Self-Complementary Recognition of Supramolecular Urea–Aminotriazines in Solution and on Surfaces

Embrechts, Anika; Velders, Aldrik H.; Schönherr, Holger; Vancso, G. Julius

doi:10.1021/la203433z

Cited by 14 publications

(22 citation statements)

References 37 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[49] Thep resence of TA enables K + [15C5] 2 one-quarter extension in lifetime (t 0 ), three-fold acceleration in the formation rate (k on ), and ad ecrease in the dissociation rate (k off ). Thes eemingly rapid k off of 62.2 and 77.0 s À1 is in fact comparable to that of supramolecular complexes (e.g.,7 .6-50 s À1 for the urea-aminotriazine pair [50,51] )a nd that of cell adhesion proteins (7-200 s À1 ). [52][53][54] Thev alues of k off for K + [15C5] 2 are actually orders of magnitude lower than those of 1-to-1 M n+ [crown] complexation (10 2 -10 7 s À1 ).…”

Section: Angewandte Chemiementioning

confidence: 99%

“…Forboth conditions,without or with the co-assembly of TA,the properties associated with mechanical rupturing are essentially the same,such as thermally induced f b and x b .T he derived barrier width, x b ( % 0.13 nm), is on the same order of magnitude as the simulated K + -O distance (0.183 nm) for K + [15C5] 2 reported in aDFT study. Thes eemingly rapid k off of 62.2 and 77.0 s À1 is in fact comparable to that of supramolecular complexes (e.g.,7 .6-50 s À1 for the urea-aminotriazine pair [50,51] )a nd that of cell adhesion proteins (7-200 s À1 ). Thes eemingly rapid k off of 62.2 and 77.0 s À1 is in fact comparable to that of supramolecular complexes (e.g.,7 .6-50 s À1 for the urea-aminotriazine pair [50,51] )a nd that of cell adhesion proteins (7-200 s À1 ).…”

Section: Angewandte Chemiementioning

confidence: 99%

See 1 more Smart Citation

Force Spectroscopy of Metal–Crown Ether Multivalency: Effect of Local Environments on Energy Landscape and Sensing Kinetics

2015

View full text Add to dashboard Cite

Sandwichcomplexation involving alkali or alkalineearth metals,m ultivalency,a nd effects associated with local environments is widely encountered in biological and synthetic systems yet the mechanic properties remain unexplored. Herein, AFM (atomic force microscopy)-based single-molecule force spectroscopyi se mployed to investigate ac lassical model of ). The effect of local environments is significant on association yet less critical on dissociation pathways.Molecular recognition through reversible noncovalent and multivalent interactions operating collectively with neighboring functionalities is one of the most significant features of chemical and biological systems.Among the sensing elements and synergistically acting components,m oieties of crown ethers [1][2][3] have long been acknowledged and are still actively involved in contemporary challenges;t on ame af ew: ionchannel transport, [4][5][6] modulating protein surface properties, [7] monitoring the motion of aguest molecule on amultitopic host, [8,9] template-assisted synthesis, [2,[10][11][12][13] switchable performance in catalysis [14,15] and in molecular machines, [12,13,16,17] and energy storage.[18] To achieve these tasks effectively and repeatedly,r eversible dissociation that restores the host configuration is as important as the step of associative recognition. However,t he mechanical nature to evaluate the reversibility for metal-crown ether complexes has yet been reported. Further surprisingly,literature work on thermodynamic and kinetic parameters in the solution phase [19] is scarce for the famous sandwich complexes, M n+ [crown] 2 ,t hat have been utilized in many phenomenal sensing applications.[20] Taking advantage of AFM-based (atomic force microscopy) single-molecule force spectroscopy, [21][22][23] we will quantitatively show here the mechanic strengths,free-energy landscapes,and the kinetic parameters of the dissociation of metal-crown ether complexes.Them odel system is M n+ [15C5] 2 and the experimental concept is illustrated in Figure 1Awith moieties of 15-crown5ether immobilized on Au substrate by sulfur-gold (RS-Au) .The grey and black traces indicate the directions of tip approaching toward and retracting from the substrate, respectively. To prepare panels Dand F, acquired for each case are 1000 force-distance traces in which 226 traces exhibit rupture forces for the former and 203 traces for the latter.The solid curves are Gaussian fitting from which the peak positions were determined.T he bin width of unbinding forces in the histograms is 5pN. Force measurements were performed with aloading rate of 10.5 nN s À1 (with an apparent spring constant of 0.035 nN nm À1 and aretraction velocity of 300 nm s À1 ).

show abstract

Section: Angewandte Chemiementioning

confidence: 99%

Section: Angewandte Chemiementioning

confidence: 99%

Force Spectroscopy of Metal–Crown Ether Multivalency: Effect of Local Environments on Energy Landscape and Sensing Kinetics

2015

View full text Add to dashboard Cite

show abstract

“…c o m / l o c a t e / t e t l e t coated quartz crystal chips via strong interactions between the bisthiol unit and gold. 18 To increase the hydrophilic interactions with polar solvent and the biocompatibility of isoprenoid chain, these probes had a tetraethyleneglycol (TEG) linker 19 to link isoprenoid tails and the lipoic acid moiety by an ether and ester bond, respectively (Scheme 1). Alcohols 1a-1d were treated with CBr 4 /PPh 3 to give bromides 2a-2d, which were converted to 3a-3d via Williamson etherification in good yields.…”

Section: Contents Lists Available At Sciencedirectmentioning

confidence: 99%

Synthesis of isoprenoid chain-contained chemical probes for an investigation of molecular interactions by using quartz crystal microbalance

Liu

Zhang

Hou

et al. 2013

Tetrahedron Letters

View full text Add to dashboard Cite

“…Thus DAD-ADA pairs are thermally weaker than DDD-AAA complexes [35]. In 2011 Embrechts et al showed that such cooperative effects also influences the mechanical stability of tetravalent interactions [36]. They performed DFS on UAT dimers (DADA–ADAD pairs) with UPy dimers (DDAA–AADD pairs) in hexadecane.…”

Section: Introductionmentioning

confidence: 99%

Mechanical stability of bivalent transition metal complexes analyzed by single-molecule force spectroscopy

Gensler¹,

Eidamshaus²,

Taszarek³

et al. 2015

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

SummaryMultivalent biomolecular interactions allow for a balanced interplay of mechanical stability and malleability, and nature makes widely use of it. For instance, systems of similar thermal stability may have very different rupture forces. Thus it is of paramount interest to study and understand the mechanical properties of multivalent systems through well-characterized model systems. We analyzed the rupture behavior of three different bivalent pyridine coordination complexes with Cu2+ in aqueous environment by single-molecule force spectroscopy. Those complexes share the same supramolecular interaction leading to similar thermal off-rates in the range of 0.09 and 0.36 s−1, compared to 1.7 s−1 for the monovalent complex. On the other hand, the backbones exhibit different flexibility, and we determined a broad range of rupture lengths between 0.3 and 1.1 nm, with higher most-probable rupture forces for the stiffer backbones. Interestingly, the medium-flexible connection has the highest rupture forces, whereas the ligands with highest and lowest rigidity seem to be prone to consecutive bond rupture. The presented approach allows separating bond and backbone effects in multivalent model systems.

show abstract

Self-Complementary Recognition of Supramolecular Urea–Aminotriazines in Solution and on Surfaces

Cited by 14 publications

References 37 publications

Force Spectroscopy of Metal–Crown Ether Multivalency: Effect of Local Environments on Energy Landscape and Sensing Kinetics

Force Spectroscopy of Metal–Crown Ether Multivalency: Effect of Local Environments on Energy Landscape and Sensing Kinetics

Synthesis of isoprenoid chain-contained chemical probes for an investigation of molecular interactions by using quartz crystal microbalance

Mechanical stability of bivalent transition metal complexes analyzed by single-molecule force spectroscopy

Contact Info

Product

Resources

About