A 500% increased fluorescence quantum yield is measured compared to the HBC derivative. The pentaphene compound, obtained by a modified Scholl oxidation, is also emissive in the solid-state, due to the packing motif in the crystal.
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