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Degen P Optenhostert T Rehage H Verhaelen C Lange M Polkowska J Klärner FG 《Langmuir : the ACS journal of surfaces and colloids》2007,23(23):11611-11616
Molecular clips and tweezers are able to selectively bind electron-deficient aromatic and aliphatic substrates. By means of pressure-area isotherms and Brewster angle microscopy (BAM), the self-association process and phase behavior of dimethylene-bridged molecular clips and tetramethylene-bridged molecular tweezers each substituted with two acetoxy groups as polar head groups were investigated. In a series of experiments, we observed that the molecular surface area of the clips and tweezers only depended on the skeletal structure and not on the polar groups. The measured areas agreed with the effective molecular diameters of the molecules if the aromatic side walls of the clips or tweezers were assumed to be aligned perpendicularly to the water surface. We compared the phase behavior of the pure molecular clips and tweezers with that of the host-guest complexes of these molecules, which were formed with 1,2,4,5-tetracyanobenzene (TCNB) as the guest molecule. For the clips with a central benzene (I) and naphthalene spacer unit (II), the complex formation with TCNB had no measurable influence on the phase diagrams of the films. We observed, however, a dramatic difference in the BAM images and pi-A isotherms between the pure molecular tweezers III and its complex with TCNB (TCNB@III). In addition to the pi-A isotherms, we used the surface potential (V)-area (A) isotherms to compare the pure tweezers III with the corresponding complex (TCNB@III). There was a strong difference in the maximum surface potential value for the pure tweezers (450 mV) and that for the complex (300 mV). In additional experiments, we prepared LB layers of such molecules, which were investigated by fluorescence spectroscopy. In comparison to the pure tweezers III, a luminescence emission of charge-transfer (CT) origin was observed for the host-guest complex (TCNB@III) fixed on the solid substrate. It turned out that the spectra were in good agreement with the results observed in chloroform solution. 相似文献
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Molecular tweezers are simple molecular receptors that can be characterized by the presence of two flat pincers separated by a more or less rigid tether. They have the ability to form complexes with a substrate molecule by gripping the substrate between the tips of the tweezers in a similar manner to that of mechanical tweezers. Kl?rner et al. synthesized one of the structurally simplest molecular tweezers, which is reported to bind electrodeficient aromatic and aliphatic substrates as well as organic cations. Complexes between these molecular tweezers and electron-rich aromatic, aliphatic, or anionic substrates have not been observed. Inspired by several recent reports that describe the interaction of hexafluorobenzene with electron-rich sites of molecules, we conducted a theoretical study to show the possibility of building molecular tweezers, based on those synthesized by Kl?rner, which were able to bind to anions and thus increase their potential as molecular receptors. We characterized complexes formed between several fluorinated derivatives of simple tweezers and an iodine anion, and analyzed the nature of the intermolecular interactions as well as the energetics for the process of complexation. The stabilization trend reflected by the energetic results when fluorine substituents were added to benzene rings confirms our hypothesis about the possibility of obtaining neutral tweezers composed of aromatic rings that can bind anions. 相似文献
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This study applies a novel computational method to study molecular recognition for three sets of synthetic hosts: molecular clips, molecular tweezers, and a synthetic barbiturate receptor. The computed standard free energies of binding for the 12 binding reactions agree closely with experiment and provide insight into the roles of configurational entropy, preorganization, and induced fit in the systems studied. The computed changes in configurational entropy are comparable in magnitude to the changes in mean potential plus solvation energy, and they result primarily from changes in the average width of the energy wells upon binding. A strong correlation is observed between the changes in configurational energy and configurational entropy upon binding, resulting in near-linear compensation analogous to classical entropy-enthalpy compensation. 相似文献
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Taken to the molecular level, the concept of “tweezers” opens a rich and fascinating field at the convergence of molecular recognition, biomimetic chemistry and nanomachines. Composed of a spacer bridging two interaction sites, the behaviour of molecular tweezers is strongly influenced by the flexibility of their spacer. Operating through an “induced‐fit” recognition mechanism, flexible molecular tweezers select the conformation(s) most appropriate for substrate binding. Their adaptability allows them to be used in a variety of binding modes and they have found applications in chirality signalling. Rigid spacers, on the contrary, display a limited number of binding states, which lead to selective and strong substrate binding following a “lock and key” model. Exquisite selectivity may be expressed with substrates as varied as C60, nanotubes and natural cofactors, and applications to molecular electronics and enzyme inhibition are emerging. At the crossroad between flexible and rigid spacers, stimulus‐responsive molecular tweezers controlled by ionic, redox or light triggers belong to the realm of molecular machines, and, applied to molecular tweezing, open doors to the selective binding, transport and release of their cargo. Applications to controlled drug delivery are already appearing. The past 30 years have seen the birth of molecular tweezers; the next many years to come will surely see them blooming in exciting applications. 相似文献
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Oligo Tr?ger's bases are compounds containing two or more Tr?ger's base subunits (1,5-methanodiareno[b,f][1,5]diazocines) sharing one or more arene parts. Due to their interesting molecular shapes, these compounds are studied as chiral molecular tweezers, clips, cavitands, clefts, calixes, etc. This review includes all available data on oligo Tr?ger's bases, and introduces their preparation and properties to a wide audience. 相似文献
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A novel type of molecular tweezers with different chiral center and cleft has been designed and prepared by usingα-hyodeoxycholic acid as spacer and D/L-amino acid methyl ester as chiral arm attached at 3-position.Their structures were elucidated by ~1H NMR,FTIR and elemental analysis.Their recognition properties for various D/L-amino acid methyl esters were also investigated.The preliminary results indicated that these chiral single-armed molecular tweezers exhibited good recognition ability for D/L-ami... 相似文献
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摘要 以α-猪去氧胆酸为隔离基,在3位桥联不同的D,L-氨基酸甲酯作手性臂,合成了具有不同手性中心和裂穴的新型分子钳受体。结构均经1H NMR、IR及元素分析确证,并考察了其对D/L-氨基酸甲酯的识别性能。初步研究表明,这类分子钳对D/L-氨基酸甲酯具有良好的识别性能,其结合常数(Ka)可达5.24 × 103 L•mol-1。 相似文献
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Application of the synthetic methodology developed in our laboratory yields molecular clips and tweezers with corannulene pincers and cyclooctadiene or cyclooctatetraene tethers. These highly nonplanar systems possess a potential for binding guest molecules of various sizes. One of the clips, bis(benzocorannulene)[a,e]cyclooctadiene, exists in a ‘open’ chair conformation encapsulating solvating nitrobenzene in the solid state, while it is expected to prefer an internally π-π stacked twist-boat conformation in the gas phase. 相似文献
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Masakazu Yoshikawa Katsunori Koso Kyoichi Yonetani Satoshi Kitamura Satoshi Kimura 《Journal of polymer science. Part A, Polymer chemistry》2005,43(2):385-396
Molecularly imprinted polymeric membranes were prepared from various oligopeptide tweezers by the adoption of N‐α‐tert‐butoxycarbonyl‐D ‐tryptophan (Boc‐D ‐Trp) or N‐α‐tert‐butoxycarbonyl‐L ‐tryptophan (Boc‐L ‐Trp) as a print molecule. The chiral recognition ability of the formed molecular recognition sites was dependent on the absolute configuration of the print molecule adopted in the membrane preparation (molecular imprinting) process, whereas the candidate oligopeptide tweezers consisted of the L ‐amino acid residues. In other words, the membranes imprinted by the D ‐isomer recognized the D ‐isomer in preference to the corresponding L ‐isomer, and vice versa. The affinity constant between the target molecule and the chiral recognition site from the oligopeptide tweezers was higher than that from a single‐strand oligopeptide derivative. Those membranes selectively transported the enantiomer, which was preferentially incorporated into the membrane by dialysis. The permselectivities for these membranes exceeded their adsorption selectivities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 385–396, 2005 相似文献
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Talbiersky P Bastkowski F Klärner FG Schrader T 《Journal of the American Chemical Society》2008,130(30):9824-9828
Artificial molecular clips and tweezers, designed for cofactor and amino acid recognition, are able to inhibit the enzymatic activity of alcohol dehydrogenase (ADH). IC50 values and kinetic investigations point to two different new mechanisms of interference with the NAD(+)-dependent oxidoreductase: While the clip seems to pull the cofactor out of its cleft, the tweezer docks onto lysine residues around the active site. Both modes of action can be reverted to some extent, by appropriate additives. However, while cofactor depletion by clip 1 was in part restored by subsequent NAD(+) addition, the tweezer (2) inhibition requires the competitive action of lysine derivatives. Lineweaver-Burk plots indicate a competitive mechanism for the clip, with respect to both substrate and cofactor, while the tweezer clearly follows a noncompetitive mechanism. Conformational analysis by CD spectroscopy demonstrates significant ADH denaturation in both cases. However, only the latter case (tweezer-lysine) is reversible, in full agreement with the above-detailed enzyme switch experiments. The complexes of ADH with clips or tweezer can be visualized in a nondenaturing gel electrophoresis, where the complexes migrate toward the anode, in contrast to the pure enzyme which approaches the cathode. Supramolecular chemistry has thus been employed as a means to control protein function with the specificity of artificial hosts opening new avenues for this endeavor. 相似文献
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This article discusses most recent work and progress in the direction of a rational design of small molecule receptors that efficiently interfere with the biological function of a particular receptor or enzyme-some of which are therapeutically relevant. More specifically, the following topics are highlighted here: the inhibition of voltage-dependent potassium channels of the K(v)1.x family by designed porphyrin and calix[4]arene ligands, the structural and functional recovery of the tetramerization domain of mutated P53 protein by tailored calix[4]arene ligands and the control over LDH activity by supramolecular signaling. Finally a new way to modulate NAD(+)-dependent enzymatic activities by molecular clips and tweezers is presented. 相似文献
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芳杂环类多重氢键分子钳人工受体对中性分子的识别性能研究 总被引:3,自引:1,他引:2
根据多点氢键识别原理,设计合成了新的分子钳受体1~6。研究了其对巴比妥 、尿素、二苯甲酮、戊二酰亚胺等中性分子的识别性能。用差紫外光谱法测定了结 合常数和自由能变化(ΔG)。结果表明,所有分子钳受体与所考察的客体分子均 形成1:1型超分子配合物,识别作用的推动力主要为多重氢键的协同作用。讨论了 主客体间尺寸/形状、几何互补等因素对形成超分子配合物的影响。并利用~1H NMR、计算机模拟作辅助手段对实验结果和现象进行了解释。 相似文献