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| Open AccessHigh-throughput discovery of organic cages and catenanes using computational screening fused with robotic synthesis
Supramolecular assemblies remain of great importance to a variety of fields, yet their targeted design and synthesis remains highly challenging. Here, Cooper and colleagues combine computational screening with high-throughput robotic synthesis and discover 33 new organic cage molecules that form cleanly in one-pot syntheses.
- R. L. Greenaway
- , V. Santolini
- & A. I. Cooper
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Article
| Open AccessDynamic and programmable morphology and size evolution via a living hierarchical self-assembly strategy
Controlling shape-shift and size-growth in nanostructures are important developments in nanoscience but controlling morphology change with an instant on/off function remains challenging. Here the authors demonstrate control over morphology and size transformation of POSS molecules based on living thiol-disulfide exchange reactions.
- Xing Wang
- , Peiyuan Gao
- & Decheng Wu
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| Open AccessCreating two self-assembly micro-environments to achieve supercrystals with dual structures using polyhedral nanoparticles
Crystals with multiple structures often perform special functions in nature, inspiring the creation of synthetic analogues. Here, the authors subject polyhedral nanoparticles to two self-assembly micro-environments to realize supercrystals with dual structures, in which the order of the surface layer differs from the bulk structure.
- Yih Hong Lee
- , Chee Leng Lay
- & Xing Yi Ling
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Article
| Open AccessSelf-assembly of metal–organic polyhedra into supramolecular polymers with intrinsic microporosity
Porosity in metal–organic materials typically relies on highly ordered crystalline networks, which hinders material processing and morphological control. Here, the authors use metal–organic polyhedra as porous monomers in supramolecular polymerization to produce colloidal spheres and gels with intrinsic microporosity.
- Arnau Carné-Sánchez
- , Gavin A. Craig
- & Shuhei Furukawa
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Article
| Open AccessPositive and negative regulation of carbon nanotube catalysts through encapsulation within macrocycles
Doping carbon nanomaterials with heteroatoms is the most common way to change their catalytic activity. Here, the authors show that the catalytic properties of single-walled carbon nanotubes can be modified by non-covalently encapsulating them within electron-accepting or electron-donating macrocycles to form rotaxane-like structures.
- Matías Blanco
- , Belén Nieto-Ortega
- & Emilio M. Pérez
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| Open AccessSelf-assembly of multi-stranded perylene dye J-aggregates in columnar liquid-crystalline phases
Perylene bisimides (PBI) exhibit interesting photophysical and self-assembly properties but detailed understanding of the correlation between packing motif and spectroscopic properties is lacking. Here the authors report on self-assembling of PBIs in liquid crystalline phases to give aggregates with J- and H-type coupling contribution between the chromophores.
- Stefanie Herbst
- , Bartolome Soberats
- & Frank Würthner
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Article
| Open AccessA biomimetic chiral-driven ionic gate constructed by pillar[6]arene-based host–guest systems
Uptake and release of glucose is regulated by glucose-sensitive ion channels, but complexity of the system impedes investigation of the gating behavior under physiological conditions. Here the authors use a pillararene based artificial ion channel to mimic and investigate chirality driven switching of a glucose ion channel.
- Yue Sun
- , Fan Zhang
- & Haibing Li
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Article
| Open AccessControl over the emerging chirality in supramolecular gels and solutions by chiral microvortices in milliseconds
Symmetry breaking and chiral amplification are fundamental principles in chemistry and biology but the control of initial chiral bias remains a great challenge. Here the authors show that chiral microvortices can lead to a selection of initial chiral bias of supramolecular systems composed of achiral molecules.
- Jiashu Sun
- , Yike Li
- & Minghua Liu
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Article
| Open AccessDirect observation of exciton–exciton interactions
Some photo-physical processes in multichromophore systems might get triggered only if two excitations are present. Here, the authors introduce exciton–exciton-interaction 2D spectroscopy, which is a non-linear optical method that can selectively track the time evolution of such effects.
- Jakub Dostál
- , Franziska Fennel
- & Tobias Brixner
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Article
| Open AccessFormation of self-assembled gold nanoparticle supercrystals with facet-dependent surface plasmonic coupling
Macroscopically large supercrystals are very difficult to assemble from metallic nanoparticles. Here, the authors use a binary solvent diffusion method to form sub-millimeter gold nanoparticle supercrystals with rare hcp symmetry, and discover that they exhibit facet-dependent optical properties.
- Kaifu Bian
- , Hattie Schunk
- & Hongyou Fan
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Article
| Open AccessThermally triggered polyrotaxane translational motion helps proton transfer
Proton exchange is critical in many applications, such as in conductive proton exchange membranes, but achieving fast proton exchange still remains a challenge. Here the authors report fast proton exchange in a rotaxane based polymer by exploiting thermally triggered translational motion of the mechanically bonded rotaxane.
- Xiaolin Ge
- , Yubin He
- & Tongwen Xu
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Article
| Open AccessAchieving high permeability and enhanced selectivity for Angstrom-scale separations using artificial water channel membranes
Synthetic polymeric membranes used for separations suffer from permeability-selectivity trade-offs. Here the authors demonstrate how a bioinspired pillar[5]arene artificial water channel embedded in a copolymer membrane can improve selectivity while still achieving high permeability.
- Yue-xiao Shen
- , Woochul Song
- & Manish Kumar
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Article
| Open AccessA transient self-assembling self-replicator
Understanding self-replication and persistence in an out-of-equilibrium state is key to designing systems with new properties mimicking “living systems”. Here, the authors developed a synthetic small molecule system in which a transient surfactant replicator is responsible for both an autocatalytic aggregation pathway and a destructive pathway.
- Ignacio Colomer
- , Sarah M. Morrow
- & Stephen P. Fletcher
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Article
| Open AccessIn vivo production of RNA nanostructures via programmed folding of single-stranded RNAs
RNA nanostructures have been demonstrated in a range of biological applications, but their assembly and delivery to cells is difficult. Here the authors demonstrate the in vivo assembly of a RNA nanostructure from a single transcript inside the cellular environment.
- Mo Li
- , Mengxi Zheng
- & Chengde Mao
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Article
| Open AccessIn situ redox reactions facilitate the assembly of a mixed-valence metal-organic nanocapsule
New approaches are required to access metal-organic assemblies with unusual structural properties. Here, the authors use an in situ redox reaction to obtain a mixed-valence, Mn(II)/Mn(III)-containing metal-organic nanocapsule with an odd number of metal ions.
- Asanka S. Rathnayake
- , Hector W. L. Fraser
- & Jerry L. Atwood
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Article
| Open AccessSelf-selection of dissipative assemblies driven by primitive chemical reaction networks
Selection and persistence of chemical non-equilibrium species is crucial for the emergence of life and the exact mechanisms remain elusive. Here the authors show that phase separation is an efficient way to control selection of chemical species when primitive carboxylic acids are brought out-of-equilibrium by high-energy condensing agents.
- Marta Tena-Solsona
- , Caren Wanzke
- & Job Boekhoven
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Article
| Open AccessSupramolecularly directed rotary motion in a photoresponsive receptor
Unidirectional rotation in a synthetic molecular motor is typically driven by intrinsic asymmetry or sequences of chemical transformations. Here, the authors control the direction of a molecule’s rotation through supramolecular binding of a chiral guest and subsequent transfer of its chiral information.
- Sander J. Wezenberg
- & Ben L. Feringa
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Article
| Open AccessStepwise control of host–guest interaction using a coordination polymer gel
Achieving precise control of host–guest interactions in artificial systems is difficult. Here the authors use the thermodynamics of a system in equilibrium to control stepwise release and capture of cyclodextrin (guest) using a coordination polymer as the host and temperature as the stimulus.
- Rahul Dev Mukhopadhyay
- , Gourab Das
- & Ayyappanpillai Ajayaghosh
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Article
| Open AccessCoulombic-enhanced hetero radical pairing interactions
Homo radical spin-pairing interactions between two identical aromatic radicals are common in supramolecular chemistry, but hetero interactions between two different aromatic radicals are seldom observed. Here, the authors find that hetero radical pairing between a radical cation and a radical anion, together with Coulombic attraction, can drive host-guest recognition, representing a new supramolecular recognition motif.
- Xujun Zheng
- , Yang Zhang
- & Hao Li
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Article
| Open AccessHollow organic capsules assemble into cellular semiconductors
Perylene diimide-bithiophene macrocycles are electroactive and shape-persistent hosts. Here, the authors describe their self-assembly into a cellular organic semiconducting film whose voids are electrically sensitive to different guests, and which can function as the active layer in a field-effect transistor device.
- Boyuan Zhang
- , Raúl Hernández Sánchez
- & Colin Nuckolls
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Article
| Open AccessA multistage rotational speed changing molecular rotor regulated by pH and metal cations
Molecular rotors with rotational speed modulation have not yet been well established. Here, the authors report a pH and metal cation triggered molecular rotor, which allows for a four stage speed modulation in the slow-to-fast frequency range.
- Yingying Wu
- , Guangxia Wang
- & Ying Wang
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Article
| Open AccessRatchet-free solid-state inertial rotation of a guest ball in a tight tubular host
Though dynamics of molecules are generally restricted by intermolecular contacts, C60 fullerene is able to rotate freely despite being tightly bound inside a molecular host. Here, the authors study the solid-state dynamics of this host-guest system to understand the anomalous relationship between tight association and low friction.
- Taisuke Matsuno
- , Yusuke Nakai
- & Hiroyuki Isobe
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Article
| Open AccessNanographenes as electron-deficient cores of donor-acceptor systems
Nanographenes in donor-acceptor π-systems generally serve as electron-donating moieties but the reversed structures are hardly reported. Here, the authors present a facile synthetic protocol towards reversed donor-acceptor nanographenes by amination and demonstrate fine property tuning by varying the donating ability of the aniline groups.
- Yu-Min Liu
- , Hao Hou
- & Klaus Müllen
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Article
| Open AccessSupramolecular Kandinsky circles with high antibacterial activity
Nested structures are common throughout nature and art, yet remain challenging synthetic targets in supramolecular chemistry. Here, the authors design multitopic terpyridine ligands that coordinate into nested concentric hexagons, and show that these discrete supramolecules display potent antimicrobial activity.
- Heng Wang
- , Xiaomin Qian
- & Xiaopeng Li
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Article
| Open AccessWarm/cool-tone switchable thermochromic material for smart windows by orthogonally integrating properties of pillar[6]arene and ferrocene
Materials for smart windows usually possess single functionality, thus developing materials that regulate solar energy whilst changing color to affect human emotion is desirable. Here the authors combine pillar[6]arenes and ferrocene/ferrocenium groups to produce warm/cool tone-switchable thermochromic materials.
- Sai Wang
- , Zuqiang Xu
- & Leyong Wang
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Article
| Open AccessSupramolecular latching system based on ultrastable synthetic binding pairs as versatile tools for protein imaging
Although protein-ligand pairs are useful tools for bioimaging, they are susceptible to enzymatic degradation and interference from endogenous species. Here, the authors show that a synthetic and bioorthogonal cucurbit[7]uril-guest binding pair can be used to visualize proteins in cells, overcoming limitations of protein-based platforms.
- Kyung Lock Kim
- , Gihyun Sung
- & Kimoon Kim
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Article
| Open AccessSimultaneous complementary photoswitching of hemithioindigo tweezers for dynamic guest relocalization
Controlling complex photoresponsive systems while minimizing light input is highly challenging. Here, the authors report two photoswitchable molecular tweezers responding to the same light signals with opposite changes in their binding affinities towards a guest molecule allowing for its “light-economic” relocation.
- Sandra Wiedbrauk
- , Thomas Bartelmann
- & Henry Dube
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Article
| Open AccessChiral induction in covalent organic frameworks
Controlling chirality and function in metal organic frameworks has been an achievement, but very difficult to carry out in covalent organic frameworks. Here the authors show chiral covalent organic frameworks that are crystallized from achiral precursors by chiral catalytic induction.
- Xing Han
- , Jie Zhang
- & Yong Cui
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Article
| Open AccessBiomimetic temporal self-assembly via fuel-driven controlled supramolecular polymerization
Modulating the structural and transient characteristics of synthetic nanostructures can be achieved by temporal control of supramolecular assemblies. Here the authors show a biomimetic, ATP-selective and fuel-driven controlled supramolecular polymerization of a phosphate receptor functionalised monomer.
- Ananya Mishra
- , Divya B. Korlepara
- & Subi J. George
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Article
| Open AccessUnderstanding and tailoring ligand interactions in the self-assembly of branched colloidal nanocrystals into planar superlattices
The self-organization of nanocrystals into complex superlattices involves the interplay of different interactions. Here, the authors systematically reveal the effects of particle shape and ligand coverage on the assembly behavior of branched octapods into planar superlattices.
- Andrea Castelli
- , Joost de Graaf
- & Milena P. Arciniegas
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Article
| Open AccessUniform two-dimensional square assemblies from conjugated block copolymers driven by π–π interactions with controllable sizes
Crystallization-driven processes play a vital role in preparing 2D nanostructures which makes structures with high symmetry hard to access. Here the authors present a non-crystallization approach which is based on π–π interactions of a copolymer for the fabrication of 2D symmetric structures with good dimensional control.
- Liang Han
- , Meijing Wang
- & Feng He
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Article
| Open AccessControl over multiple molecular states with directional changes driven by molecular recognition
Multistate molecular systems usually rely on external energy inputs to switch between states. Here, the authors show that a bispyridyl calixpyrrole system directed by only weak noncovalent interactions and metal coordination can access six discrete structural states, with directional and sequential control.
- Takehiro Hirao
- , Dong Sub Kim
- & Jonathan L. Sessler
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| Open AccessDirect observation of single-molecule hydrogen-bond dynamics with single-bond resolution
Hydrogen-bonds are widely found in many systems, such as DNAs and supramolecular assemblies, but it remains challenging to detect their dynamics at a molecular level. Here, Zhou et al. study the stochastic arrangement of hydrogen bonds using single-molecule junctions connected to graphene electrodes.
- Ce Zhou
- , Xingxing Li
- & Xuefeng Guo
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Article
| Open AccessRetrosynthesis of multi-component metal−organic frameworks
The crystal engineering of metal–organic frameworks has led to the construction of complex structures, but has yet to reach the same level of sophistication as organic synthesis. Here, Zhou and colleagues use retrosynthetic chemistry to design and produce complex multi-component frameworks.
- Shuai Yuan
- , Jun-Sheng Qin
- & Hong-Cai Zhou
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Article
| Open AccessPolyrotaxane-based supramolecular theranostics
Multifunctional nanomedicine platforms are highly promising for anticancer therapy. Here, the authors design polyrotaxane-based theranostic nanoparticles that combine targeted drug delivery with photothermal behaviour to exhibit potent anti-tumour effects in vivo.
- Guocan Yu
- , Zhen Yang
- & Xiaoyuan Chen
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Article
| Open AccessAn unusual type of polymorphism in a liquid crystal
Polymorphism is a property that allows a material to exist in two or more crystal structures. Here the authors observe thermal-induced structural polymorphism in a bent-core liquid crystal compound and show that by choosing the cooling rate, different structures with distinct structural colours are obtained.
- Lin Li
- , Mirosław Salamończyk
- & Torsten Hegmann
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Article
| Open AccessPhysical basis of amyloid fibril polymorphism
Amyloid fibril structures can display polymorphism. Here the authors reveal the cryo-EM structures of several different fibril morphologies of a peptide derived from an amyloidogenic immunoglobulin light chain and present a mathematical analysis of physical factors that influence fibril polymorphism.
- William Close
- , Matthias Neumann
- & Marcus Fändrich
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Article
| Open AccessReversible chromism of spiropyran in the cavity of a flexible coordination cage
Under confinement, molecular switches lose the conformational freedom often needed to isomerize. Here, the authors show that a flexible coordination cage can adapt its shape to guide the photoisomerization of encapsulated spiropyrans, rendering them reversibly photochromic even within the confines of the cavity.
- Dipak Samanta
- , Daria Galaktionova
- & Rafal Klajn
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Article
| Open AccessSelf-assembly of emissive supramolecular rosettes with increasing complexity using multitopic terpyridine ligands
Metal coordination of multitopic ligands is a powerful approach to building complex, functional architectures. Here, the authors construct three generations of fluorescent supramolecular rosettes by coordination of aggregation-induced emissive ligands, including a 2nd-generation macrocycle that emits pure white light.
- Guang-Qiang Yin
- , Heng Wang
- & Xiaopeng Li
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Article
| Open AccessWalking and rolling of crystals induced thermally by phase transition
Mechanical motions of molecular crystals have been limited to in-place movement or slow crawling. Here, the authors describe chiral azobenzene crystals that walk or roll quickly forward in response to heating or cooling, offering new modes of material locomotion.
- Takuya Taniguchi
- , Haruki Sugiyama
- & Hideko Koshima
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Article
| Open AccessA supramolecular lanthanide separation approach based on multivalent cooperative enhancement of metal ion selectivity
Lanthanide ions possess similar chemical properties, making their separation from one another challenging. Here the authors show that a tris-tridentate ligand causes high-precision metal ion self-sorting, leading to the selective assembly of tetrahedral M4L4 cages across the lanthanide series.
- Xiao-Zhen Li
- , Li-Peng Zhou
- & Qing-Fu Sun
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Article
| Open AccessHigher-generation type III-B rotaxane dendrimers with controlling particle size in three-dimensional molecular switching
The complexity of rotaxane dendrimers poses a great synthetic challenge and the synthesis of higher generation rotaxane dendrimers has therefore rarely been reported. Here the authors report the synthesis of acid-base switchable rotaxane dendrimers up to generation 4 and demonstrate the uptake and release of guest molecules.
- Chak-Shing Kwan
- , Rundong Zhao
- & Ken Cham-Fai Leung
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Article
| Open AccessElucidation of the origin of chiral amplification in discrete molecular polyhedra
The sergeants-and-soldiers effect, in which a few chiral units induce chirality in a large number of achiral molecules, is difficult to quantify at the molecular level. Here, the authors devise an elegant strategy—combining theory and a system of pure organic polyhedra with chiral and achiral vertices—to understand the mechanism of chiral amplification in discrete molecular assemblies.
- Yu Wang
- , Hongxun Fang
- & Xiaoyu Cao
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Article
| Open AccessGeometric isotope effect of deuteration in a hydrogen-bonded host–guest crystal
Deuterating a hydrogen bond can change the bond’s geometry, a phenomenon known as the geometric isotope effect (GIE). Here, the authors find that a hydrogen-bonded host–guest crystal, imidazolium hydrogen terephthalate, exhibits significant GIE on its hydrogen bonds, changing its crystal phases and bulk dielectric properties.
- Chao Shi
- , Xi Zhang
- & Wen Zhang
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Article
| Open AccessSequence-regulated copolymerization based on periodic covalent positioning of monomers along one-dimensional nanochannels
Achieving sequence control in polymers is limited by the relative monomer reactivity and thus often statistically random copolymers are obtained. Here the authors show sequence control in radical polymerizations by immobilising the monomer on a porous coordination polymer and subsequent polymerization with a second free monomer.
- Shuto Mochizuki
- , Naoki Ogiwara
- & Takashi Uemura
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Article
| Open AccessUnusual multiscale mechanics of biomimetic nanoparticle hydrogels
Achieving simultaneous high storage and loss moduli in gels is difficult due to the opposite chemical structure requirements needed for such properties. Here the authors show a spectrum of gels containing CdTe nanoparticles stabilized by glutathione that have such properties which can be rationalised through the developed model.
- Yunlong Zhou
- , Pablo F. Damasceno
- & Nicholas A. Kotov
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Article
| Open AccessControlling protein activity by dynamic recruitment on a supramolecular polymer platform
DNA-origami allows the precise recruitment of DNA-protein conjugates but lacks the dynamics found in natural protein assemblies. Here the authors present a synthetic polymer platform that combines the dynamics of supramolecular polymers with the programmability of DNA-mediated protein recruitment.
- Sjors P. W. Wijnands
- , Wouter Engelen
- & Maarten Merkx
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Article
| Open AccessAntimicrobial peptide capsids of de novo design
With the growing threat of antibiotic resistance, unconventional approaches to antimicrobial discovery are needed. Here, the authors present a peptide topology that mimics virus architecture and assembles into antimicrobial capsids that disrupt bacterial membranes upon contact.
- Emiliana De Santis
- , Hasan Alkassem
- & Maxim G. Ryadnov
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| Open AccessTransient two-dimensional vibrational spectroscopy of an operating molecular machine
A deeper understanding of the mechanics of molecular machines is limited by the fast motions which are in the nanosecond or picosecond timescale. Here the authors present a real-time observation of structural changes in a rotaxane-based molecular shuttle by transient two-dimensional infrared spectroscopy.
- Matthijs R. Panman
- , Chris N. van Dijk
- & Sander Woutersen