Rotaxanes
Anion recognition as a method for templating pseudorotaxane formation. (1/49)
Two thread-shaped cations, pyridinium nicotinamide and imidazolium, as their chloride and hexafluorophosphate salts, were studied with regards to complexation with hydrogen-bond-donating acyclic and macrocyclic ligands. In the latter case, the cations form pseudorotaxanes templated by the chloride anion but not hexafluorophosphate. This formation is a function of the coupling of ion-pairing between the cation and chloride anion and subsequent recognition of the anion by the macrocyclic diamide, which provides the driving force for interpenetration. We propose that this anion template principle is a general method for the construction of pseudorotaxanes and could be applied to other cationic threads, anions, and macrocyclic species. (+info)From reactants to products via simple hydrogen-bonding networks: Information transmission in chemical reactions. (2/49)
The transmission of information is ubiquitous in nature and often occurs through supramolecular hydrogen bonding processes. Here we report that there is a remarkable correlation during synthesis between the efficiency of the hydrogen-bond-directed assembly of peptide-based [2]rotaxanes and the symmetry distortion of the macrocycle in the structure of the final product. It transpires that the ability of the flexible macrocycle-precursor to wrap around an unsymmetrical hydrogen bonding template affects both the reaction yield and a quantifiable measure of the symmetry distortion of the macrocycle in the product. When the yields of peptide rotaxane-forming reactions are high, so is the symmetry distortion in the macrocycle; when the yields are low, indicating a poor fit between the components, the macrocycle symmetry is relatively unaffected by the thread. Thus during a synthetic sequence, as in complex biological assembly processes, hydrogen bonding can code and transmit "information"--in this case a distortion from symmetry--between chemical entities by means of a supramolecularly driven multicomponent assembly process. If this phenomenon is general, it could have far reaching consequences for the use of supramolecular-directed reactions in organic chemistry. (+info)Photoisomerization of a rotaxane hydrogen bonding template: light-induced acceleration of a large amplitude rotational motion. (3/49)
Establishing methods for controlling aspects of large amplitude submolecular movements is a prerequisite for the development of artificial devices that function through rotary motion at the molecular level. Here we demonstrate that the rate of rotation of the interlocked components of fumaramide-derived [2]rotaxanes can be accelerated, by >6 orders of magnitude, by isomerizing them to the corresponding maleamide [2]rotaxanes by using light. (+info)Chemical peristalsis. (4/49)
Molecules that emulate in part the remarkable capabilities of protein motors were recently chemically synthesized. A promising approach is based on physically interlocked macromolecular complexes such as rotaxanes and catenanes. Using the latter, Leigh et al. [Leigh, D. A., Wong, J. K. Y., Dehez, F. & Zerbetto, F. (2003) Nature 424, 174-179] constructed a molecular rotor in which two small rings are induced by pulses of light to move unidirectionally around a third, larger ring. The mechanism is similar to that by which a peristaltic pump operates. Unlike macroscopic peristalsis, however, in which a traveling wave forces material through a series of one-way valves, the chemical peristaltic mechanism does not directly cause the small rings to move but only alters the energetics, with the motion itself arising by thermal activation over energy barriers. Engines operating by this mechanism are "Brownian" motors. Here we describe a minimal two-state mechanism for a catenane-based molecular motor. Although fluctuations caused by equilibrium processes cannot drive directed motion, nonequilibrium fluctuations, whether generated externally or by a far-from-equilibrium chemical reaction, can drive rotation even against an external torque. We discuss a possible architecture for input and output of information and energy between the motor and its environment and give a simple expression for the maximum thermodynamic efficiency. The proposed Brownian motor mechanism is consistent with the high efficiency observed by Yasuda et al. [Yasuda, Y., Noji, H., Kinoshita, K. & Yoshida, M. (1998) Cell 93, 1117-1124] for the F(1)-ATP synthase operating as an ATP-powered molecular rotor. (+info)A reversible molecular valve. (5/49)
In everyday life, a macroscopic valve is a device with a movable control element that regulates the flow of gases or liquids by blocking and opening passageways. Construction of such a device on the nanoscale level requires (i) suitably proportioned movable control elements, (ii) a method for operating them on demand, and (iii) appropriately sized passageways. These three conditions can be fulfilled by attaching organic, mechanically interlocked, linear motor molecules that can be operated under chemical, electrical, or optical stimuli to stable inorganic porous frameworks (i.e., by self-assembling organic machinery on top of an inorganic chassis). In this article, we demonstrate a reversibly operating nanovalve that can be turned on and off by redox chemistry. It traps and releases molecules from a maze of nanoscopic passageways in silica by controlling the operation of redox-activated bistable [2]rotaxane molecules tethered to the openings of nanopores leading out of a nanoscale reservoir. (+info)Probing the structure of a rotaxane with two-dimensional infrared spectroscopy. (6/49)
Femtosecond 2D-IR spectroscopy has been used to study the structure of a [2]rotaxane composed of a benzylic amide macrocycle that is mechanically interlocked onto a succinamide-based thread. Both the macrocycle and the thread contain carbonyl groups, and by determining the coupling between the stretching modes of these groups from the cross-peaks in the 2D-IR spectrum, the structure of the macrocycle-thread system has been probed. Our results demonstrate that 2D-IR spectroscopy can be used to observe structural changes in molecular devices on a picosecond time scale. (+info)Autonomous artificial nanomotor powered by sunlight. (7/49)
Light excitation powers the reversible shuttling movement of the ring component of a rotaxane between two stations located at a 1.3-nm distance on its dumbbell-shaped component. The photoinduced shuttling movement, which occurs in solution, is based on a "four-stroke" synchronized sequence of electronic and nuclear processes. At room temperature the deactivation time of the high-energy charge-transfer state obtained by light excitation is approximately 10 micros, and the time period required for the ring-displacement process is on the order of 100 micros. The rotaxane behaves as an autonomous linear motor and operates with a quantum efficiency up to approximately 12%. The investigated system is a unique example of an artificial linear nanomotor because it gathers together the following features: (i) it is powered by visible light (e.g., sunlight); (ii) it exhibits autonomous behavior, like motor proteins; (iii) it does not generate waste products; (iv) its operation can rely only on intramolecular processes, allowing in principle operation at the single-molecule level; (v) it can be driven at a frequency of 1 kHz; (vi) it works in mild environmental conditions (i.e., fluid solution at ambient temperature); and (vii) it is stable for at least 10(3) cycles. (+info)Evaluation of synthetic linear motor-molecule actuation energetics. (8/49)
By applying atomic force microscope (AFM)-based force spectroscopy together with computational modeling in the form of molecular force-field simulations, we have determined quantitatively the actuation energetics of a synthetic motor-molecule. This multidisciplinary approach was performed on specifically designed, bistable, redox-controllable [2]rotaxanes to probe the steric and electrostatic interactions that dictate their mechanical switching at the single-molecule level. The fusion of experimental force spectroscopy and theoretical computational modeling has revealed that the repulsive electrostatic interaction, which is responsible for the molecular actuation, is as high as 65 kcal.mol(-1), a result that is supported by ab initio calculations. (+info)I'm sorry for any confusion, but "rotaxanes" is not a term commonly used in medical definitions. Rotaxanes are actually a concept from the field of chemistry, specifically supramolecular chemistry. They refer to mechanically interlocked molecules, consisting of a dumbbell-shaped component with two large rings that thread onto the ends of the dumbbell and cannot come off, much like a macrocycle around an axle.
While rotaxanes have potential applications in various fields, including nanotechnology and materials science, they are not directly related to medical definitions or human health. If you have any questions about medical terminologies or concepts, I'd be happy to help with those instead!
Cyclobutanes are a class of organic compounds that contain a four-membered carbon ring. The carbons in this ring are bonded to each other in a cyclic arrangement, forming a square-like structure. These compounds can be found naturally or synthesized in the laboratory and play important roles in various chemical reactions and biological processes.
Cyclobutanes are relatively uncommon in nature due to the strain associated with having four carbons in a small ring. This strain makes the molecules more reactive, which can lead to interesting chemical properties. For example, cyclobutanes can undergo ring-opening reactions when exposed to heat or light, leading to the formation of new chemical bonds and the release of energy.
In biology, cyclobutane rings are found in certain types of DNA damage, such as those caused by ultraviolet (UV) radiation. These damages can lead to mutations and may contribute to the development of skin cancer. However, cells have mechanisms for repairing this type of DNA damage, helping to prevent these negative outcomes.
Overall, while cyclobutanes are relatively simple molecules, they have important implications in chemistry and biology, making them a fascinating area of study.
Rotaxane
Polyrotaxane
Pauson-Khand reaction
Polyyne
Catenane
Mechanically interlocked molecular architectures
Ribosomally synthesized and post-translationally modified peptides
Polycatenane
Carbon nanotube chemistry
William Dichtel
Christoph Weder
Supramolecular chemistry
Viologen
Cluster of Excellence Frankfurt Macromolecular Complexes
Nanotechnology
Vincenzo Balzani
Α-Cyclodextrin
Jean-Pierre Sauvage
Cyclodextrin
Alexandra Slawin
Harry Anderson (chemist)
Cucurbituril
Cycloparaphenylene
Cyanostar
Ramesh Jasti
Molecular machine
Kinetic isotope effect
Soft matter
Copper compounds
Copper
Rotaxane - Wikipedia
Bringing Functional Groups into Rotaxanes - ChemistryViews
Enhancing the selectivity of prolinamide organocatalysts using the mechanical bond in [2]rotaxanes - Chemical Science (RSC...
A vinylic rotaxane cross-linker for toughened network polymers from the radical polymerization of vinyl monomers - Polymer...
Controlling the Rate of Shuttling Motions in [2]Rotaxanes by Electrostatic Interactions: A Cation as Solvent-Tunable Brake -...
Toward daisy chain polymers: 'Wittig exchange' of stoppers in [2]rotaxane monomers - Fingerprint - Waseda University
A new protocol for rotaxane synthesis - Stoddart Mechanostereochemistry Group
Electrochemically addressable trisradical rotaxanes organized within a metal-organic framework<...
Molecular 'Wheels' Facilitate Development of Industrial Soft Polymers
Molecular meccano 13. Self-assembly of [n]rotaxanes bearing dendritic stoppers - Stoddart Mechanostereochemistry Group
Redox-controlled self-inclusion of a lasso-type pseudo[1]rotaxane • Sonderforschungsbereich 765
MALDI-MS Imaging Analysis of Noninflammatory Type III Rotaxane Dendrimers<...
Controlling dynamics in extended molecular frameworks | Nature Reviews Chemistry
Segmented polyurethanes containing movable rotaxane units on the main chain: Synthesis, structure, and mechanical properties<...
Formation and characterization of polymetallic {CrxMy} rings in vacuo | Nature Synthesis
Nanotechnology - Wikipedia
Marcel Drabbels - People - EPFL
"Rotaxane Rings Promote Oblique Packing and Extended Lifetimes in DNA-T" by Matthew S. Barclay, Simon K. Roy et al.
Prediction and clarification of structures of (bio)molecules on surfaces
Intrinsic chirality of triple‐layered naphthalenophane and related graphs | SpringerLink
Vauthey Research Group - Group Members
publication list | Max Planck Institute for Polymer Research
Yusuke Matsuoka - Search Results - PubMed
Organic Division South East Regional Meeting
GBMI - Grup de Biotecnologia Molecular i Industrial
The Journal of Organic Chemistry | Vol 82, No 17
Physics Department, TUM | Module CH3216
Press release: The 2016 Nobel Prize in Chemistry - NobelPrize.org
Synthesis7
- Much of the research concerning rotaxanes and other mechanically interlocked molecular architectures, such as catenanes, has been focused on their efficient synthesis or their utilization as artificial molecular machines. (wikipedia.org)
- The earliest reported synthesis of a rotaxane in 1967 relied on the statistical probability that if two halves of a dumbbell-shaped molecule were reacted in the presence of a macrocycle that some small percentage would connect through the ring. (wikipedia.org)
- However, the synthesis of rotaxanes has advanced significantly and efficient yields can be obtained by preorganizing the components utilizing hydrogen bonding, metal coordination, hydrophobic forces, covalent bonds, or coulombic interactions. (wikipedia.org)
- Synthesis of thiophene-capped [2]rotaxanes. (mpg.de)
- 2022 ) Polyyne [3]rotaxanes: Synthesis via dicobalt carbonyl complexes and enhanced stability. (academictree.org)
- Mechanochemical synthesis of the smallest [2]rotaxane. (beilstein-journals.org)
- Mechanochemical liquid-assisted one-pot two-step synthesis of [2]rotaxanes under high-speed vibrati. (beilstein-journals.org)
Catenanes1
- Landmark achievements of his lab include the first synthetic Brownian ratchet molecular motors (2003), synthetic molecular machines able to perform macroscopic work (2005), the invention of catalytic routes to rotaxanes, catenanes and knots, and the first molecular weaving (2020). (gonzaga.edu)
Functional rotaxanes1
- So far, the repertoire of available functional rotaxanes as building blocks for the preparation of stimuli-responsive polymers remains limited. (chemistryviews.org)
Molecular11
- A rotaxane (from Latin rota 'wheel', and axis 'axle') is a mechanically interlocked molecular architecture consisting of a dumbbell-shaped molecule which is threaded through a macrocycle (see graphical representation). (wikipedia.org)
- Rotaxane-based molecular machines have been of initial interest for their potential use in molecular electronics as logic molecular switching elements and as molecular shuttles. (wikipedia.org)
- Controlling the position of the macrocycle allows the rotaxane to function as a molecular switch, with each possible location of the macrocycle corresponding to a different state. (wikipedia.org)
- Rotaxane based systems have also been shown to function as molecular muscles. (wikipedia.org)
- Researchers have manipulated structures called rotaxanes that could pave the way for new possibilities in molecular computing, sensors, and drug delivery. (designnews.com)
- Hokkaido University researchers Minami Ebe, Asuka Soga, Takuya Isono, and Toshifumi Satoh, who worked with rotaxanes, or interlocked molecular structures, in their research to develop what are called 'network polymers. (designnews.com)
- Scientists from Hokkaido University and other institutions in Japan worked with rotaxanes, or interlocked molecular structures, in their research to develop what are called 'network polymers. (designnews.com)
- The team has taken current research surrounding these structures further through the creation of macro-rotaxanes that have multicyclic wheels interlocked with several high-molecular-weight axles. (designnews.com)
- En 1996, il est retourné aux Pays-Bas pour joindre le FOM Institute for Atomic and Molecular Physics à Amsterdam où il a mis au point un nouveau type de " streak cameras " pour l infrarouge. (epfl.ch)
- Among his developments based on rotaxanes are a molecular lift, a molecular muscle and a molecule-based computer chip. (nobelprize.org)
- The third application is based on the idea that low-barrier molecular rotary motors having rotaxane architecture can be constructed using a cucurbituril host and a polyyne guest serving as stator and rotator, respectively. (openu.ac.il)
Polymers2
- According to the researchers, this kind of rotaxane bearing functional groups is a powerful platform for preparing stimuli-responsive polymers. (chemistryviews.org)
- A [2]rotaxane cross-linker ( RC ) with one vinyl group in each component was designed and synthesized as a vinylic cross-linker for highly toughened network polymers, which were prepared from the radical polymerization of n -butyl acrylate and 2-ethylhexyl acrylate in the presence of 0.5 mol% of RC . (rsc.org)
Molecule3
- The partial macrocycle then undergoes a ring closing reaction around the dumbbell-shaped molecule, forming the rotaxane. (wikipedia.org)
- Rotaxanes are composed of a linear 'axle' molecule penetrating one or more cyclic 'wheel' molecules, with bulky groups at the end of the axle that prevent the wheels from coming off. (designnews.com)
- Article: Akira Harada, Osaka University, Single-Molecule Imaging of Rotaxanes Immobilized on Glass Substrates: Observation of Rotary Movement, Angewandte Chemie International Edition 2008, 47, No. 32, 6077? (science20.com)
20201
- 2020 ) Photochemical Unmasking of Polyyne Rotaxanes. (academictree.org)
Axle3
- Da-Hui Qu and colleagues, East China University of Science and Technology, Shanghai, have designed, synthesized, and characterized a functional [2]rotaxane with two alkenyl bonds on the macrocycle and the axle, respectively. (chemistryviews.org)
- A series of rotaxanes, with phenolic axle centerpieces and tetralactam macrocycles as the wheels, has been prepared in good yields. (uni-regensburg.de)
- 83%) using a [2]rotaxane diol that has a hydroxy group in each wheel and axle component. (elsevierpure.com)
Abstract1
- abstract = "The organization of trisradical rotaxanes within the channels of a Zr6-based metal-organic framework (NU-1000) has been achieved postsynthetically by solvent-assisted ligand incorporation. (york.ac.uk)
Dumbbell-shaped1
- To do this, they built upon their previous work, published last year, in which they developed a type of polyurethane that contains stress-sensing rotaxane consisting of ring-shaped fluorescent molecules threaded on dumbbell-shaped molecules featuring so-called "quencher groups" - which decrease the fluorescence intensity of a given substance - at their centre. (canplastics.com)
Structures5
- We think the multicyclic structures in these macro-rotaxanes could be useful as non-leaching additives, permanently retained in a polymer network by the way they hold onto several neighboring polymer chains," he said. (designnews.com)
- Rotaxane dendrimers with hyperbranched macromolecular interlocked structures and size modulation capacity demonstrate drug binding and release ability upon external stimuli. (edu.hk)
- The traditional prepolymer method was applied to introduce rotaxane structures at different locations in the soft segment and at the boundary between soft and hard segments. (elsevierpure.com)
- Differential scanning calorimetry (DSC), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT-IR), and synchrotron X-ray measurements revealed that the phase-separated structures of the SPUs were almost independent of the amount of rotaxane. (elsevierpure.com)
- The highly movable rotaxane scaffold was even effective for toughening the SPU, which is a physically cross-linked network, without changing their phase-separated structures. (elsevierpure.com)
Precursors1
- Robust Zr(IV)-carboxylate bonds are forged between the Zr clusters of NU-1000 and carboxylic acid groups of rotaxane precursors (semirotaxanes) as part of this building block replacement strategy. (york.ac.uk)
Electrostatic1
- Instead of suppressing the shuttling motion completely, as observed in other rotaxanes, our rotaxane is the first system in which electrostatic interactions modulate the speed of the mechanical motion between a fast and a slow motion state as a response to a reversible external stimulus. (uni-regensburg.de)
Pseudorotaxane1
- This dynamic complex or pseudorotaxane is then converted to the rotaxane by reacting the ends of the threaded guest with large groups, preventing disassociation. (wikipedia.org)
Fraser Stoddart1
- The second step was taken by Fraser Stoddart in 1991, when he developed a rotaxane . (nobelprize.org)
Cyclic2
- Cyclic voltammetry measurements performed on electroactive thin films of the resulting material indicate that redox-active viologen subunits located on the rotaxane components can be accessed electrochemically in the solid state. (york.ac.uk)
- In the current study, the researchers developed three new polyurethanes that glowed blue, green or orange when stretched, demonstrating that the colour can be tailored simply by using different cyclic fluorescent rings in the rotaxanes. (canplastics.com)
Fluorescent1
- Chapter VIII demonstrates using a nanohoop rotaxane as a fluorescent probe for H2S. (uoregon.edu)
Molecules2
- A diacylaminopyridine moiety was incorporated into the thread for directing [2]rotaxane formation further allowing the association of complementary small molecules. (rsc.org)
- This gave snapshots of individual rotaxane molecules in the form of emission patterns. (science20.com)
Compounds1
- This paves the way to create even more complex geometric compounds such as 'rotaxane' and 'trefoil knot' at a similar scale. (nanowerk.com)
Researchers2
- As the subject of their study the researchers chose a rotaxane. (science20.com)
- The researchers showed that the cuff of the rotaxane does not rotate if the sample is dry. (science20.com)
Macrocycle2
- To obtain a reasonable quantity of rotaxane, the macrocycle was attached to a solid-phase support and treated with both halves of the dumbbell 70 times and then severed from the support to give a 6% yield. (wikipedia.org)
- one part of the thread is then threaded to the macrocycle, forming a semi rotaxane, and end is closed of by the other part of the thread forming the rotaxane. (wikipedia.org)
Rotary1
- The rotary movement of a chromophore-modified alpha-cyclodextrin (alpha-CD) was studied in a rotaxane structure attached to a glass substrate. (science20.com)
Mechanical1
- The mechanical properties of the formed SPUs were evaluated via tensile tests, and we determined that the introduction of an appropriate amount of rotaxane structure improved their extensibility, toughness, and stress-relaxing properties. (elsevierpure.com)
Structure1
- The threaded rotaxane structure is confirmed in the gas phase by tandem mass spectrometric experiments through a detailed fragmentation pattern analysis, in solution by NMR spectroscopy, and in the solid state through X-ray crystallography. (uni-regensburg.de)
Representation1
- a) Schematic representation for the construction of a [2]rotaxane. (beilstein-journals.org)
Rings2
- Rotaxane Rings Promote Oblique Packing and Extended Lifetimes in DNA-T" by Matthew S. Barclay, Simon K. Roy et al. (boisestate.edu)
- Here, we show that adding rotaxane rings to squaraine dyes templated with DNA promotes an elusive oblique packing arrangement with highly desirable optical properties. (boisestate.edu)
Groups1
- The induction of active and functional groups make the preparation of rotaxanes more difficult and complicated. (chemistryviews.org)
Components1
- The two components of a rotaxane are kinetically trapped since the ends of the dumbbell (often called stoppers) are larger than the internal diameter of the ring and prevent dissociation (unthreading) of the components since this would require significant distortion of the covalent bonds. (wikipedia.org)
Systems1
- The rotaxane-based systems were tested as organocatalysts in asymmetric enamine-mediated processes, revealing a significantly improved catalytic ability if compared with the non-interlocked thread. (rsc.org)
Chain1
- One side of the rotaxane chain is terminated by a bulky stopper bearing three long alkyl chains to prevent the macrocyclic moiety from slipping out the thread. (chemistryviews.org)
Interest1
- The research reflects a renewed interest in working with rotaxanes, which initially were regarded as chemical curiosities by the scientific community. (designnews.com)
Method2
- The method of slipping is one which exploits the thermodynamic stability of the rotaxane. (wikipedia.org)
- Herein, we reported a novel method to display the in situ spatial distribution of label-free monodispersed type III rotaxane dendrimers (RDs) G1 (first generation, size ∼1.5 nm) and G2 (second generation, size ∼5 nm) that were explored as potential drug vehicles in spleen tissue by using matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-MSI). (edu.hk)
Type1
- The self-inclusion behavior of a tetrathiafulvalene-containing lasso-type pseudo[1]rotaxane can be reversibly switched between a threaded and non-threaded state by redox-stimuli. (sfb765.de)
Chemical1
- These rotaxane machines can be manipulated both by chemical and photochemical inputs. (wikipedia.org)