46 results on '"Valkenier H"'
Search Results
2. Electric-field control of interfering transport pathways in a single-molecule anthraquinone transistor
- Author
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Koole, M., Thijssen, J. M., Valkenier, H., Hummelen, J. C., and van der Zant, H. S. J.
- Subjects
Condensed Matter - Mesoscale and Nanoscale Physics - Abstract
It is understood that molecular conjugation plays an important role in charge transport through single-molecule junctions. Here, we investigate electron transport through an anthraquinone based single-molecule three-terminal device. With the use of an electric-field induced by a gate electrode, the molecule is reduced resulting into a ten-fold increase in the off-resonant differential conductance. Theoretical calculations link the change in differential conductance to a reduction-induced change in conjugation, thereby lifting destructive interference of transport pathways., Comment: Nano Letters (2015)
- Published
- 2015
- Full Text
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3. Statistical analysis of single-molecule breaking traces
- Author
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Frisenda, R., Perrin, M. L., Valkenier, H., Hummelen, J. C., and Van der Zant, H. S. J.
- Subjects
Conductance ,Energy levels ,I-V characteristics ,Molecular electronics ,Single molecules - Published
- 2013
4. Evidence for Quantum Interference in SAMs of Arylethynylene Thiolates in Tunneling Junctions with Eutectic Ga–In (EGaIn) Top-Contacts
- Author
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Fracasso, D., Valkenier, H., Hummelen, J. C., Solomon, Gemma Clare, Chiechi, R. C., Fracasso, D., Valkenier, H., Hummelen, J. C., Solomon, Gemma Clare, and Chiechi, R. C.
- Published
- 2011
5. Controlling the interparticle distance in a 2D molecule–nanoparticle network
- Author
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Guédon, C M, primary, Zonneveld, J, additional, Valkenier, H, additional, Hummelen, J C, additional, and van der Molen, S J, additional
- Published
- 2011
- Full Text
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6. Introduction to the themed issue in honour of Prof. Kees Hummelen
- Author
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Valkenier, Hennie, Vanderzande, Dirk, Meijerink, Andries, Prato, Maurizio, Sub Condensed Matter and Interfaces, Condensed Matter and Interfaces, Sub Condensed Matter and Interfaces, Condensed Matter and Interfaces, Valkenier, H, Vanderzande, D, Meijerink, A, and Prato, M
- Subjects
Honour ,Materials science ,media_common.quotation_subject ,Materials Chemistry ,General Chemistry ,Classics ,media_common - Abstract
Guest editors Hennie Valkenier, Dirk Vanderzande, Andries Meijerink and Maurizio Prato introduce this Journal of Materials Chemistry C issue in honour of Professor Kees Hummelen on the occasion of his retirement.
- Published
- 2021
7. Anion transporters based on halogen, chalcogen, and pnictogen bonds: towards biological applications.
- Author
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Singh A, Torres-Huerta A, Meyer F, and Valkenier H
- Abstract
Motivated by their potential biological applications, anion receptors are increasingly explored as transmembrane transporters for anions. The vast majority of the reported anion transporters rely on hydrogen bonding to interact with the anions. However, in recent decades, halogen, chalcogen, and pnictogen bonding, collectively referred to as sigma-hole interactions, have received increasing attention. Most research efforts on these interactions have focused on crystal engineering, anion sensing, and organocatalysis. In recent years, however, these sigma-hole interactions have also been explored more widely in synthetic anion transporters. This perspective shows why synthetic transporters are promising candidates for biological applications. We provide a comprehensive review of the compounds used to transport anions across membranes, with a particular focus on how the binding atoms and molecular design affect the anion transport activity and selectivity. Few cell studies have been reported for these transporters based on sigma-hole interactions and we highlight the critical need for further biological studies on the toxicity, stability, and deliverability of these compounds to explore their full potential in biological applications, such as the treatment of cystic fibrosis., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)
- Published
- 2024
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8. A Semiflexible Tetrahydrazone Macrocycle for Binding of Pyrophosphate and Smaller Anions.
- Author
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Halgreen L, Torres-Huerta A, Norvaisa K, De Leener G, Tumanov N, Wouters J, Bartik K, and Valkenier H
- Abstract
Macrocyclization has proven to be a useful design strategy in the development of efficient anion receptors. In addition to the ring size, the overall preorganization due to structural rigidity is key. To explore this in the context of developing an efficient pyrophosphate receptor, three macrocycles featuring a 26-membered interior ring size and similar H-bonding motifs have been synthesized, and their anion binding ability has been investigated. Computational studies and nuclear magnetic resonance (NMR) data showed different degrees of preorganization as a result of differences in flexibility. The interaction of the three macrocycles with chloride, dihydrogen phosphate, and dihydrogen pyrophosphate was investigated in solution by NMR and ultraviolet-visible spectroscopy and in the solid state by X-ray crystallography. The tetrahydrazone-based macrocycle featuring intermediate flexibility exhibited the best affinity for all three anions investigated. Our results suggest that in addition to the proper preorganization of binding groups in a macrocycle a certain degree of flexibility is also required for an optimal affinity with the target guest.
- Published
- 2024
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9. Tuning CH Hydrogen Bond-Based Receptors toward Picomolar Anion Affinity via the Inductive Effect of Distant Substituents.
- Author
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Chvojka M, Madea D, Valkenier H, and Šindelář V
- Abstract
Inspired by nature, artificial hydrogen bond-based anion receptors have been developed to achieve high anion selectivity; however, their binding affinity is usually low. The potency of these receptors is usually increased by the introduction of aryl substituents, which withdraw electrons from their binding site through the resonance effect. Here, we show that the polarization of the C(sp
3 )-H binding site of bambusuril receptors, and thus their potency to bind anions, can be modulated by the inductive effect. The presence of electron-withdrawing groups on benzyl substituents of bambusurils significantly increases their binding affinities to halides, resulting in the strongest iodide receptor reported to date with an association constant greater than 1013 M-1 in acetonitrile. A Hammett plot showed that while the bambusuril affinity toward halides linearly increases with the electron-withdrawing power of their substituents, their binding selectivity remains essentially unchanged., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)- Published
- 2024
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10. Transmembrane Transport of Inorganic Phosphate by a Strapped Calix[4]pyrrole.
- Author
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Cataldo A, Norvaisa K, Halgreen L, Bodman SE, Bartik K, Butler SJ, and Valkenier H
- Abstract
Synthetic anion receptors are increasingly being explored for the transport of anions across lipid membranes because of their potential therapeutic applications. A considerable amount of research focuses on the transport of chloride, whereas the transmembrane transport of inorganic phosphate has not been reported to date, despite the biological relevance of this anion. Here we present a calix[4]pyrrole with a bisurea strap that functions as a receptor and transporter for H
2 PO4 - P NMR spectroscopy, we demonstrate that this receptor can transport phosphate into vesicles by H31 P NMR spectroscopy, we demonstrate that this receptor can transport phosphate into vesicles by H2 PO4 antiport, H- /Cl- antiport, H2 /H4 - uniport, and Cs+ /H2 PO4 - symport mechanisms. This first example of inorganic phosphate transport by a neutral receptor opens perspectives for the future development of transporters for various biological phosphates.- Published
- 2023
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11. Transmembrane transport of fluoride studied by time-resolved emission spectroscopy.
- Author
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Cataldo A, Chvojka M, Park G, Šindelář V, Gabbaï FP, Butler SJ, and Valkenier H
- Abstract
Here we present a new method to monitor fluoride transmembrane transport into liposomes using a europium(III) complex. We take advantage of the long emission lifetime of this probe to measure the transport activity of a fluorescent transporter. The high sensitivity, selectivity, and versatility of the assay allowed us to study different types of fluoride transporters and unravel their mechanisms of action.
- Published
- 2023
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12. Transmembrane Transport of Bicarbonate by Anion Receptors.
- Author
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Martínez-Crespo L and Valkenier H
- Subjects
- Biological Transport, Ion Transport, Bicarbonates
- Abstract
The development of synthetic anion transporters is motivated by their potential application as treatment for diseases that originate from deficient anion transport by natural proteins. Transport of bicarbonate is important for crucial biological functions such as respiration and digestion. Despite this biological relevance, bicarbonate transport has not been as widely studied as chloride transport. Herein we present an overview of the synthetic receptors that have been studied as bicarbonate transporters, together with the different assays used to perform transport studies in large unilamellar vesicles. We highlight the most active transporters and comment on the nature of the functional groups present in active and inactive compounds. We also address recent mechanistic studies that have revealed different processes that can lead to net transport of bicarbonate, as well as studies reported in cells and tissues, and comment on the key challenges for the further development of bicarbonate transporters., (© 2022 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)
- Published
- 2022
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13. Dissecting transmembrane bicarbonate transport by 1,8-di(thio)amidocarbazoles.
- Author
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Maslowska-Jarzyna K, Cataldo A, Marszalik A, Ignatikova I, Butler SJ, Stachowiak R, Chmielewski MJ, and Valkenier H
- Subjects
- Biological Transport, Carbazoles, Carbon Dioxide, Chlorides, Europium, Hydrogen-Ion Concentration, Ion Transport, Ionophores pharmacology, Lipid Bilayers, Liposomes, Anti-Infective Agents, Bicarbonates
- Abstract
Synthetic ionophores able to transport bicarbonate and chloride anions across lipid bilayers are appealing for their wide range of potential biological applications. We have studied the bicarbonate and chloride transport by carbazoles with two amido/thioamido groups using a bicarbonate-sensitive europium(III) probe in liposomes and found a highly remarkable transporter concentration dependence. This can be explained by a combination of two distinct transport mechanisms: HCO
3 - /Cl- exchange and a combination of unassisted CO2 diffusion and HCl transport, of which the respective contributions were quantified. The compounds studied were found to be highly potent HCl transporters. Based on the mechanistic insights on anion transport, we have tested the antimicrobial activity of these compounds and found a good correlation with their ion transport properties and a high activity against Gram-positive bacteria.- Published
- 2022
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14. Dynamic covalent chemistry with azines.
- Author
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Dascalu AE, Halgreen L, Torres-Huerta A, and Valkenier H
- Abstract
Dynamic covalent chemistry is used in many applications that require both the stability of covalent bonds and the possibility to exchange building blocks. Here we present azines as a dynamic covalent functional group that combines the best characteristics of imines and acylhydrazones. We show that azines are stable in the presence of water and that dynamic combinatorial libraries of azines and aldehydes equilibrate in less than an hour.
- Published
- 2022
- Full Text
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15. Monofunctionalized Fluorinated Bambusurils and Their Conjugates for Anion Transport and Extraction.
- Author
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De Simone NA, Chvojka M, Lapešová J, Martínez-Crespo L, Slávik P, Sokolov J, Butler SJ, Valkenier H, and Šindelář V
- Subjects
- Anions chemistry, Lipid Bilayers chemistry, Chlorides chemistry, Crown Ethers
- Abstract
Bambusurils are macrocyclic molecules that are known for their high binding affinity and selectivity toward anions. Here, we present the preparation of two bambusurils bearing fluorinated substituents and one carboxylic function. These monofunctionalized bambusurils were conjugated with crown ether and cholesterol units. The resulting conjugates were successfully tested in liquid-liquid extraction of inorganic salts and chloride/bicarbonate transport across lipid bilayers.
- Published
- 2022
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16. Calix[6]arenes with halogen bond donor groups as selective and efficient anion transporters.
- Author
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Singh A, Torres-Huerta A, Vanderlinden T, Renier N, Martínez-Crespo L, Tumanov N, Wouters J, Bartik K, Jabin I, and Valkenier H
- Subjects
- Anions chemistry, Chlorides, Hydrogen Bonding, Ion Transport, Calixarenes chemistry, Halogens chemistry
- Abstract
Here we present the anion binding and anion transport properties of a series of calix[6]arenes decorated on their small rim with either halogen bond or hydrogen bond donating groups. We show that the halogen bond donating iodotriazole groups enable highly selective transport of chloride and nitrate anions, without transport of protons or hydroxide, at rates similar to those observed with thiourea or squaramide groups.
- Published
- 2022
- Full Text
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17. Hydrazones in anion transporters: the detrimental effect of a second binding site.
- Author
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Martínez-Crespo L, Halgreen L, Soares M, Marques I, Félix V, and Valkenier H
- Abstract
Synthetic anion transporters can be developed using anion receptors that are able to bind the anion and stabilize it in the lipophilic interior of a bilayer membrane, and they usually contain functional groups with acidic NHs, such as ureas, thioureas and squaramides. To assess the suitability of acylhydrazones as a new functional group for the preparation of anion transporters, we have studied a family of thioureas functionalized with these and related functional groups.
1 H NMR titrations and DFT calculations indicate that the thioureas bearing acylhydrazone groups behave as chloride receptors with two separate binding sites, of which the acylhydrazone binds weaker than the thiourea. Chloride transport studies show that the additional binding site has a detrimental effect on thiourea-based transporters, and this phenomenon is also observed for bis(thio)ureas with two separate binding sites. We propose that the presence of a second anion binding unit hinders the transport activity of the thiourea due to additional interactions with the phospholipids of the membrane. In agreement with this hypothesis, extensive molecular dynamics simulations suggest that the molecules will tend to be positioned in the water/lipid interface, driven by the interaction of the NHs of the thiourea and of the acylhydrazone groups with the POPC polar head groups and water molecules. Moreover, the interaction energies show that the poorest transporters have indeed the strongest interactions with the membrane phospholipids, inhibiting chloride transport. This detrimental effect of additional functional groups on transport activity should be considered when designing new ion transporters, unless these groups cooperatively promote anion recognition and transmembrane transport.- Published
- 2021
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18. Transmembrane Transport of Bicarbonate Unravelled.
- Author
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Martínez-Crespo L, Hewitt SH, De Simone NA, Šindelář V, Davis AP, Butler S, and Valkenier H
- Abstract
Invited for the cover of this issue are Dr. Stephen Butler, Dr. Hennie Valkenier and co-workers at Université Libre de Bruxelles, Loughborough University, Masaryk University, and the University of Bristol. The image depicts the transport of bicarbonate anions versus the spontaneous diffusion of CO
2 across the lipid bilayer of a liposome. Read the full text of the article at 10.1002/chem.202100491., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)- Published
- 2021
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19. Molecular Recognition.
- Author
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Mooibroek TJ, Scheiner S, and Valkenier H
- Subjects
- Catalysis, Hydrogen Bonding, Molecular Structure, Nanotechnology, Structure-Activity Relationship, Drug Development, Pharmaceutical Preparations chemistry
- Published
- 2021
- Full Text
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20. Transmembrane transport of copper(i) by imidazole-functionalised calix[4]arenes.
- Author
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Renier N, Reinaud O, Jabin I, and Valkenier H
- Abstract
Here we present the first synthetic transmembrane transporters for Cu
+ . Calix[4]arenes with two imidazole groups have a linear coordination motif, which allows selective extraction of Cu+ into chloroform. Transmembrane transport of Cu+ into liposomes was investigated with a newly developed assay and the results open the way to biomedical applications of these Cu+ ionophores.- Published
- 2020
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21. Synthesis and Binding Properties of a Tren-Capped Hexahomotrioxacalix[3]arene.
- Author
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Zahim S, Ajami D, Laurent P, Valkenier H, Reinaud O, Luhmer M, and Jabin I
- Abstract
The straightforward synthesis of a new hexahomotrioxacalix[3]arene-based ligand capped by a tren subunit was developed and the binding properties of the corresponding zinc complex were explored by NMR spectroscopy. Similarly to the closely related calix[6]tren-based systems, the homooxacalixarene core ensures the mononuclearity of the zinc complex and the metal center displays a labile coordination site for exogenous guests. However, very different host-guest properties were observed: i) in CDCl
3 , the zinc complex strongly binds a water molecule and is reluctant to recognize other neutral guests, ii) in CD3 CN, the exo-coordination of anions prevails. Thus, in strong contrast to the calix[6]tren-based systems, the coordination of neutral guests that thread through the small rim and fill the polyaromatic cavity was not observed. This unique behaviour is likely due to the fact that the 18-membered ethereal macrocycle is too small to let a molecule threading through it. This work illustrates the key role played by the second coordination sphere in the binding properties of metal complexes., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)- Published
- 2020
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22. Limits of thiol chemistry revealed by quantitative analysis of mixed layers of thiolated-PEG ligands grafted onto gold nanoparticles.
- Author
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Retout M, Brunetti E, Valkenier H, and Bruylants G
- Abstract
Hypothesis: The functionalization of gold nanoparticles is commonly based on the use of thiol groups for the anchoring of organic ligands. To functionalize gold nanoparticles with mixed layers in defined proportions, different thiolated ligands are often used and assumed to graft equally on the surface. This assumption is however generally not verified and a quantitative investigation of the grafting density of mixed organic layers of thiolated ligands is therefore required., Experiments: Gold nanoparticles were exposed to solutions containing various proportions of two PEG ligands containing a thiol group at one extremity and a methoxy, carboxylate, or alkyne group at the other. A systematic study was performed on the resulting particles in order to quantify the composition of the PEG layer by quantitative
1 H NMR spectroscopy., Findings: Our results showed that the grafting of the PEG ligands with either a carboxylate or an alkyne group is strongly hindered in the presence of the methylated PEG ligands, despite the use of identical thiol anchoring groups. This is the first report on the quantification of mixed layers of PEGylated ligands on gold nanoparticles that demonstrates the severe limits of thiol chemistry for the functionalization of gold nanoparticles with mixed monolayers., (Copyright © 2019 Elsevier Inc. All rights reserved.)- Published
- 2019
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23. Anion carriers as potential treatments for cystic fibrosis: transport in cystic fibrosis cells, and additivity to channel-targeting drugs.
- Author
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Li H, Valkenier H, Thorne AG, Dias CM, Cooper JA, Kieffer M, Busschaert N, Gale PA, Sheppard DN, and Davis AP
- Abstract
Defective anion transport is a hallmark of the genetic disease cystic fibrosis (CF). One approach to restore anion transport to CF cells utilises alternative pathways for transmembrane anion transport, including artificial anion carriers (anionophores). Here, we screened 22 anionophores for biological activity using fluorescence emission from the halide-sensitive yellow fluorescent protein. Three compounds possessed anion transport activity similar to or greater than that of a bis-( p -nitrophenyl)ureidodecalin previously shown to have promising biological activity. Anion transport by these anionophores was concentration-dependent and persistent. All four anionophores mediated anion transport in CF cells, and their activity was additive to rescue of the predominant disease-causing variant F508del-CFTR using the clinically-licensed drugs lumacaftor and ivacaftor. Toxicity was variable but minimal at the lower end. The results provide further evidence that anionophores, by themselves or together with other treatments that restore anion transport, offer a potential therapeutic strategy for CF., (This journal is © The Royal Society of Chemistry 2019.)
- Published
- 2019
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24. Repositioning Chloride Transmembrane Transporters: Transport of Organic Ion Pairs.
- Author
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Grauwels G, Valkenier H, Davis AP, Jabin I, and Bartik K
- Abstract
Given the biological importance of organic cations, the facilitated transport of organic ion pairs could find many applications. Calix[6]arene tris(thio)ureas, which possess a cavity that can accommodate primary ammonium ions, can not only act as carriers for Cl
- /NO3 - antiport but can also perform the cotransport of PrNH3 H and1 H and35 Cl NMR experiments involving shift reagents. The cotransport of PrNH3 Cl was also observed by receptors deprived of a cavity, but the presence of the cavity conveys an advantage, as the cotransport by calix[6]arenes was observed to be more efficient than the Cl- /NO3 - antiport, which is not the case with receptors without a cavity. The role played by the cavity was further highlighted by the disappearance of this advantage when using a bulky ammonium ion, which cannot be complexed within the cavity., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)- Published
- 2019
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25. Anion Recognition by a Bioactive Diureidodecalin Anionophore: Solid-State, Solution, and Computational Studies.
- Author
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Jurček O, Valkenier H, Puttreddy R, Novák M, Sparkes HA, Marek R, Rissanen K, and Davis AP
- Subjects
- Binding Sites, Computers, Molecular, Crystallography, X-Ray, Magnetic Resonance Spectroscopy, Molecular Conformation, Anions chemistry, Chlorides chemistry, Nitrophenols chemistry, Urea chemistry
- Abstract
Recent work has identified a bis-(p-nitrophenyl)ureidodecalin anion carrier as a promising candidate for biomedical applications, showing good activity for chloride transport in cells yet almost no cytotoxicity. To underpin further development of this and related compounds, a detailed structural and binding investigation is reported. Crystal structures of the transporter as five solvates confirm the diaxial positioning of urea groups while revealing a degree of conformational flexibility. Structures of complexes with Cl
- , Br- , NO3 - , SO4 2- H NMR binding studies revealed exceptionally high affinities for anions in DMSO, decreasing in the order SO- >H1 H NMR binding studies revealed exceptionally high affinities for anions in DMSO, decreasing in the order SO4 2- >H2 PO4 - ≈HCO3 - ≈AcO- . Analysis of the binding results suggests that selectivity is determined mainly by the H-bond acceptor strength of different anions, but is also modulated by receptor geometry.4 - >Cl- >Br- >NO3 - >I- . Analysis of the binding results suggests that selectivity is determined mainly by the H-bond acceptor strength of different anions, but is also modulated by receptor geometry., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)- Published
- 2018
- Full Text
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26. Grafting of Oligo(ethylene glycol)-Functionalized Calix[4]arene-Tetradiazonium Salts for Antifouling Germanium and Gold Surfaces.
- Author
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Blond P, Mattiuzzi A, Valkenier H, Troian-Gautier L, Bergamini JF, Doneux T, Goormaghtigh E, Raussens V, and Jabin I
- Abstract
Biosensors that can determine protein concentration and structure are highly desired for biomedical applications. For the development of such biosensors, the use of Fourier transform infrared (FTIR) spectroscopy with the attenuated internal total reflection (ATR) configuration is particularly attractive, but it requires appropriate surface functionalization of the ATR optical element. Indeed, the surface has to specifically interact with a target protein in close contact with the optical element and must display antifouling properties to prevent nonspecific adsorption of other proteins. Here, we report robust monolayers of calix[4]arenes bearing oligo(ethylene glycol) (oEG) chains, which were grafted on germanium and gold surfaces via their tetradiazonium salts. The formation of monolayers of oEGylated calix[4]arenes was confirmed by AFM, IR, and contact angle measurements. The antifouling properties of these modified surfaces were studied by ATR-FTIR spectroscopy and fluorescence microscopy, and the nonspecific absorption of bovine serum albumin was found to be reduced by 85% compared to that of unmodified germanium. In other words, the organic coating by oEGylated calix[4]arenes provides remarkable antifouling properties, opening the way for the design of germanium- or gold-based biosensors.
- Published
- 2018
- Full Text
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27. Anthracene Bisureas as Powerful and Accessible Anion Carriers.
- Author
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Dias CM, Valkenier H, and Davis AP
- Abstract
Synthetic anion carriers (anionophores) have potential as biomedical research tools and as treatments for conditions arising from defective natural transport systems (notably cystic fibrosis). Highly active anionophores that are readily accessible and easily deliverable are especially valuable. Previous work has resulted in steroid and trans-decalin based anionophores with exceptional activity for chloride/nitrate exchange in vesicles, but poor accessibility and deliverability. This work shows that anthracene 1,8-bisureas can fulfil all three criteria. In particular, a bis-nitrophenyl derivative is prepared in two steps from commercial starting materials, yet shows comparable transport activity to the best currently known. Moreover, unlike earlier highly active systems, it does not need to be preincorporated in test vesicles but can be introduced subsequent to vesicle formation. This transporter also shows the ability to transfer between vesicles, and is therefore uniquely effective for anion transport at low transporter loadings. The results suggest that anthracene bisureas are promising candidates for application in biological research and medicine., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
- Published
- 2018
- Full Text
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28. Anion transport by ortho-phenylene bis-ureas across cell and vesicle membranes.
- Author
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Dias CM, Li H, Valkenier H, Karagiannidis LE, Gale PA, Sheppard DN, and Davis AP
- Subjects
- Anions metabolism, Bacterial Proteins, Cell Membrane metabolism, Halogens pharmacology, Intracellular Membranes metabolism, Luminescent Proteins, Urea chemistry, Urea metabolism, Ion Transport, Phenylenediamines chemistry, Urea analogs & derivatives
- Abstract
Ortho-Phenylene bis-ureas serve as anionophores in cells expressing halide-sensitive yellow fluorescent protein, as well as in synthetic vesicles. Activities can reach high levels, and are strongly dependent on the deliverability of the transporters.
- Published
- 2018
- Full Text
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29. Controlled Functionalization of Gold Nanoparticles with Mixtures of Calix[4]arenes Revealed by Infrared Spectroscopy.
- Author
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Valkenier H, Malytskyi V, Blond P, Retout M, Mattiuzzi A, Goole J, Raussens V, Jabin I, and Bruylants G
- Abstract
Labile ligands such as thiols and carboxylates are commonly used to functionalize AuNPs, though little control over the composition is possible when mixtures of ligands are used. It was shown recently that robustly functionalized AuNPs can be obtained through the reductive grafting of calix[4]arenes bearing diazonium groups on the large rim. Here, we report a calix[4]arene-tetradiazonium decorated by four oligo(ethylene glycol) chains on the small rim, which upon grafting gave AuNPs with excellent stability thanks to the C-Au bonds. Mixtures of this calixarene and one with four carboxylate groups were grafted on AuNPs. The resulting particles were analyzed by infrared spectroscopy, which revealed that the composition of the ligand shell clearly reflected the ratio of calixarenes that was present in solution. This strategy opens the way to robustly protected AuNPs with well-defined numbers of functional or postfunctionalizable groups.
- Published
- 2017
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30. Extremely robust and post-functionalizable gold nanoparticles coated with calix[4]arenes via metal-carbon bonds.
- Author
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Troian-Gautier L, Valkenier H, Mattiuzzi A, Jabin I, den Brande NV, Mele BV, Hubert J, Reniers F, Bruylants G, Lagrost C, and Leroux Y
- Abstract
Gold nanoparticles stabilized with a thin layer of post-functionalizable calix[4]arenes were prepared through the reductive grafting of a calix[4]arene-tetra-diazonium salt. These particles show exceptional stability towards extreme pH, F(-), NaCl, and upon drying. Post-functionalization of the calix-layer was demonstrated, opening the way to a wide range of applications.
- Published
- 2016
- Full Text
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31. Targeted anion transporter delivery by coiled-coil driven membrane fusion.
- Author
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Mora NL, Bahreman A, Valkenier H, Li H, Sharp TH, Sheppard DN, Davis AP, and Kros A
- Abstract
Synthetic anion transporters (anionophores) have potential as biomedical research tools and therapeutics. However, the efficient and specific delivery of these highly lipophilic molecules to a target cell membrane is non-trivial. Here, we investigate the delivery of a powerful anionophore to artificial and cell membranes using a coiled-coil-based delivery system inspired by SNARE membrane fusion proteins. Incorporation of complementary lipopeptides into the lipid membranes of liposomes and cell-sized giant unilamellar vesicles (GUVs) facilitated the delivery of a powerful anionophore into GUVs, where its anion transport activity was monitored in real time by fluorescence microscopy. Similar results were achieved using live cells engineered to express a halide-sensitive fluorophore. We conclude that coiled-coil driven membrane fusion is a highly efficient system to deliver anionophores to target cell membranes.
- Published
- 2016
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32. Tilting and Tumbling in Transmembrane Anion Carriers: Activity Tuning through n-Alkyl Substitution.
- Author
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Edwards SJ, Marques I, Dias CM, Tromans RA, Lees NR, Félix V, Valkenier H, and Davis AP
- Abstract
Anion transport by synthetic carriers (anionophores) holds promise for medical applications, especially the treatment of cystic fibrosis. Among the factors which determine carrier activity, the size and disposition of alkyl groups is proving remarkably important. Herein we describe a series of dithioureidodecalin anionophores, in which alkyl substituents on one face are varied from C
0 to C10 in two-carbon steps. Activities increase then decrease as the chain length grows, peaking quite sharply at C6 . Molecular dynamics simulations showed the transporter chloride complexes releasing chloride as they approach the membrane-aqueous interface. The free transporter then stays at the interface, adopting an orientation that depends on the alkyl substituent. If chloride release is prevented, the complex is positioned similarly. Longer chains tilt the binding site away from the interface, potentially freeing the transporter or complex to move through the membrane. However, chains which are too long can also slow transport by inhibiting movement, and especially reorientation, within the phospholipid bilayer., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)- Published
- 2016
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33. Efficient, non-toxic anion transport by synthetic carriers in cells and epithelia.
- Author
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Li H, Valkenier H, Judd LW, Brotherhood PR, Hussain S, Cooper JA, Jurček O, Sparkes HA, Sheppard DN, and Davis AP
- Subjects
- Animals, Anions metabolism, Bacterial Proteins genetics, Cell Membrane drug effects, Cell Membrane metabolism, Cell Proliferation drug effects, Cell Survival drug effects, Chlorine metabolism, Cyclohexanes pharmacokinetics, Cyclohexanes toxicity, Cystic Fibrosis Transmembrane Conductance Regulator genetics, Dogs, Drug Carriers chemistry, Drug Design, Electrophysiological Phenomena, Epithelial Cells drug effects, HeLa Cells, Humans, Hydrogen Bonding, Ion Transport, Luminescent Proteins genetics, Madin Darby Canine Kidney Cells, Microscopy, Fluorescence, Molecular Structure, Naphthalenes pharmacokinetics, Naphthalenes toxicity, Phosphatidylcholines chemistry, Rats, Inbred F344, Steroids pharmacokinetics, Steroids toxicity, Cyclohexanes chemistry, Cystic Fibrosis Transmembrane Conductance Regulator metabolism, Epithelial Cells metabolism, Naphthalenes chemistry, Steroids chemistry
- Abstract
Transmembrane anion transporters (anionophores) have potential for new modes of biological activity, including therapeutic applications. In particular they might replace the activity of defective anion channels in conditions such as cystic fibrosis. However, data on the biological effects of anionophores are scarce, and it remains uncertain whether such molecules are fundamentally toxic. Here, we report a biological study of an extensive series of powerful anion carriers. Fifteen anionophores were assayed in single cells by monitoring anion transport in real time through fluorescence emission from halide-sensitive yellow fluorescent protein. A bis-(p-nitrophenyl)ureidodecalin shows especially promising activity, including deliverability, potency and persistence. Electrophysiological tests show strong effects in epithelia, close to those of natural anion channels. Toxicity assays yield negative results in three cell lines, suggesting that promotion of anion transport may not be deleterious to cells. We therefore conclude that synthetic anion carriers are realistic candidates for further investigation as treatments for cystic fibrosis.
- Published
- 2016
- Full Text
- View/download PDF
34. Sterically geared tris-thioureas; transmembrane chloride transporters with unusual activity and accessibility.
- Author
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Valkenier H, Dias CM, Porter Goff KL, Jurček O, Puttreddy R, Rissanen K, and Davis AP
- Subjects
- Anions metabolism, Crystallography, X-Ray, Ion Transport, Models, Molecular, Molecular Structure, Thiourea chemical synthesis, Chlorides metabolism, Thiourea chemistry, Thiourea metabolism
- Abstract
Tris-N-arylthioureas derived in one step from 1,3,5-tris(aminomethyl)-2,4,6-triethylbenzene are remarkably effective anion carriers. With optimised aryl substituents their activities come close to the best currently known, suggesting that they might find use as readily available standards in anion transport research.
- Published
- 2015
- Full Text
- View/download PDF
35. Biotin[6]uril Esters: Chloride-Selective Transmembrane Anion Carriers Employing C-H···Anion Interactions.
- Author
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Lisbjerg M, Valkenier H, Jessen BM, Al-Kerdi H, Davis AP, and Pittelkow M
- Subjects
- Anions chemistry, Bridged-Ring Compounds chemical synthesis, Esters chemical synthesis, Hydrogen Bonding, Macrocyclic Compounds chemical synthesis, Molecular Conformation, Bridged-Ring Compounds chemistry, Chlorides chemistry, Esters chemistry, Macrocyclic Compounds chemistry
- Abstract
Biotin[6]uril hexaesters represent a new class of anionophores which operate solely through C-H···anion interactions. The use of soft H-bond donors favors the transport of less hydrophilic anions (e.g., Cl(-), NO3(-)) over hard, stongly hydrated anions (e.g., HCO3(-) and SO4(2-)). Especially relevant is the selectivity between chloride and bicarbonate, the major inorganic anions in biological systems.
- Published
- 2015
- Full Text
- View/download PDF
36. High-affinity anion binding by steroidal squaramide receptors.
- Author
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Edwards SJ, Valkenier H, Busschaert N, Gale PA, and Davis AP
- Abstract
Exceptionally powerful anion receptors have been constructed by placing squaramide groups in axial positions on a steroidal framework. The steroid preorganizes the squaramide NH groups such that they can act cooperatively on a bound anion, while maintaining solubility in nonpolar media. The acidic NH groups confer higher affinities than previously-used ureas or thioureas. Binding constants exceeding 10(14) M(-1) have been measured for tetraethylammonium salts in chloroform by employing a variation of Cram's extraction procedure. The receptors have also been studied as transmembrane anion carriers in unilamellar vesicles. Unusually their activities do not correlate with anion affinities, thus suggesting an upper limit for binding strength in the design of anion carriers., (© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.)
- Published
- 2015
- Full Text
- View/download PDF
37. Visualization and quantification of transmembrane ion transport into giant unilamellar vesicles.
- Author
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Valkenier H, López Mora N, Kros A, and Davis AP
- Subjects
- Biological Transport, Ion Transport, Microscopy, Fluorescence, Ionophores metabolism, Ions metabolism, Unilamellar Liposomes metabolism
- Abstract
Transmembrane ion transporters (ionophores) are widely investigated as supramolecular agents with potential for biological activity. Tests are usually performed in synthetic membranes that are assembled into large unilamellar vesicles (LUVs). However transport must be followed through bulk properties of the vesicle suspension, because LUVs are too small for individual study. An alternative approach is described whereby ion transport can be revealed and quantified through direct observation. The method employs giant unilamellar vesicles (GUVs), which are 20-60 μm in diameter and readily imaged by light microscopy. This allows characterization of individual GUVs containing transporter molecules, followed by studies of transport through fluorescence emission from encapsulated indicators. The method provides new levels of certainty and relevance, given that the GUVs are similar in size to living cells. It has been demonstrated using a highly active anion carrier, and should aid the development of compounds for treating channelopathies such as cystic fibrosis., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
- Published
- 2015
- Full Text
- View/download PDF
38. Large negative differential conductance in single-molecule break junctions.
- Author
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Perrin ML, Frisenda R, Koole M, Seldenthuis JS, Gil JA, Valkenier H, Hummelen JC, Renaud N, Grozema FC, Thijssen JM, Dulić D, and van der Zant HS
- Abstract
Molecular electronics aims at exploiting the internal structure and electronic orbitals of molecules to construct functional building blocks. To date, however, the overwhelming majority of experimentally realized single-molecule junctions can be described as single quantum dots, where transport is mainly determined by the alignment of the molecular orbital levels with respect to the Fermi energies of the electrodes and the electronic coupling with those electrodes. Particularly appealing exceptions include molecules in which two moieties are twisted with respect to each other and molecules in which quantum interference effects are possible. Here, we report the experimental observation of pronounced negative differential conductance in the current-voltage characteristics of a single molecule in break junctions. The molecule of interest consists of two conjugated arms, connected by a non-conjugated segment, resulting in two coupled sites. A voltage applied across the molecule pulls the energy of the sites apart, suppressing resonant transport through the molecule and causing the current to decrease. A generic theoretical model based on a two-site molecular orbital structure captures the experimental findings well, as confirmed by density functional theory with non-equilibrium Green's functions calculations that include the effect of the bias. Our results point towards a conductance mechanism mediated by the intrinsic molecular orbitals alignment of the molecule.
- Published
- 2014
- Full Text
- View/download PDF
39. Preorganized bis-thioureas as powerful anion carriers: chloride transport by single molecules in large unilamellar vesicles.
- Author
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Valkenier H, Judd LW, Li H, Hussain S, Sheppard DN, and Davis AP
- Subjects
- Anions chemistry, Chlorides administration & dosage, Chlorides chemistry, Humans, Ion Transport, Models, Molecular, Nitrates administration & dosage, Nitrates chemistry, Anions administration & dosage, Cholesterol chemistry, Phosphatidylcholines chemistry, Thiourea chemistry, Unilamellar Liposomes chemistry
- Abstract
Transmembrane anion carriers (anionophores) have potential in biological research and medicine, provided high activities can be obtained. There is particular interest in treating cystic fibrosis (CF), a genetic illness caused by deficient anion transport. Previous work has found that anionophore designs featuring axial ureas on steroid and trans-decalin scaffolds can be especially effective. Here we show that replacement of ureas by thioureas yields substantial further enhancements. Six new bis-thioureas have been prepared and tested for Cl(-)/NO3(-) exchange in 1-palmitoyl-2-oleoylphosphatidylcholine/cholesterol large unilamellar vesicles (LUVs). The bis-thioureas are typically >10 times more effective than the corresponding ureas and are sufficiently active that transport by molecules acting singly in LUVs is readily detected. The highest activity is shown by decalin 9, which features N-(3,5-bis(trifluoromethyl)phenyl)thioureido and octyl ester substituents. A single molecule of transporter 9 in a 200 nm vesicle promotes Cl(-)/NO3(-) exchange with a half-life of 45 s and an absolute rate of 850 chloride anions per second. Weight-for-weight, this carrier is only slightly less effective than CFTR, the natural anion channel associated with CF.
- Published
- 2014
- Full Text
- View/download PDF
40. Cross-conjugation and quantum interference: a general correlation?
- Author
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Valkenier H, Guédon CM, Markussen T, Thygesen KS, van der Molen SJ, and Hummelen JC
- Abstract
We discuss the relationship between the π-conjugation pattern, molecular length, and charge transport properties of molecular wires, both from an experimental and a theoretical viewpoint. Specifically, we focus on the role of quantum interference in the conductance properties of cross-conjugated molecules. For this, we compare experiments on two series of dithiolated wires. The first set we synthesized consists of three dithiolated oligo(phenylene ethynylene) (OPE) benchmark compounds with increasing length. The second series synthesized comprises three molecules with different π-conjugation patterns, but identical lengths, i.e. an anthracene (linear conjugation), an anthraquinone (cross-conjugation), and a dihydroanthracene (broken conjugation) derivative. To benchmark reliable trends, conductance experiments on these series have been performed by various techniques. Here, we compare data obtained by conductive-probe atomic force microscopy (CP-AFM) for self-assembled monolayers (SAMs) with single-molecule break junction and multi-molecule EGaIn data from other groups. For the benchmark OPE-series, we consistently find an exponential decay of the conductance with molecular length characterized by β = 0.37 ± 0.03 Å(-1) (CP-AFM). Remarkably, for the second series, we do not only find that the linearly conjugated anthracene-containing wire is the most conductive, but also that the cross-conjugated anthraquinone-containing wire is less conductive than the broken-conjugated derivative. We attribute the low conductance values for the cross-conjugated species to quantum interference effects. Moreover, by theoretical modeling, we show that destructive quantum interference is a robust feature for cross-conjugated structures and that the energy at which complete destructive interference occurs can be tuned by the choice of side group. The latter provides an outlook for future devices in this fascinating field connecting chemistry and physics.
- Published
- 2014
- Full Text
- View/download PDF
41. Making a match for Valinomycin: steroidal scaffolds in the design of electroneutral, electrogenic anion carriers.
- Author
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Valkenier H and Davis AP
- Subjects
- Anions chemistry, Drug Carriers chemistry, Molecular Structure, Steroids metabolism, Valinomycin metabolism, Drug Design, Models, Biological, Steroids chemistry, Valinomycin chemistry
- Abstract
The natural product Valinomycin is a well-known transmembrane cation carrier. Despite being uncharged, this molecule can extract potassium ions from water without counterions and ferry them through a membrane interior. Because it only transports positive ions, it is electrogenic, mediating a flow of charge across the membrane. Equivalent agents for anions would be valuable research tools and may have therapeutic applications, especially in the treatment of "channelopathies" such as cystic fibrosis. However, no such molecules have been found in nature. In this Account, we describe our research toward synthetic and rationally designed "anti-Valinomycins". As our core approach to this problem, we used the steroid nucleus, provided by cholic acid, as a scaffold for the assembly of anion receptors. By positioning H-bond donors on this framework, especially urea and thiourea groups in conformationally constrained axial positions, we created binding sites capable of exceptionally high affinities (up to 10(11) M(-1) for R4N(+)Cl(-) in chloroform). The extended hydrocarbon surface of the steroid helped to maintain compatibility with nonpolar media. When we tested these "cholapods" for chloride transport in vesicles, they provided the first evidence for electrogenic anion transport mediated by electroneutral organic carriers: in other words, they are the first authenticated anti-Valinomycins. They also proved active in live cells that we grew and assayed in an Ussing chamber. In subsequent work, we have shown that the cholapods can exhibit very high activities, with transport observed down to carrier/lipid ratios of 1:250,000. We also understand some of the effects of structure on the activity of these molecules. For example, in most cases, powerful transporters also act as powerful receptors. On the other hand, some modifications which favor binding do not promote transport. We gained functional advantages by cyclizing the cholapod architecture, which encloses the anion binding site. We could also simplify the structure without compromising function. A steroid-inspired trans-decalin framework has proved highly effective and may lead to agents with practical advantages. Changing an ester side-chain in this system revealed a surprising effect, whereby increased length and/or lipophilicity resulted in substantially raised activity. Although much remains to be discovered about these anionophores, their high activities and intrinsic tuneabilities bode well for applications. In future work, we plan to develop and exploit these molecules as tools for biophysical research and to explore the possibility of useful biological activity.
- Published
- 2013
- Full Text
- View/download PDF
42. Observation of quantum interference in molecular charge transport.
- Author
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Guédon CM, Valkenier H, Markussen T, Thygesen KS, Hummelen JC, and van der Molen SJ
- Abstract
As the dimensions of a conductor approach the nanoscale, quantum effects begin to dominate, and it becomes possible to control the conductance through direct manipulation of the electron wavefunction. Such control has been demonstrated in various mesoscopic devices at cryogenic temperatures, but it has proved to be difficult to exert control over the wavefunction at higher temperatures. Molecules have typical energy level spacings (∼eV) that are much larger than the thermal energy at 300 K (∼25 meV), and are therefore natural candidates for such experiments. Previously, phenomena such as giant magnetoresistance, Kondo effects and conductance switching have been observed in single molecules, and theorists have predicted that it should also be possible to observe quantum interference in molecular conductors, but until now all the evidence for such behaviour has been indirect. Here, we report the observation of destructive quantum interference in charge transport through two-terminal molecular junctions at room temperature. We studied five different rigid π-conjugated molecular wires, all of which form self-assembled monolayers on a gold surface, and find that the degree of interference can be controlled by simple chemical modifications of the molecular wire.
- Published
- 2012
- Full Text
- View/download PDF
43. Correlations between molecular structure and single-junction conductance: a case study with oligo(phenylene-ethynylene)-type wires.
- Author
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Kaliginedi V, Moreno-García P, Valkenier H, Hong W, García-Suárez VM, Buiter P, Otten JL, Hummelen JC, Lambert CJ, and Wandlowski T
- Abstract
The charge transport characteristics of 11 tailor-made dithiol-terminated oligo(phenylene-ethynylene) (OPE)-type molecules attached to two gold electrodes were studied at a solid/liquid interface in a combined approach using an STM break junction (STM-BJ) and a mechanically controlled break junction (MCBJ) setup. We designed and characterized 11 structurally distinct dithiol-terminated OPE-type molecules with varied length and HOMO/LUMO energy. Increase of the molecular length and/or of the HOMO-LUMO gap leads to a decrease of the single-junction conductance of the linearly conjugate acenes. The experimental data and simulations suggest a nonresonant tunneling mechanism involving hole transport through the molecular HOMO, with a decay constant β = 3.4 ± 0.1 nm(-1) and a contact resistance R(c) = 40 kΩ per Au-S bond. The introduction of a cross-conjugated anthraquinone or a dihydroanthracene central unit results in lower conductance values, which are attributed to a destructive quantum interference phenomenon for the former and a broken π-conjugation for the latter. The statistical analysis of conductance-distance and current-voltage traces revealed details of evolution and breaking of molecular junctions. In particular, we explored the effect of stretching rate and junction stability. We compare our experimental results with DFT calculations using the ab initio code SMEAGOL and discuss how the structure of the molecular wires affects the conductance values.
- Published
- 2012
- Full Text
- View/download PDF
44. Evidence for quantum interference in SAMs of arylethynylene thiolates in tunneling junctions with eutectic Ga-In (EGaIn) top-contacts.
- Author
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Fracasso D, Valkenier H, Hummelen JC, Solomon GC, and Chiechi RC
- Abstract
This paper compares the current density (J) versus applied bias (V) of self-assembled monolayers (SAMs) of three different ethynylthiophenol-functionalized anthracene derivatives of approximately the same thickness with linear-conjugation (AC), cross-conjugation (AQ), and broken-conjugation (AH) using liquid eutectic Ga-In (EGaIn) supporting a native skin (~1 nm thick) of Ga(2)O(3) as a nondamaging, conformal top-contact. This skin imparts non-Newtonian rheological properties that distinguish EGaIn from other top-contacts; however, it may also have limited the maximum values of J observed for AC. The measured values of J for AH and AQ are not significantly different (J ≈ 10(-1)A/cm(2) at V = 0.4 V). For AC, however, J is 1 (using log averages) or 2 (using Gaussian fits) orders of magnitude higher than for AH and AQ. These values are in good qualitative agreement with gDFTB calculations on single AC, AQ, and AH molecules chemisorbed between Au contacts that predict currents, I, that are 2 orders of magnitude higher for AC than for AH at 0 < |V| < 0.4 V. The calculations predict a higher value of I for AQ than for AH; however, the magnitude is highly dependent on the position of the Fermi energy, which cannot be calculated precisely. In this sense, the theoretical predictions and experimental conclusions agree that linearly conjugated AC is significantly more conductive than either cross-conjugated AQ or broken conjugate AH and that AQ and AH cannot necessarily be easily differentiated from each other. These observations are ascribed to quantum interference effects. The agreement between the theoretical predictions on single molecules and the measurements on SAMs suggest that molecule-molecule interactions do not play a significant role in the transport properties of AC, AQ, and AH.
- Published
- 2011
- Full Text
- View/download PDF
45. Formation of high-quality self-assembled monolayers of conjugated dithiols on gold: base matters.
- Author
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Valkenier H, Huisman EH, van Hal PA, de Leeuw DM, Chiechi RC, and Hummelen JC
- Subjects
- Alkynes chemistry, Ethers chemistry, Ethylamines chemistry, Molecular Structure, Solutions, Toluene chemistry, Ethylamines chemical synthesis, Gold chemistry, Membranes, Artificial, Toluene analogs & derivatives
- Abstract
This Article reports a systematic study on the formation of self-assembled monolayers (SAMs) of conjugated molecules for molecular electronic (ME) devices. We monitored the deprotection reaction of acetyl protected dithiols of oligophenylene ethynylenes (OPEs) in solution using two different bases and studied the quality of the resulting SAMs on gold. We found that the optimal conditions to reproducibly form dense, high-quality monolayers are 9-15% triethylamine (Et(3)N) in THF. The deprotection base tetrabutylammonium hydroxide (Bu(4)NOH) leads to less dense SAMs and the incorporation of Bu(4)N into the monolayer. Furthermore, our results show the importance of the equilibrium concentrations of (di)thiolate in solution on the quality of the SAM. To demonstrate the relevance of these results for molecular electronics applications, large-area molecular junctions were fabricated using no base, Et(3)N, and Bu(4)NOH. The magnitude of the current-densities in these devices is highly dependent on the base. A value of β=0.15 Å(-1) for the exponential decay of the current-density of OPEs of varying length formed using Et(3)N was obtained., (© 2011 American Chemical Society)
- Published
- 2011
- Full Text
- View/download PDF
46. An MCBJ case study: The influence of π-conjugation on the single-molecule conductance at a solid/liquid interface.
- Author
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Hong W, Valkenier H, Mészáros G, Manrique DZ, Mishchenko A, Putz A, García PM, Lambert CJ, Hummelen JC, and Wandlowski T
- Abstract
π-Conjugation plays an important role in charge transport through single molecular junctions. We describe in this paper the construction of a mechanically controlled break-junction setup (MCBJ) equipped with a highly sensitive log I-V converter in order to measure ultralow conductances of molecular rods trapped between two gold leads. The current resolution of the setup reaches down to 10 fA. We report single-molecule conductance measurements of an anthracene-based linearly conjugated molecule (AC), of an anthraquinone-based cross-conjugated molecule (AQ), and of a dihydroanthracene-based molecule (AH) with a broken conjugation. The quantitative analysis of complementary current-distance and current-voltage measurements revealed details of the influence of π-conjugation on the single-molecule conductance.
- Published
- 2011
- Full Text
- View/download PDF
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