Molecular machine#Biological

{{Short description|Molecular-scale artificial or biological device}}

Molecular machines are a class of molecules typically described as an assembly of a discrete number of molecular components intended to produce mechanical movements in response to specific stimuli, mimicking macromolecular devices such as switches and motors. Naturally occurring or biological molecular machines are responsible for vital living processes such as DNA replication and ATP synthesis. Kinesins and ribosomes are examples of molecular machines, and they often take the form of multi-protein complexes. For the last several decades, scientists have attempted, with varying degrees of success, to miniaturize machines found in the macroscopic world. The first example of an artificial molecular machine (AMM) was reported in 1994, featuring a rotaxane with a ring and two different possible binding sites. In 2016 the Nobel Prize in Chemistry was awarded to Jean-Pierre Sauvage, Sir J. Fraser Stoddart, and Bernard L. Feringa for the design and synthesis of molecular machines.Image:Kinesin_walking.gif walking on a microtubule is a molecular biological machine using protein domain dynamics on nanoscales.]]

AMMs have diversified rapidly over the past few decades and their design principles, properties, and characterization methods have been outlined better. A major starting point for the design of AMMs is to exploit the existing modes of motion in molecules, such as rotation about single bonds or cis-trans isomerization. Different AMMs are produced by introducing various functionalities, such as the introduction of bistability to create switches. A broad range of AMMs has been designed, featuring different properties and applications; some of these include molecular motors, switches, and logic gates. A wide range of applications have been demonstrated for AMMs, including those integrated into polymeric, liquid crystal, and crystalline systems for varied functions (such as materials research, homogenous catalysis and surface chemistry).

Terminology

Several definitions describe a "molecular machine" as a class of molecules typically described as an assembly of a discrete number of molecular components intended to produce mechanical movements in response to specific stimuli. The expression is often more generally applied to molecules that simply mimic functions that occur at the macroscopic level. A few prime requirements for a molecule to be considered a "molecular machine" are: the presence of moving parts, the ability to consume energy, and the ability to perform a task.{{cite journal |last1=Cheng |first1=C. |last2=Stoddart |first2=J. F. |title=Wholly Synthetic Molecular Machines |journal=ChemPhysChem |date=2016 |volume=17 |issue=12 |pages=1780–1793 |doi=10.1002/cphc.201501155|pmid=26833859 |s2cid=205704375 |doi-access=free }} Molecular machines differ from other stimuli-responsive compounds that can produce motion (such as cis-trans isomers) in their relatively larger amplitude of movement (potentially due to chemical reactions) and the presence of a clear external stimulus to regulate the movements (as compared to random thermal motion).{{cite journal |last1=Vincenzo |first1=V. |last2=Credi |first2=A. |last3=Raymo |first3=F. M. |last4=Stoddart |first4=J. F. |title=Artificial Molecular Machines |journal=Angewandte Chemie International Edition |date=2000 |volume=39 |issue=19 |pages=3348–3391 |doi=10.1002/1521-3773(20001002)39:19<3348::AID-ANIE3348>3.0.CO;2-X|pmid=11091368 |bibcode=2000AngCh..39.3348B }} Piezoelectric, magnetostrictive, and other materials that produce a movement due to external stimuli on a macro-scale are generally not included, since despite the molecular origin of the motion the effects are not useable on the molecular scale.{{cn|date=December 2024}}

This definition generally applies to synthetic molecular machines, which have historically gained inspiration from the naturally occurring biological molecular machines (also referred to as "nanomachines"). Biological machines are considered to be nanoscale devices (such as molecular proteins) in a living system that convert various forms of energy to mechanical work in order to drive crucial biological processes such as intracellular transport, muscle contractions, ATP generation and cell division.{{cite journal |last1=Huang |first1=T. J. |last2=Juluri |first2=B. K. |title=Biological and biomimetic molecular machines |journal=Nanomedicine |date=2008 |volume=3 |issue=1 |pages=107–124 |doi=10.2217/17435889.3.1.107|pmid=18393670 }}{{cite journal |last1=Kinbara |first1=K. |last2=Aida |first2=T. |title=Toward Intelligent Molecular Machines: Directed Motions of Biological and Artificial Molecules and Assemblies |journal=Chemical Reviews |date=2005 |volume=105 |issue=4 |pages=1377–1400 |doi=10.1021/cr030071r|pmid=15826015 }}

History

{{Rquote

|align=right

|quote=What would be the utility of such machines? Who knows? I cannot see exactly what would happen, but I can hardly doubt that when we have some control of the arrangement of things on a molecular scale we will get an enormously greater range of possible properties that substances can have, and of the different things we can do.

|author= Richard Feynman

|source= There's Plenty of Room at the Bottom

}}

Biological molecular machines have been known and studied for years given their vital role in sustaining life, and have served as inspiration for synthetically designed systems with similar useful functionality. The advent of conformational analysis, or the study of conformers to analyze complex chemical structures, in the 1950s gave rise to the idea of understanding and controlling relative motion within molecular components for further applications. This led to the design of "proto-molecular machines" featuring conformational changes such as cog-wheeling of the aromatic rings in triptycenes.{{cite journal |last1=Kay |first1=E. R. |last2=Leigh |first2=D. A. |title=Rise of the molecular machines |journal=Angewandte Chemie International Edition |date=2015 |volume=54 |issue=35 |pages=10080–10088 |doi=10.1002/anie.201503375|pmid=26219251 |pmc=4557038 }} By 1980, scientists could achieve desired conformations using external stimuli and utilize this for different applications. A major example is the design of a photoresponsive crown ether containing an azobenzene unit, which could switch between cis and trans isomers on exposure to light and hence tune the cation-binding properties of the ether.{{cite journal |last1=Shinkai |first1=S. |last2=Nakaji |first2=T. |last3=Nishida |first3=Y. |last4=Ogawa |first4=T. |last5=Manabe |first5=O. |title=Photoresponsive crown ethers. 1. Cis-trans isomerism of azobenzene as a tool to enforce conformational changes of crown ethers and polymers |journal=Journal of the American Chemical Society |date=1980 |volume=102 |issue=18 |pages=5860–5865 |doi=10.1021/ja00538a026|bibcode=1980JAChS.102.5860S }} In his seminal 1959 lecture There's Plenty of Room at the Bottom, Richard Feynman alluded to the idea and applications of molecular devices designed artificially by manipulating matter at the atomic level.{{cite journal |last1=Feynman |first1=R. |title=There's Plenty of Room at the Bottom |journal=Engineering and Science |authorlink = Richard Feynman |date=1960 |volume=23 |issue=5 |pages=22–36 |url=https://calteches.library.caltech.edu/1976/1/1960Bottom.pdf}} This was further substantiated by Eric Drexler during the 1970s, who developed ideas based on molecular nanotechnology such as nanoscale "assemblers",{{cite journal |last1=Drexler |first1=K. E. |title=Molecular engineering: An approach to the development of general capabilities for molecular manipulation |journal=Proceedings of the National Academy of Sciences |date=1981 |volume=78 |issue=9 |pages=5275–5278 |authorlink=K. Eric Drexler |doi=10.1073/pnas.78.9.5275|pmid=16593078 |pmc=348724 |bibcode=1981PNAS...78.5275D |doi-access=free }} though their feasibility was disputed.{{cite news |last1=Baum |first1=R. |title=Drexler and Smalley make the case for and against 'molecular assemblers' |url=https://pubsapp.acs.org/cen/coverstory/8148/8148counterpoint.html |access-date=16 January 2023 |work=C&EN |volume=81 |issue=48 |date=1 December 2003 |pages=37–42}}

File:Molecular shuttle first report.png unit (green), but shifts to the biphenol unit (red) when the benzidine gets protonated (purple) as a result of electrochemical oxidation or lowering of the pH.|The first example of an artificial molecular machine (a switchable molecular shuttle). The positively charged ring (blue) is initially positioned over the benzidine unit (green), but shifts to the biphenol unit (red) when the benzidine gets protonated (purple) as a result of electrochemical oxidation or lowering of the pH.]]

Though these events served as inspiration for the field, the actual breakthrough in practical approaches to synthesize artificial molecular machines (AMMs) took place in 1991 with the invention of a "molecular shuttle" by Sir Fraser Stoddart.{{cite journal |last1=Anelli |first1=P. L. |last2=Spencer |first2=N. |last3=Stoddart |first3=J. F. |title=A molecular shuttle |journal=Journal of the American Chemical Society |date=1991 |volume=113 |issue=13 |pages=5131–5133 |doi=10.1021/ja00013a096|pmid=27715028 |s2cid=39993887 |doi-access=free |bibcode=1991JAChS.113.5131A }} Building upon the assembly of mechanically linked molecules such as catenanes and rotaxanes as developed by Jean-Pierre Sauvage in the early 1980s,{{cite journal |last1=Dietrich-Buchecker |first1=C. O. |last2=Sauvage |first2=J. P. |last3=Kintzinger |first3=J. P. |title=Une nouvelle famille de molecules : les metallo-catenanes |journal=Tetrahedron Letters |date=1983 |volume=24 |issue=46 |pages=5095–5098 |doi=10.1016/S0040-4039(00)94050-4 |trans-title=A new family of molecules: metallo-catenanes |language=French}}{{cite journal |last1=Dietrich-Buchecker |first1=C. O. |last2=Sauvage |first2=J. P. |last3=Kern |first3=J. M. |title=Templated synthesis of interlocked macrocyclic ligands: the catenands |journal=Journal of the American Chemical Society |date=May 1984 |volume=106 |issue=10 |pages=3043–3045 |doi=10.1021/ja00322a055|bibcode=1984JAChS.106.3043D }} this shuttle features a rotaxane with a ring that can move across an "axle" between two ends or possible binding sites (hydroquinone units). This design realized the well-defined motion of a molecular unit across the length of the molecule for the first time. In 1994, an improved design allowed control over the motion of the ring by pH variation or electrochemical methods, making it the first example of an AMM. Here the two binding sites are a benzidine and a biphenol unit; the cationic ring typically prefers staying over the benzidine ring, but moves over to the biphenol group when the benzidine gets protonated at low pH or if it gets electrochemically oxidized.{{cite journal |last1=Bissell |first1=R. A |last2=Córdova |first2=E. |last3=Kaifer |first3=A. E. |last4=Stoddart |first4=J. F. |title=A chemically and electrochemically switchable molecular shuttle |journal=Nature |date=1994 |volume=369 |issue=6476 |pages=133–137 |doi=10.1038/369133a0|bibcode=1994Natur.369..133B |s2cid=44926804 }} In 1998, a study could capture the rotary motion of a decacyclene molecule on a copper-base metallic surface using a scanning tunneling microscope.{{cite journal |last1=Gimzewski |first1=J. K. |last2=Joachim |first2=C. |last3=Schlittler |first3=R. R. |last4=Langlais |first4=V. |last5=Tang |first5=H. |last6=Johannsen |first6=I. |title=Rotation of a Single Molecule Within a Supramolecular Bearing |journal=Science |date=1998 |volume=281 |issue=5376 |pages=531–533 |doi=10.1126/science.281.5376.531|pmid=9677189 |bibcode=1998Sci...281..531G }} Over the following decade, a broad variety of AMMs responding to various stimuli were invented for different applications.{{cite journal |last1=Balzani |first1=V. |last2=Credi |first2=A. |last3=Raymo |first3=F. M. |last4=Stoddart |first4=J. F. |title=Artificial Molecular Machines |journal=Angewandte Chemie International Edition |date=2000 |volume=39 |issue=19 |pages=3348–3391 |doi=10.1002/1521-3773(20001002)39:19<3348::AID-ANIE3348>3.0.CO;2-X|pmid=11091368 |bibcode=2000AngCh..39.3348B }}{{cite journal |last1=Erbas-Cakmak |first1=S. |last2=Leigh |first2=D. A. |last3=McTernan |first3=C. T. |last4=Nussbaumer |first4=A. L. |title=Artificial Molecular Machines |journal=Chemical Reviews |date=2015 |volume=115 |issue=18 |pages=10081–10206 |doi=10.1021/acs.chemrev.5b00146|pmid=26346838 |pmc=4585175 }} In 2016, the Nobel Prize in Chemistry was awarded to Sauvage, Stoddart, and Bernard L. Feringa for the design and synthesis of molecular machines.{{cite news |author=Staff |title=The Nobel Prize in Chemistry 2016 |url=https://www.nobelprize.org/nobel_prizes/chemistry/laureates/2016/press.html |date=5 October 2016 |work=Nobel Foundation |access-date=5 October 2016 }}{{cite news |last1=Chang |first1=Kenneth |last2=Chan |first2=Sewell |title=3 Makers of 'World's Smallest Machines' Awarded Nobel Prize in Chemistry |url=https://www.nytimes.com/2016/10/06/science/nobel-prize-chemistry.html |date=5 October 2016 |work=New York Times |access-date=5 October 2016 }}

Artificial molecular machines

Over the past few decades, AMMs have diversified rapidly and their design principles, properties, and characterization methods{{cite journal |last1=Nogales |first1=E. |last2=Grigorieff |first2=N. |title=Molecular Machines: putting the pieces together. |journal=The Journal of Cell Biology |date=2001 |volume=152 |issue=1 |pages=F1-10 |doi=10.1083/jcb.152.1.f1 |pmid=11149934|pmc=2193665 }} have been outlined more clearly. A major starting point for the design of AMMs is to exploit the existing modes of motion in molecules. For instance, single bonds can be visualized as axes of rotation,{{cite journal |last1=Jiang |first1=X. |last2=Rodríguez-Molina |first2=B. |last3=Nazarian |first3=N. |last4=Garcia-Garibay |first4=M. A. |title=Rotation of a Bulky Triptycene in the Solid State: Toward Engineered Nanoscale Artificial Molecular Machines |journal=Journal of the American Chemical Society |date=2014 |volume=136 |issue=25 |pages=8871–8874 |doi=10.1021/ja503467e|pmid=24911467 |bibcode=2014JAChS.136.8871J }} as can be metallocene complexes.{{cite journal |last1=Kai |first1=H. |last2=Nara |first2=S. |last3=Kinbara |first3=K. |last4=Aida |first4=T. |title=Toward Long-Distance Mechanical Communication: Studies on a Ternary Complex Interconnected by a Bridging Rotary Module |journal=Journal of the American Chemical Society |date=2008 |volume=130 |issue=21 |pages=6725–6727 |doi=10.1021/ja801646b|pmid=18447353 |bibcode=2008JAChS.130.6725K }} Bending or V-like shapes can be achieved by incorporating double bonds, that can undergo cis-trans isomerization in response to certain stimuli (typically irradiation with a suitable wavelength), as seen in numerous designs consisting of stilbene and azobenzene units.{{cite journal |last1=Kamiya |first1=Y. |last2=Asanuma |first2=H. |title=Light-Driven DNA Nanomachine with a Photoresponsive Molecular Engine |journal=Accounts of Chemical Research |date=2014 |volume=47 |issue=6 |pages=1663–1672 |doi=10.1021/ar400308f|pmid=24617966 }} Similarly, ring-opening and -closing reactions such as those seen for spiropyran and diarylethene can also produce curved shapes.{{cite journal |last1=Morimoto |first1=M. |last2=Irie |first2=M. |title=A Diarylethene Cocrystal that Converts Light into Mechanical Work |journal=Journal of the American Chemical Society |date=2010 |volume=132 |issue=40 |pages=14172–14178 |doi=10.1021/ja105356w|pmid=20858003 |bibcode=2010JAChS.13214172M }} Another common mode of movement is the circumrotation of rings relative to one another as observed in mechanically interlocked molecules (primarily catenanes). While this type of rotation can not be accessed beyond the molecule itself (because the rings are confined within one another), rotaxanes can overcome this as the rings can undergo translational movements along a dumbbell-like axis.{{cite journal |last1=Stoddart |first1=J. F. |title=The chemistry of the mechanical bond |journal=Chemical Society Reviews |date=2009 |volume=38 |issue=6 |pages=1802–1820 |doi=10.1039/B819333A|pmid=19587969 }} Another line of AMMs consists of biomolecules such as DNA and proteins as part of their design, making use of phenomena like protein folding and unfolding.{{cite journal |last1=Mao |first1=X. |last2=Liu |first2=M. |last3=Li |first3=Q. |last4=Fan |first4=C. |last5=Zuo |first5=X. |title=DNA-Based Molecular Machines |journal=JACS Au |date=2022 |volume=2 |issue=11 |pages=2381–2399 |doi=10.1021/jacsau.2c00292|pmid=36465542 |pmc=9709946 }}{{cite journal |last1=Saper |first1=G. |last2=Hess |first2=H. |title=Synthetic Systems Powered by Biological Molecular Motors |journal=Chemical Reviews |date=2020 |volume=120 |issue=1 |pages=288–309 |doi=10.1021/acs.chemrev.9b00249|pmid=31509383 |s2cid=202562979 }}

File:Molecular machine principle 1.pngs. b) Bending due to cis-trans isomerization. c) Translational motion of a ring along the dumbbell-like rotaxane axis. d) Rotation of interlocked rings in a catenane|Some common types of motion seen in some simple components of artificial molecular machines. a) Rotation around single bonds and in sandwich-like metallocenes. b) Bending due to cis-trans isomerization. c) Translational motion of a ring (blue) between two possible binding sites (red) along the dumbbell-like rotaxane axis (purple). d) Rotation of interlocked rings (depicted as blue and red rectangles) in a catenane.]]

AMM designs have diversified significantly since the early days of the field. A major route is the introduction of bistability to produce molecular switches, featuring two distinct configurations for the molecule to convert between. This has been perceived as a step forward from the original molecular shuttle which consisted of two identical sites for the ring to move between without any preference, in a manner analogous to the ring flip in an unsubstituted cyclohexane. If these two sites are different from each other in terms of features like electron density, this can give rise to weak or strong recognition sites as in biological systems — such AMMs have found applications in catalysis and drug delivery. This switching behavior has been further optimized to acquire useful work that gets lost when a typical switch returns to its original state.

Inspired by the use of kinetic control to produce work in natural processes, molecular motors are designed to have a continuous energy influx to keep them away from equilibrium to deliver work.

Various energy sources are employed to drive molecular machines today, but this was not the case during the early years of AMM development. Though the movements in AMMs were regulated relative to the random thermal motion generally seen in molecules, they could not be controlled or manipulated as desired. This led to the addition of stimuli-responsive moieties in AMM design, so that externally applied non-thermal sources of energy could drive molecular motion and hence allow control over the properties. Chemical energy (or "chemical fuels") was an attractive option at the beginning, given the broad array of reversible chemical reactions (heavily based on acid-base chemistry) to switch molecules between different states.{{cite journal |last1=Biagini |first1=C. |last2=Di Stefano |first2=S. |title=Abiotic Chemical Fuels for the Operation of Molecular Machines |journal=Angewandte Chemie International Edition |date=2020 |volume=59 |issue=22 |pages=8344–8354 |doi=10.1002/anie.201912659|pmid=31898850 |s2cid=209676880 }} However, this comes with the issue of practically regulating the delivery of the chemical fuel and the removal of waste generated to maintain the efficiency of the machine as in biological systems. Though some AMMs have found ways to circumvent this,{{cite journal |last1=Tatum |first1=L. A. |last2=Foy |first2=J. T. |last3=Aprahamian |first3=I. |title=Waste Management of Chemically Activated Switches: Using a Photoacid To Eliminate Accumulation of Side Products |journal=Journal of the American Chemical Society |date=2014 |volume=136 |issue=50 |pages=17438–17441 |doi=10.1021/ja511135k|pmid=25474221 |doi-access=free |bibcode=2014JAChS.13617438T }} more recently waste-free reactions such based on electron transfers or isomerization have gained attention (such as redox-responsive viologens). Eventually, several different forms of energy (electric,{{cite journal |last1=Le Poul |first1=N. |last2=Colasson |first2=B. |title=Electrochemically and Chemically Induced Redox Processes in Molecular Machines |journal=ChemElectroChem |date=2015 |volume=2 |issue=4 |pages=475–496 |doi=10.1002/celc.201402399}} magnetic,{{cite journal |last1=Thomas |first1=C. R. |last2=Ferris |first2=D. P. |last3=Lee |first3=J.-H. |last4=Choi |first4=E. |last5=Cho |first5=M. H. |last6=Kim |first6=E. S. |last7=Stoddart |first7=J. F. |last8=Shin |first8=J.-S. |last9=Cheon |first9=J. |last10=Zink |first10=J. I. |title=Noninvasive Remote-Controlled Release of Drug Molecules in Vitro Using Magnetic Actuation of Mechanized Nanoparticles |journal=Journal of the American Chemical Society |date=2010 |volume=132 |issue=31 |pages=10623–10625 |doi=10.1021/ja1022267|pmid=20681678 |bibcode=2010JAChS.13210623T }} optical{{cite journal |last1=Balzani |first1=V. |last2=Credi |first2=A. |last3=Venturi |first3=M. |title=Light powered molecular machines |journal=Chemical Society Reviews |date=2009 |volume=38 |issue=6 |pages=1542–1550 |doi=10.1039/B806328C|pmid=19587950 }} and so on) have become the primary energy sources used to power AMMs, even producing autonomous systems such as light-driven motors.{{cite journal |last1=Balzani |first1=V. |last2=Clemente-León |first2=M. |last3=Credi |first3=A. |last4=Ferrer |first4=B. |last5=Venturi |first5=M. |last6=Flood |first6=A. H. |last7=Stoddart |first7=J. F. |title=Autonomous artificial nanomotor powered by sunlight |journal=Proceedings of the National Academy of Sciences |date=2006 |volume=103 |issue=5 |pages=1178–1183 |doi=10.1073/pnas.0509011103|pmid=16432207 |pmc=1360556 |bibcode=2006PNAS..103.1178B |doi-access=free }}

= Types =

Various AMMs are tabulated below along with indicative images:{{Cite journal|last1=Erbas-Cakmak|first1=Sundus|last2=Leigh|first2=David A.|last3=McTernan|first3=Charlie T.|last4=Nussbaumer|first4=Alina L.|title=Artificial Molecular Machines|journal=Chemical Reviews|volume=115|issue=18|pages=10081–10206|doi=10.1021/acs.chemrev.5b00146|pmid=26346838|pmc=4585175|year=2015}}

class="wikitable"
Type	Details	Image
style="vertical-align: top;" \|Molecular balance \|A molecule that can interconvert between two or more conformational or configurational states in response to the dynamic of multiple intra- and intermolecular driving forces,{{Cite journal\|last1=Paliwal\|first1=S.\|last2=Geib\|first2=S.\|last3=Wilcox\|first3=C. S.\|date=1994\|title=Molecular Torsion Balance for Weak Molecular Recognition Forces. Effects of "Tilted-T" Edge-to-Face Aromatic Interactions on Conformational Selection and Solid-State Structure\|journal=Journal of the American Chemical Society\|volume=116\|issue=10\|pages=4497–4498\|doi=10.1021/ja00089a057\|bibcode=1994JAChS.116.4497P }}{{Cite journal\|last1=Mati\|first1=Ioulia K.\|last2=Cockroft\|first2=Scott L.\|date=2010\|title=Molecular balances for quantifying non-covalent interactions\|journal=Chemical Society Reviews\|volume=39\|issue=11\|pages=4195–4205\|doi=10.1039/B822665M\|pmid=20844782\|url=https://www.pure.ed.ac.uk/ws/files/10097959/Molecular_balances_for_quantifying_non_covalent_interactions.pdf\|hdl=20.500.11820/7ce18ff7-1196-48a1-8c67-3bc3f6b46946\|s2cid=263667 \|hdl-access=free}} such as hydrogen bonding, solvophobic or hydrophobic effects,{{Cite journal\|last1=Y.\|first1=Lixu\|last2=A.\|first2=Catherine\|last3=Cockroft\|first3=S. L.\|date=2015\|title=Quantifying Solvophobic Effects in Nonpolar Cohesive Interactions\|journal=Journal of the American Chemical Society\|volume=137\|issue=32\|pages=10084–10087\|doi=10.1021/jacs.5b05736\|pmid=26159869\|bibcode=2015JAChS.13710084Y \|issn=0002-7863\|hdl=20.500.11820/604343eb-04aa-4d90-82d2-0998898400d2\|url=https://www.pure.ed.ac.uk/ws/files/24692670/scockroft.docx\|hdl-access=free}} π interactions,{{Cite journal\|last1=L.\|first1=Ping\|last2=Z.\|first2=Chen\|last3=Smith\|first3=M. D.\|last4=Shimizu\|first4=K. D.\|date=2013\|title=Comprehensive Experimental Study of N-Heterocyclic π-Stacking Interactions of Neutral and Cationic Pyridines\|journal=The Journal of Organic Chemistry\|volume=78\|issue=11\|pages=5303–5313\|doi=10.1021/jo400370e\|pmid=23675885}} and steric and dispersion interactions.{{Cite journal\|last1=Hwang\|first1=J.\|last2=Li\|first2=P.\|last3=Smith\|first3=M. D.\|last4=Shimizu\|first4=K. D.\|date=2016\|title=Distance-Dependent Attractive and Repulsive Interactions of Bulky Alkyl Groups\|journal=Angewandte Chemie International Edition\|volume=55\|issue=28\|pages=8086–8089\|doi=10.1002/anie.201602752\|pmid=27159670\|doi-access=free}} The distinct conformers of a molecular balance can show different interactions with the same molecule, such that analyzing the ratio of the conformers and the energies for these interactions can enable quantification of different properties (such as CH-π or arene-arene interactions, see image).{{cite journal \|last1=Carroll \|first1=W. R. \|last2=Zhao \|first2=C. \|last3=Smith \|first3=M. D. \|last4=Pellechia \|first4=P. J. \|last5=Shimizu \|first5=K. D. \|title=A Molecular Balance for Measuring Aliphatic CH−π Interactions \|journal=Organic Letters \|date=2011 \|volume=13 \|issue=16 \|pages=4320–4323 \|doi=10.1021/ol201657p\|pmid=21797218 }}{{cite journal \|last1=Carroll \|first1=W. R. \|last2=Pellechia \|first2=P. \|last3=Shimizu \|first3=K. D. \|title=A Rigid Molecular Balance for Measuring Face-to-Face Arene−Arene Interactions \|journal=Organic Letters \|date=2008 \|volume=10 \|issue=16 \|pages=3547–3550 \|doi=10.1021/ol801286k\|pmid=18630926 }} \|File:Molecular balance example.png
style="vertical-align: top;" \|Molecular hinge \|A molecular hinge is a molecule that can typically rotate in a crank-like motion around a rigid axis, such as a double bond or aromatic ring, to switch between reversible configurations.{{cite journal \|last1=Kassem \|first1=Salma \|last2=van Leeuwen \|first2=Thomas \|last3=Lubbe \|first3=Anouk S. \|last4=Wilson \|first4=Miriam R. \|last5=Feringa \|first5=Ben L. \|last6=Leigh \|first6=David A. \|title=Artificial molecular motors \|journal=Chemical Society Reviews \|date=2017 \|volume=46 \|issue=9 \|pages=2592–2621 \|doi=10.1039/C7CS00245A\|pmid=28426052 \|url=https://pure.rug.nl/ws/files/49449226/c7cs00245a_1_.pdf }} Such configurations must have distinguishable geometries; for instance, azobenzene groups in a linear molecule may undergo cis-trans isomerization{{cite journal \|last1=Bandara \|first1=H. M. Dhammika \|last2=Burdette \|first2=S. C. \|title=Photoisomerization in different classes of azobenzene \|journal=Chemical Society Reviews \|date=2012 \|volume=41 \|issue=5 \|pages=1809–1825 \|doi=10.1039/c1cs15179g\|pmid=22008710 }} when irradiated with ultraviolet light, triggering a reversible transition to a bent or V-shaped conformation (see image).{{cite journal \|last1=Wang \|first1=J. \|last2=Jiang \|first2=Q. \|last3=Hao \|first3=X. \|last4=Yan \|first4=H.\|last5=Peng \|first5=H. \|last6=Xiong \|first6=B.\|last7=Liao \|first7=Y. \|last8=Xie \|first8=X. \|title=Reversible photo-responsive gel–sol transitions of robust organogels based on an azobenzene-containing main-chain liquid crystalline polymer \|journal=RSC Advances \|date=2020 \|volume=10 \|issue=7 \|pages=3726–3733 \|doi=10.1039/C9RA10161F\|pmid=35492656 \|pmc=9048773 \|bibcode=2020RSCAd..10.3726W \|doi-access=free }}{{cite journal \|last1=Hada \|first1=M.\|last2=Yamaguchi \|first2=D. \|last3=Ishikawa \|first3=T.\|last4=Sawa \|first4=T. \|last5=Tsuruta \|first5=K.\|last6=Ishikawa \|first6=K. \|last7=Koshihara \|first7=S.-y. \|last8=Hayashi \|first8=Y. \|last9=Kato \|first9=T.\|title=Ultrafast isomerization-induced cooperative motions to higher molecular orientation in smectic liquid-crystalline azobenzene molecules \|journal=Nature Communications \|date=13 September 2019 \|volume=10 \|issue=1 \|pages=4159 \|doi=10.1038/s41467-019-12116-6 \|pmid=31519876 \|pmc=6744564 \|bibcode=2019NatCo..10.4159H \|language=en \|issn=2041-1723\|doi-access=free }}{{cite journal \|last1=Garcia-Amorós \|first1=J.\|last2=Reig \|first2=M. \|last3=Cuadrado \|first3=A. \|last4=Ortega \|first4=M. \|last5=Nonell \|first5=S. \|last6=Velasco \|first6=D. \|title=A photoswitchable bis-azo derivative with a high temporal resolution \|journal=Chemical Communications \|date=2014 \|volume=50 \|issue=78 \|pages=11462–11464 \|doi=10.1039/C4CC05331A\|pmid=25132052 }} Molecular hinges have been adapted for applications such as nucleobase recognition,{{cite journal \|last1=Hamilton \|first1=A. D. \|last2=Van Engen \|first2=D. \|title=Induced fit in synthetic receptors: nucleotide base recognition by a molecular hinge \|journal=Journal of the American Chemical Society \|date=1987 \|volume=109 \|issue=16 \|pages=5035–5036 \|doi=10.1021/ja00250a052\|bibcode=1987JAChS.109.5035H }} peptide modifications,{{cite journal \|last1=Dumy \|first1=P. \|last2=Keller \|first2=M. \|last3=Ryan \|first3=D. E. \|last4=Rohwedder \|first4=B. \|last5=Wöhr \|first5=T. \|last6=Mutter \|first6=M. \|title=Pseudo-Prolines as a Molecular Hinge: Reversible Induction of cis Amide Bonds into Peptide Backbones \|journal=Journal of the American Chemical Society \|date=1997 \|volume=119 \|issue=5 \|pages=918–925 \|doi=10.1021/ja962780a\|bibcode=1997JAChS.119..918D }} and visualizing molecular motion.{{cite journal \|last1=Ai \|first1=Y. \|last2=Chan \|first2=M. H.-Y. \|last3=Chan \|first3=A. K.-W. \|last4=Ng \|first4=M. \|last5=Li \|first5=Y. \|last6=Yam \|first6=V. W.-W. \|title=A platinum(II) molecular hinge with motions visualized by phosphorescence changes \|journal=Proceedings of the National Academy of Sciences \|date=2019 \|volume=116 \|issue=28 \|pages=13856–13861 \|doi=10.1073/pnas.1908034116\|pmid=31243146 \|pmc=6628644 \|bibcode=2019PNAS..11613856A \|doi-access=free }} \|File:Molecular hinge example.png
style="vertical-align: top;" \|Molecular logic gate \|A molecule that performs a logical operation on one or more logic inputs and produces a single logic output.{{cite journal \|last1=Erbas-Cakmak \|first1=S. \|last2=Kolemen \|first2=S. \|last3=Sedgwick \|first3=A. C. \|last4=Gunnlaugsson \|first4=T. \|last5=James \|first5=T. D. \|last6=Yoon \|first6=J. \|last7=Akkaya \|first7=E. U. \|title=Molecular logic gates: the past, present and future \|journal=Chemical Society Reviews \|date=2018 \|volume=47 \|issue=7 \|pages=2228–2248 \|doi=10.1039/C7CS00491E\|pmid=29493684 \|hdl=11693/50034 \|hdl-access=free }} Modelled on logic gates, these molecules have slowly replaced the conventional silicon-based machinery. Several applications have come forth, such as water quality examination, food safety examination, metal ion detection, and pharmaceutical studies.{{cite journal \|last1=de Silva \|first1=A. P. \|title=Molecular Logic Gate Arrays \|journal=Chemistry: An Asian Journal \|date=2011 \|volume=6 \|issue=3 \|pages=750–766 \|doi=10.1002/asia.201000603\|pmid=21290607 }}{{cite journal \|last1=Liu \|first1=L. \|last2=Liu \|first2=P. \|last3=Ga \|first3=L. \|last4=Ai \|first4=J. \|title=Advances in Applications of Molecular Logic Gates \|journal=ACS Omega \|date=2021 \|volume=6 \|issue=45 \|pages=30189–30204 \|doi=10.1021/acsomega.1c02912\|pmid=34805654 \|pmc=8600522 }} The first example of a molecular logic gate was reported in 1993, featuring a receptor (see image) where the emission intensity could be treated as a tunable output if the concentrations of protons and sodium ions were to be considered as inputs.{{cite journal \|last1=de Silva \|first1=P. A. \|last2=Gunaratne \|first2=N. H. Q. \|last3=McCoy \|first3=C. P. \|title=A molecular photoionic AND gate based on fluorescent signalling \|journal=Nature \|date=1993 \|volume=364 \|issue=6432 \|pages=42–44 \|doi=10.1038/364042a0\|bibcode=1993Natur.364...42D \|s2cid=38260349 }} \|File:Molecular logic gate example.png
style="vertical-align: top;" \|Molecular motor \|A molecule that is capable of directional rotary motion around a single or double bond and produce useful work as a result (as depicted in the image).{{cite journal \|last1=Lancia \|first1=F. \|last2=Ryabchun \|first2=A. \|last3=Katsonis \|first3=N. \|title=Life-like motion driven by artificial molecular machines \|journal=Nature Reviews Chemistry \|date=2019 \|volume=3 \|issue=9 \|pages=536–551 \|doi=10.1038/s41570-019-0122-2\|s2cid=199661943 }}{{cite journal \|last1=Mickler \|first1=M. \|last2=Schleiff \|first2=E. \|last3=Hugel \|first3=T. \|title=From Biological towards Artificial Molecular Motors \|journal=ChemPhysChem \|date=2008 \|volume=9 \|issue=11 \|pages=1503–1509 \|doi=10.1002/cphc.200800216\|pmid=18618534 }}{{cite journal \| last1 = Carroll \| first1 = GT \| last2 = Pollard \| first2 = MM \| last3 = van Delden \| first3 = RA \| last4 = Feringa \| first4 = BL \| year = 2010 \| title = Controlled rotary motion of light-driven molecular motors assembled on a gold surface \| doi = 10.1039/C0SC00162G \| journal = Chemical Science \| volume = 1 \| issue = 1\| pages = 97–101 \| url = https://pure.rug.nl/ws/files/2613578/2010ChemSciCarroll1.pdf \| hdl = 11370/4fb63d6d-d764-45e3-b3cb-32a4c629b942 \| s2cid = 97346507 \| hdl-access = free }} Carbon nanotube nanomotors have also been produced.{{cite journal \|last1=Fennimore \|first1=A. M. \|last2=Yuzvinsky \|first2=T. D. \|last3=Han \|first3=Wei-Qiang \|last4=Fuhrer \|first4=M. S. \|last5=Cumings \|first5=J. \|last6=Zettl \|first6=A. \|title=Rotational actuators based on carbon nanotubes \|journal=Nature \|date=24 July 2003 \|volume=424 \|issue=6947 \|pages=408–410 \|doi=10.1038/nature01823\|pmid=12879064 \|bibcode=2003Natur.424..408F \|s2cid=2200106 }} Single bond rotary motors{{cite journal \|last1=Kelly \|first1=T. Ross \|last2=De Silva \|first2=Harshani \|last3=Silva \|first3=Richard A. \|title=Unidirectional rotary motion in a molecular system \|journal=Nature \|date=9 September 1999 \|volume=401 \|issue=6749 \|pages=150–152 \|doi=10.1038/43639\|pmid=10490021 \|bibcode=1999Natur.401..150K \|s2cid=4351615 }} are generally activated by chemical reactions whereas double bond rotary motors{{cite journal \|last1=Koumura \|first1=Nagatoshi \|last2=Zijlstra \|first2=Robert W. J. \|last3=van Delden \|first3=Richard A. \|last4=Harada \|first4=Nobuyuki \|last5=Feringa \|first5=Ben L. \|title=Light-driven monodirectional molecular rotor \|journal=Nature \|date=9 September 1999 \|volume=401 \|issue=6749 \|pages=152–155 \|doi=10.1038/43646 \|pmid=10490022 \|url=https://pure.rug.nl/ws/files/3616669/1999NatureKoumura.pdf \|bibcode=1999Natur.401..152K \|s2cid=4412610 \|hdl=11370/d8399fe7-11be-4282-8cd0-7c0adf42c96f \|hdl-access=free }} are generally fueled by light. The rotation speed of the motor can also be tuned by careful molecular design.{{cite journal \|last1=Vicario \|first1=Javier \|last2=Meetsma \|first2=Auke \|last3=Feringa \|first3=Ben L. \|title=Controlling the speed of rotation in molecular motors. Dramatic acceleration of the rotary motion by structural modification \|journal=Chemical Communications \|volume=116 \|date=2005 \|issue=47 \|pages=5910–2 \|doi=10.1039/B507264F\|pmid=16317472 \|url=https://www.rug.nl/research/portal/en/publications/controlling-the-speed-of-rotation-in-molecular-motors-dramatic-acceleration-of-the-rotary-motion-by-structural-modification(002a32ff-d6bf-4078-a546-c2a1ace86aa2).html }} \|File:MD rotor 250K 1ns.gif
style="vertical-align: top;" \|Molecular necklace \|A class of mechanically interlocked molecules derived from catenanes where a large macrocycle backbone connects at least three small rings in the shape of a necklace (see image for example). A molecular necklace consisting of a large macrocycle threaded by n-1 rings (hence comprising n rings) is represented as [n]MN.{{cite journal \|last1=Zhang \|first1=Z. \|last2=Zhao \|first2=J. \|last3=Guo \|first3=Z. \|last4=Zhang \|first4=H. \|last5=Pan \|first5=H. \|last6=Wu \|first6=Q. \|last7=You \|first7=W. \|last8=Yu \|first8=W. \|last9=Yan \|first9=X. \|title=Mechanically interlocked networks cross-linked by a molecular necklace \|journal=Nature Communications \|date=2022 \|volume=13 \|issue=1 \|pages=1393 \|doi=10.1038/s41467-022-29141-7\|pmid=35296669 \|pmc=8927564 \|bibcode=2022NatCo..13.1393Z }} The first molecular necklace was synthesized in 1992, featuring several α-cyclodextrins on a single polyethylene glycol chain backbone; the authors connected this to the idea of a "molecular abacus" proposed by Stoddart and coworkers around the same time.{{cite journal \|last1=Harada \|first1=A. \|last2=Li \|first2=J. \|last3=Kamachi \|first3=M. \|title=The molecular necklace: a rotaxane containing many threaded α-cyclodextrins \|journal=Nature \|date=1992 \|volume=356 \|issue=6367 \|pages=325–327 \|doi=10.1038/356325a0\|bibcode=1992Natur.356..325H \|s2cid=4304539 }} Several interesting applications have emerged for these molecules, such as antibacterial activity,{{cite journal \|last1=Wu \|first1=G.-Y. \|last2=Shi \|first2=X. \|last3=Phan \|first3=H. \|last4=Qu \|first4=H. \|last5=Hu \|first5=Y.-X. \|last6=Yin \|first6=G.-Q. \|last7=Zhao \|first7=X.-L. \|last8=Li \|first8=X. \|last9=Xu \|first9=L. \|last10=Yu \|first10=Q. \|last11=Yang \|first11=H.-B. \|title=Efficient self-assembly of heterometallic triangular necklace with strong antibacterial activity \|journal=Nature Communications \|date=2020 \|volume=11 \|issue=1 \|pages=3178 \|doi=10.1038/s41467-020-16940-z \|pmid=32576814 \|pmc=7311404 \|bibcode=2020NatCo..11.3178W }} desulfurization of fuels,{{cite journal \|last1=Li \|first1=S.-L. \|last2=Lan \|first2=Y.-Q. \|last3=Sakurai \|first3=H. \|last4=Xu \|first4=Q. \|title=Unusual Regenerable Porous Metal-Organic Framework Based on a New Triple Helical Molecular Necklace for Separating Organosulfur Compounds \|journal=Chemistry: A European Journal \|date=2012 \|volume=18 \|issue=51 \|pages=16302–16309 \|doi=10.1002/chem.201203093\|pmid=23168579 }} and piezoelectricity.{{cite journal \|last1=Seo \|first1=J. \|last2=Kim \|first2=B. \|last3=Kim \|first3=M.-S. \|last4=Seo \|first4=J.-H. \|title=Optimization of Anisotropic Crystalline Structure of Molecular Necklace-like Polyrotaxane for Tough Piezoelectric Elastomer \|journal=ACS Macro Letters \|date=2021 \|volume=10 \|issue=11 \|pages=1371–1376 \|doi=10.1021/acsmacrolett.1c00567\|pmid=35549010 }} \|File:Molecular necklace example.png
style="vertical-align: top;" \|Molecular propeller \|A molecule that can propel fluids when rotated, due to its special shape that is designed in analogy to macroscopic propellers (see schematic image on right). It has several molecular-scale blades attached at a certain pitch angle around the circumference of a nanoscale shaft.{{cite journal \|last1=Simpson \|first1=Christopher D. \|last2=Mattersteig \|first2=Gunter \|last3=Martin \|first3=Kai \|last4=Gherghel \|first4=Lileta \|last5=Bauer \|first5=Roland E. \|last6=Räder \|first6=Hans Joachim \|last7=Müllen \|first7=Klaus \|title=Nanosized Molecular Propellers by Cyclodehydrogenation of Polyphenylene Dendrimers \|journal=Journal of the American Chemical Society \|date=March 2004 \|volume=126 \|issue=10 \|pages=3139–3147 \|doi=10.1021/ja036732j \|pmid=15012144 \|bibcode=2004JAChS.126.3139S }}{{cite journal \|doi=10.1103/PhysRevLett.98.266102\|pmid=17678108\|title=Chemically Tunable Nanoscale Propellers of Liquids\|journal=Physical Review Letters\|volume=98\|issue=26\|pages=266102\|year=2007\|last1=Wang\|first1=Boyang\|last2=Král\|first2=Petr\|bibcode=2007PhRvL..98z6102W}} Propellers have been shown to have interesting properties, such as variations in pumping rates for hydrophilic and hydrophobic fluids.{{cite journal \|last1=Wang \|first1=B. \|last2=Král \|first2=P. \|title=Chemically Tunable Nanoscale Propellers of Liquids \|journal=Physical Review Letters \|date=2007 \|volume=98 \|issue=26 \|pages=266102 \|doi=10.1103/PhysRevLett.98.266102\|pmid=17678108 \|bibcode=2007PhRvL..98z6102W }} \|File:Molecularpropeller.jpg
style="vertical-align: top;" \|Molecular shuttle \|A molecule capable of shuttling molecules or ions from one location to another. This is schematically depicted in the image on the right, where a ring (in green) can bind to either one of the yellow sites on the blue macrocyclic backbone.{{cite journal \|last1=Bissell \|first1=Richard A \|last2=Córdova \|first2=Emilio \|last3=Kaifer \|first3=Angel E. \|last4=Stoddart \|first4=J. Fraser \|title=A chemically and electrochemically switchable molecular shuttle \|journal=Nature \|date=12 May 1994 \|volume=369 \|issue=6476 \|pages=133–137 \|doi=10.1038/369133a0\|bibcode=1994Natur.369..133B \|s2cid=44926804 }} A common molecular shuttle consists of a rotaxane where the macrocycle can move between two sites or stations along the dumbbell backbone; controlling the properties of either site and by regulating conditions like pH can enable control over which site is selected for binding. This has led to novel applications in catalysis and drug delivery.{{cite journal\|last1=Chatterjee\|first1=M. N.\|last2=Kay\|first2=E. R.\|last3=Leigh\|first3=D. A.\|date=2006\|title=Beyond Switches: Ratcheting a Particle Energetically Uphill with a Compartmentalized Molecular Machine\|journal=Journal of the American Chemical Society\|volume=128\|issue=12\|pages=4058–4073\|doi=10.1021/ja057664z\|pmid=16551115\|bibcode=2006JAChS.128.4058C }} \|File:Molecular shuttle illustration commons.png
style="vertical-align: top;" \|Molecular switch \|A molecule that can be reversibly shifted between two or more stable states in response to certain stimuli. This change of states influences the properties of the molecule according to the state it occupies at the moment. Unlike a molecular motor, any mechanical work done due to the motion in a switch is generally undone once the molecule returns to its original state unless it is part of a larger motor-like system. The image on the right shows a hydrazone-based switch that switches in response to pH changes.{{cite journal \|last1=Kassem \|first1=S. \|last2=van Leeuwen \|first2=T. \|last3=Lubbe \|first3=A. S. \|last4=Wilson \|first4=M. R. \|last5=Feringa \|first5=B. L. \|last6=Leigh \|first6=D. A. \|title=Artificial molecular motors \|journal=Chemical Society Reviews \|date=2017 \|volume=46 \|issue=9 \|pages=2592–2621 \|doi=10.1039/C7CS00245A\|pmid=28426052 \|url=https://www.research.manchester.ac.uk/portal/en/publications/artificial-molecular-motors(0335f428-84f0-4f4f-b09a-65c37db984e0).html }} \|File:Molecular switch example.png
style="vertical-align: top;" \|Molecular tweezers \|Host molecules capable of holding items between their two arms.{{cite journal \|last1=Chen \|first1=C. W. \|last2=Whitlock \|first2=H. W. \|title=Molecular tweezers: a simple model of bifunctional intercalation \|journal=Journal of the American Chemical Society \|date=July 1978 \|volume=100 \|issue=15 \|pages=4921–4922 \|doi=10.1021/ja00483a063\|bibcode=1978JAChS.100.4921C }} The open cavity of the molecular tweezers binds items using non-covalent bonding including hydrogen bonding, metal coordination, hydrophobic forces, van der Waals forces, π interactions, or electrostatic effects.{{cite journal \|last1=Klärner \|first1=Frank-Gerrit \|last2=Kahlert \|first2=Björn \|title=Molecular Tweezers and Clips as Synthetic Receptors. Molecular Recognition and Dynamics in Receptor−Substrate Complexes \|journal=Accounts of Chemical Research \|date=December 2003 \|volume=36 \|issue=12 \|pages=919–932 \|doi=10.1021/ar0200448\|pmid=14674783 }} For instance, the image on the right depicts tweezers formed by corannulene pincers clasping a C60 fullerene molecule, termed "buckycatcher".{{cite journal \|last1=Sygula \|first1=A. \|last2=Fronczek \|first2=F. R. \|last3=Sygula \|first3=R. \|last4=Rabideau \|first4=P. W. \|last5=Olmstead \|first5=M. M. \|title=A Double Concave Hydrocarbon Buckycatcher \|journal=Journal of the American Chemical Society \|date=2007 \|volume=129 \|issue=13 \|pages=3842–3843 \|doi=10.1021/ja070616p\|pmid=17348661 \|bibcode=2007JAChS.129.3842S \|s2cid=25154754 }} Examples of molecular tweezers have been reported that are constructed from DNA and are considered DNA machines.{{cite journal \|last1=Yurke \|first1=Bernard \|last2=Turberfield \|first2=Andrew J. \|last3=Mills \|first3=Allen P. \|last4=Simmel \|first4=Friedrich C. \|last5=Neumann \|first5=Jennifer L. \|title=A DNA-fuelled molecular machine made of DNA \|journal=Nature \|date=10 August 2000 \|volume=406 \|issue=6796 \|pages=605–608 \|doi=10.1038/35020524\|pmid=10949296 \|bibcode=2000Natur.406..605Y \|s2cid=2064216 }} \|File:Buckycatcher JACS 2007 V129 p3843.jpg
style="vertical-align: top;" \|Nanocar \|Single-molecule vehicles that resemble macroscopic automobiles and are important for understanding how to control molecular diffusion on surfaces. The image on the right shows an example with wheels made of fullerene molecules. The first nanocars were synthesized by James M. Tour in 2005. They had an H-shaped chassis and 4 molecular wheels (fullerenes) attached to the four corners.{{cite journal \|last1=Shirai \|first1=Yasuhiro \|last2=Osgood \|first2=Andrew J. \|last3=Zhao \|first3=Yuming \|last4=Kelly \|first4=Kevin F. \|last5=Tour \|first5=James M. \|title=Directional Control in Thermally Driven Single-Molecule Nanocars \|journal=Nano Letters \|date=November 2005 \|volume=5 \|issue=11 \|pages=2330–2334 \|doi=10.1021/nl051915k\|pmid=16277478 \|bibcode=2005NanoL...5.2330S }} In 2011, Feringa and co-workers synthesized the first motorized nanocar which had molecular motors attached to the chassis as rotating wheels.{{cite journal \|last1=Kudernac \|first1=Tibor \|last2=Ruangsupapichat \|first2=Nopporn \|last3=Parschau \|first3=Manfred \|last4=Maciá \|first4=Beatriz \|last5=Katsonis \|first5=Nathalie \|last6=Harutyunyan \|first6=Syuzanna R. \|last7=Ernst \|first7=Karl-Heinz \|last8=Feringa \|first8=Ben L. \|title=Electrically driven directional motion of a four-wheeled molecule on a metal surface \|journal=Nature \|date=10 November 2011 \|volume=479 \|issue=7372 \|pages=208–211 \|doi=10.1038/nature10587\|pmid=22071765 \|bibcode=2011Natur.479..208K \|s2cid=6175720 }} The authors were able to demonstrate directional motion of the nanocar on a copper surface by providing energy from a scanning tunneling microscope tip. Later, in 2017, the world's first-ever nanocar race took place in Toulouse.{{cite web\|url=https://www.ladepeche.fr/article/2015/11/30/2227726-nanocar-race-la-course-de-petites-voitures-pour-grands-savants.html\| title=NanoCar Race : la course de petites voitures pour grands savants\|trans-title=NanoCar Race: the race of small cars for great scientists\|language=French\|date=November 30, 2017\|newspaper=La Dépêche du Midi\|accessdate=December 2, 2018}} \|File:Nanocar2.png

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|Molecular balance

|A molecule that can interconvert between two or more conformational or configurational states in response to the dynamic of multiple intra- and intermolecular driving forces,{{Cite journal|last1=Paliwal|first1=S.|last2=Geib|first2=S.|last3=Wilcox|first3=C. S.|date=1994|title=Molecular Torsion Balance for Weak Molecular Recognition Forces. Effects of "Tilted-T" Edge-to-Face Aromatic Interactions on Conformational Selection and Solid-State Structure|journal=Journal of the American Chemical Society|volume=116|issue=10|pages=4497–4498|doi=10.1021/ja00089a057|bibcode=1994JAChS.116.4497P }}{{Cite journal|last1=Mati|first1=Ioulia K.|last2=Cockroft|first2=Scott L.|date=2010|title=Molecular balances for quantifying non-covalent interactions|journal=Chemical Society Reviews|volume=39|issue=11|pages=4195–4205|doi=10.1039/B822665M|pmid=20844782|url=https://www.pure.ed.ac.uk/ws/files/10097959/Molecular_balances_for_quantifying_non_covalent_interactions.pdf|hdl=20.500.11820/7ce18ff7-1196-48a1-8c67-3bc3f6b46946|s2cid=263667 |hdl-access=free}} such as hydrogen bonding, solvophobic or hydrophobic effects,{{Cite journal|last1=Y.|first1=Lixu|last2=A.|first2=Catherine|last3=Cockroft|first3=S. L.|date=2015|title=Quantifying Solvophobic Effects in Nonpolar Cohesive Interactions|journal=Journal of the American Chemical Society|volume=137|issue=32|pages=10084–10087|doi=10.1021/jacs.5b05736|pmid=26159869|bibcode=2015JAChS.13710084Y |issn=0002-7863|hdl=20.500.11820/604343eb-04aa-4d90-82d2-0998898400d2|url=https://www.pure.ed.ac.uk/ws/files/24692670/scockroft.docx|hdl-access=free}} π interactions,{{Cite journal|last1=L.|first1=Ping|last2=Z.|first2=Chen|last3=Smith|first3=M. D.|last4=Shimizu|first4=K. D.|date=2013|title=Comprehensive Experimental Study of N-Heterocyclic π-Stacking Interactions of Neutral and Cationic Pyridines|journal=The Journal of Organic Chemistry|volume=78|issue=11|pages=5303–5313|doi=10.1021/jo400370e|pmid=23675885}} and steric and dispersion interactions.{{Cite journal|last1=Hwang|first1=J.|last2=Li|first2=P.|last3=Smith|first3=M. D.|last4=Shimizu|first4=K. D.|date=2016|title=Distance-Dependent Attractive and Repulsive Interactions of Bulky Alkyl Groups|journal=Angewandte Chemie International Edition|volume=55|issue=28|pages=8086–8089|doi=10.1002/anie.201602752|pmid=27159670|doi-access=free}} The distinct conformers of a molecular balance can show different interactions with the same molecule, such that analyzing the ratio of the conformers and the energies for these interactions can enable quantification of different properties (such as CH-π or arene-arene interactions, see image).{{cite journal |last1=Carroll |first1=W. R. |last2=Zhao |first2=C. |last3=Smith |first3=M. D. |last4=Pellechia |first4=P. J. |last5=Shimizu |first5=K. D. |title=A Molecular Balance for Measuring Aliphatic CH−π Interactions |journal=Organic Letters |date=2011 |volume=13 |issue=16 |pages=4320–4323 |doi=10.1021/ol201657p|pmid=21797218 }}{{cite journal |last1=Carroll |first1=W. R. |last2=Pellechia |first2=P. |last3=Shimizu |first3=K. D. |title=A Rigid Molecular Balance for Measuring Face-to-Face Arene−Arene Interactions |journal=Organic Letters |date=2008 |volume=10 |issue=16 |pages=3547–3550 |doi=10.1021/ol801286k|pmid=18630926 }}

|File:Molecular balance example.png

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|Molecular hinge

|A molecular hinge is a molecule that can typically rotate in a crank-like motion around a rigid axis, such as a double bond or aromatic ring, to switch between reversible configurations.{{cite journal |last1=Kassem |first1=Salma |last2=van Leeuwen |first2=Thomas |last3=Lubbe |first3=Anouk S. |last4=Wilson |first4=Miriam R. |last5=Feringa |first5=Ben L. |last6=Leigh |first6=David A. |title=Artificial molecular motors |journal=Chemical Society Reviews |date=2017 |volume=46 |issue=9 |pages=2592–2621 |doi=10.1039/C7CS00245A|pmid=28426052 |url=https://pure.rug.nl/ws/files/49449226/c7cs00245a_1_.pdf }} Such configurations must have distinguishable geometries; for instance, azobenzene groups in a linear molecule may undergo cis-trans isomerization{{cite journal |last1=Bandara |first1=H. M. Dhammika |last2=Burdette |first2=S. C. |title=Photoisomerization in different classes of azobenzene |journal=Chemical Society Reviews |date=2012 |volume=41 |issue=5 |pages=1809–1825 |doi=10.1039/c1cs15179g|pmid=22008710 }} when irradiated with ultraviolet light, triggering a reversible transition to a bent or V-shaped conformation (see image).{{cite journal |last1=Wang |first1=J. |last2=Jiang |first2=Q. |last3=Hao |first3=X. |last4=Yan |first4=H.|last5=Peng |first5=H. |last6=Xiong |first6=B.|last7=Liao |first7=Y. |last8=Xie |first8=X. |title=Reversible photo-responsive gel–sol transitions of robust organogels based on an azobenzene-containing main-chain liquid crystalline polymer |journal=RSC Advances |date=2020 |volume=10 |issue=7 |pages=3726–3733 |doi=10.1039/C9RA10161F|pmid=35492656 |pmc=9048773 |bibcode=2020RSCAd..10.3726W |doi-access=free }}{{cite journal |last1=Hada |first1=M.|last2=Yamaguchi |first2=D. |last3=Ishikawa |first3=T.|last4=Sawa |first4=T. |last5=Tsuruta |first5=K.|last6=Ishikawa |first6=K. |last7=Koshihara |first7=S.-y. |last8=Hayashi |first8=Y. |last9=Kato |first9=T.|title=Ultrafast isomerization-induced cooperative motions to higher molecular orientation in smectic liquid-crystalline azobenzene molecules |journal=Nature Communications |date=13 September 2019 |volume=10 |issue=1 |pages=4159 |doi=10.1038/s41467-019-12116-6 |pmid=31519876 |pmc=6744564 |bibcode=2019NatCo..10.4159H |language=en |issn=2041-1723|doi-access=free }}{{cite journal |last1=Garcia-Amorós |first1=J.|last2=Reig |first2=M. |last3=Cuadrado |first3=A. |last4=Ortega |first4=M. |last5=Nonell |first5=S. |last6=Velasco |first6=D. |title=A photoswitchable bis-azo derivative with a high temporal resolution |journal=Chemical Communications |date=2014 |volume=50 |issue=78 |pages=11462–11464 |doi=10.1039/C4CC05331A|pmid=25132052 }} Molecular hinges have been adapted for applications such as nucleobase recognition,{{cite journal |last1=Hamilton |first1=A. D. |last2=Van Engen |first2=D. |title=Induced fit in synthetic receptors: nucleotide base recognition by a molecular hinge |journal=Journal of the American Chemical Society |date=1987 |volume=109 |issue=16 |pages=5035–5036 |doi=10.1021/ja00250a052|bibcode=1987JAChS.109.5035H }} peptide modifications,{{cite journal |last1=Dumy |first1=P. |last2=Keller |first2=M. |last3=Ryan |first3=D. E. |last4=Rohwedder |first4=B. |last5=Wöhr |first5=T. |last6=Mutter |first6=M. |title=Pseudo-Prolines as a Molecular Hinge: Reversible Induction of cis Amide Bonds into Peptide Backbones |journal=Journal of the American Chemical Society |date=1997 |volume=119 |issue=5 |pages=918–925 |doi=10.1021/ja962780a|bibcode=1997JAChS.119..918D }} and visualizing molecular motion.{{cite journal |last1=Ai |first1=Y. |last2=Chan |first2=M. H.-Y. |last3=Chan |first3=A. K.-W. |last4=Ng |first4=M. |last5=Li |first5=Y. |last6=Yam |first6=V. W.-W. |title=A platinum(II) molecular hinge with motions visualized by phosphorescence changes |journal=Proceedings of the National Academy of Sciences |date=2019 |volume=116 |issue=28 |pages=13856–13861 |doi=10.1073/pnas.1908034116|pmid=31243146 |pmc=6628644 |bibcode=2019PNAS..11613856A |doi-access=free }}

|File:Molecular hinge example.png

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|Molecular logic gate

|A molecule that performs a logical operation on one or more logic inputs and produces a single logic output.{{cite journal |last1=Erbas-Cakmak |first1=S. |last2=Kolemen |first2=S. |last3=Sedgwick |first3=A. C. |last4=Gunnlaugsson |first4=T. |last5=James |first5=T. D. |last6=Yoon |first6=J. |last7=Akkaya |first7=E. U. |title=Molecular logic gates: the past, present and future |journal=Chemical Society Reviews |date=2018 |volume=47 |issue=7 |pages=2228–2248 |doi=10.1039/C7CS00491E|pmid=29493684 |hdl=11693/50034 |hdl-access=free }} Modelled on logic gates, these molecules have slowly replaced the conventional silicon-based machinery. Several applications have come forth, such as water quality examination, food safety examination, metal ion detection, and pharmaceutical studies.{{cite journal |last1=de Silva |first1=A. P. |title=Molecular Logic Gate Arrays |journal=Chemistry: An Asian Journal |date=2011 |volume=6 |issue=3 |pages=750–766 |doi=10.1002/asia.201000603|pmid=21290607 }}{{cite journal |last1=Liu |first1=L. |last2=Liu |first2=P. |last3=Ga |first3=L. |last4=Ai |first4=J. |title=Advances in Applications of Molecular Logic Gates |journal=ACS Omega |date=2021 |volume=6 |issue=45 |pages=30189–30204 |doi=10.1021/acsomega.1c02912|pmid=34805654 |pmc=8600522 }} The first example of a molecular logic gate was reported in 1993, featuring a receptor (see image) where the emission intensity could be treated as a tunable output if the concentrations of protons and sodium ions were to be considered as inputs.{{cite journal |last1=de Silva |first1=P. A. |last2=Gunaratne |first2=N. H. Q. |last3=McCoy |first3=C. P. |title=A molecular photoionic AND gate based on fluorescent signalling |journal=Nature |date=1993 |volume=364 |issue=6432 |pages=42–44 |doi=10.1038/364042a0|bibcode=1993Natur.364...42D |s2cid=38260349 }}

|File:Molecular logic gate example.png

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|Molecular motor

|A molecule that is capable of directional rotary motion around a single or double bond and produce useful work as a result (as depicted in the image).{{cite journal |last1=Lancia |first1=F. |last2=Ryabchun |first2=A. |last3=Katsonis |first3=N. |title=Life-like motion driven by artificial molecular machines |journal=Nature Reviews Chemistry |date=2019 |volume=3 |issue=9 |pages=536–551 |doi=10.1038/s41570-019-0122-2|s2cid=199661943 }}{{cite journal |last1=Mickler |first1=M. |last2=Schleiff |first2=E. |last3=Hugel |first3=T. |title=From Biological towards Artificial Molecular Motors |journal=ChemPhysChem |date=2008 |volume=9 |issue=11 |pages=1503–1509 |doi=10.1002/cphc.200800216|pmid=18618534 }}{{cite journal | last1 = Carroll | first1 = GT | last2 = Pollard | first2 = MM | last3 = van Delden | first3 = RA | last4 = Feringa | first4 = BL | year = 2010 | title = Controlled rotary motion of light-driven molecular motors assembled on a gold surface | doi = 10.1039/C0SC00162G | journal = Chemical Science | volume = 1 | issue = 1| pages = 97–101 | url = https://pure.rug.nl/ws/files/2613578/2010ChemSciCarroll1.pdf | hdl = 11370/4fb63d6d-d764-45e3-b3cb-32a4c629b942 | s2cid = 97346507 | hdl-access = free }} Carbon nanotube nanomotors have also been produced.{{cite journal |last1=Fennimore |first1=A. M. |last2=Yuzvinsky |first2=T. D. |last3=Han |first3=Wei-Qiang |last4=Fuhrer |first4=M. S. |last5=Cumings |first5=J. |last6=Zettl |first6=A. |title=Rotational actuators based on carbon nanotubes |journal=Nature |date=24 July 2003 |volume=424 |issue=6947 |pages=408–410 |doi=10.1038/nature01823|pmid=12879064 |bibcode=2003Natur.424..408F |s2cid=2200106 }} Single bond rotary motors{{cite journal |last1=Kelly |first1=T. Ross |last2=De Silva |first2=Harshani |last3=Silva |first3=Richard A. |title=Unidirectional rotary motion in a molecular system |journal=Nature |date=9 September 1999 |volume=401 |issue=6749 |pages=150–152 |doi=10.1038/43639|pmid=10490021 |bibcode=1999Natur.401..150K |s2cid=4351615 }} are generally activated by chemical reactions whereas double bond rotary motors{{cite journal |last1=Koumura |first1=Nagatoshi |last2=Zijlstra |first2=Robert W. J. |last3=van Delden |first3=Richard A. |last4=Harada |first4=Nobuyuki |last5=Feringa |first5=Ben L. |title=Light-driven monodirectional molecular rotor |journal=Nature |date=9 September 1999 |volume=401 |issue=6749 |pages=152–155 |doi=10.1038/43646 |pmid=10490022 |url=https://pure.rug.nl/ws/files/3616669/1999NatureKoumura.pdf |bibcode=1999Natur.401..152K |s2cid=4412610 |hdl=11370/d8399fe7-11be-4282-8cd0-7c0adf42c96f |hdl-access=free }} are generally fueled by light. The rotation speed of the motor can also be tuned by careful molecular design.{{cite journal |last1=Vicario |first1=Javier |last2=Meetsma |first2=Auke |last3=Feringa |first3=Ben L. |title=Controlling the speed of rotation in molecular motors. Dramatic acceleration of the rotary motion by structural modification |journal=Chemical Communications |volume=116 |date=2005 |issue=47 |pages=5910–2 |doi=10.1039/B507264F|pmid=16317472 |url=https://www.rug.nl/research/portal/en/publications/controlling-the-speed-of-rotation-in-molecular-motors-dramatic-acceleration-of-the-rotary-motion-by-structural-modification(002a32ff-d6bf-4078-a546-c2a1ace86aa2).html }}

|File:MD rotor 250K 1ns.gif

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|Molecular necklace

|A class of mechanically interlocked molecules derived from catenanes where a large macrocycle backbone connects at least three small rings in the shape of a necklace (see image for example). A molecular necklace consisting of a large macrocycle threaded by n-1 rings (hence comprising n rings) is represented as [n]MN.{{cite journal |last1=Zhang |first1=Z. |last2=Zhao |first2=J. |last3=Guo |first3=Z. |last4=Zhang |first4=H. |last5=Pan |first5=H. |last6=Wu |first6=Q. |last7=You |first7=W. |last8=Yu |first8=W. |last9=Yan |first9=X. |title=Mechanically interlocked networks cross-linked by a molecular necklace |journal=Nature Communications |date=2022 |volume=13 |issue=1 |pages=1393 |doi=10.1038/s41467-022-29141-7|pmid=35296669 |pmc=8927564 |bibcode=2022NatCo..13.1393Z }} The first molecular necklace was synthesized in 1992, featuring several α-cyclodextrins on a single polyethylene glycol chain backbone; the authors connected this to the idea of a "molecular abacus" proposed by Stoddart and coworkers around the same time.{{cite journal |last1=Harada |first1=A. |last2=Li |first2=J. |last3=Kamachi |first3=M. |title=The molecular necklace: a rotaxane containing many threaded α-cyclodextrins |journal=Nature |date=1992 |volume=356 |issue=6367 |pages=325–327 |doi=10.1038/356325a0|bibcode=1992Natur.356..325H |s2cid=4304539 }} Several interesting applications have emerged for these molecules, such as antibacterial activity,{{cite journal |last1=Wu |first1=G.-Y. |last2=Shi |first2=X. |last3=Phan |first3=H. |last4=Qu |first4=H. |last5=Hu |first5=Y.-X. |last6=Yin |first6=G.-Q. |last7=Zhao |first7=X.-L. |last8=Li |first8=X. |last9=Xu |first9=L. |last10=Yu |first10=Q. |last11=Yang |first11=H.-B. |title=Efficient self-assembly of heterometallic triangular necklace with strong antibacterial activity |journal=Nature Communications |date=2020 |volume=11 |issue=1 |pages=3178 |doi=10.1038/s41467-020-16940-z |pmid=32576814 |pmc=7311404 |bibcode=2020NatCo..11.3178W }} desulfurization of fuels,{{cite journal |last1=Li |first1=S.-L. |last2=Lan |first2=Y.-Q. |last3=Sakurai |first3=H. |last4=Xu |first4=Q. |title=Unusual Regenerable Porous Metal-Organic Framework Based on a New Triple Helical Molecular Necklace for Separating Organosulfur Compounds |journal=Chemistry: A European Journal |date=2012 |volume=18 |issue=51 |pages=16302–16309 |doi=10.1002/chem.201203093|pmid=23168579 }} and piezoelectricity.{{cite journal |last1=Seo |first1=J. |last2=Kim |first2=B. |last3=Kim |first3=M.-S. |last4=Seo |first4=J.-H. |title=Optimization of Anisotropic Crystalline Structure of Molecular Necklace-like Polyrotaxane for Tough Piezoelectric Elastomer |journal=ACS Macro Letters |date=2021 |volume=10 |issue=11 |pages=1371–1376 |doi=10.1021/acsmacrolett.1c00567|pmid=35549010 }}

|File:Molecular necklace example.png

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|Molecular propeller

|A molecule that can propel fluids when rotated, due to its special shape that is designed in analogy to macroscopic propellers (see schematic image on right). It has several molecular-scale blades attached at a certain pitch angle around the circumference of a nanoscale shaft.{{cite journal |last1=Simpson |first1=Christopher D. |last2=Mattersteig |first2=Gunter |last3=Martin |first3=Kai |last4=Gherghel |first4=Lileta |last5=Bauer |first5=Roland E. |last6=Räder |first6=Hans Joachim |last7=Müllen |first7=Klaus |title=Nanosized Molecular Propellers by Cyclodehydrogenation of Polyphenylene Dendrimers |journal=Journal of the American Chemical Society |date=March 2004 |volume=126 |issue=10 |pages=3139–3147 |doi=10.1021/ja036732j |pmid=15012144 |bibcode=2004JAChS.126.3139S }}{{cite journal |doi=10.1103/PhysRevLett.98.266102|pmid=17678108|title=Chemically Tunable Nanoscale Propellers of Liquids|journal=Physical Review Letters|volume=98|issue=26|pages=266102|year=2007|last1=Wang|first1=Boyang|last2=Král|first2=Petr|bibcode=2007PhRvL..98z6102W}} Propellers have been shown to have interesting properties, such as variations in pumping rates for hydrophilic and hydrophobic fluids.{{cite journal |last1=Wang |first1=B. |last2=Král |first2=P. |title=Chemically Tunable Nanoscale Propellers of Liquids |journal=Physical Review Letters |date=2007 |volume=98 |issue=26 |pages=266102 |doi=10.1103/PhysRevLett.98.266102|pmid=17678108 |bibcode=2007PhRvL..98z6102W }}

|File:Molecularpropeller.jpg

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|Molecular shuttle

|A molecule capable of shuttling molecules or ions from one location to another. This is schematically depicted in the image on the right, where a ring (in green) can bind to either one of the yellow sites on the blue macrocyclic backbone.{{cite journal |last1=Bissell |first1=Richard A |last2=Córdova |first2=Emilio |last3=Kaifer |first3=Angel E. |last4=Stoddart |first4=J. Fraser |title=A chemically and electrochemically switchable molecular shuttle |journal=Nature |date=12 May 1994 |volume=369 |issue=6476 |pages=133–137 |doi=10.1038/369133a0|bibcode=1994Natur.369..133B |s2cid=44926804 }} A common molecular shuttle consists of a rotaxane where the macrocycle can move between two sites or stations along the dumbbell backbone; controlling the properties of either site and by regulating conditions like pH can enable control over which site is selected for binding. This has led to novel applications in catalysis and drug delivery.{{cite journal|last1=Chatterjee|first1=M. N.|last2=Kay|first2=E. R.|last3=Leigh|first3=D. A.|date=2006|title=Beyond Switches: Ratcheting a Particle Energetically Uphill with a Compartmentalized Molecular Machine|journal=Journal of the American Chemical Society|volume=128|issue=12|pages=4058–4073|doi=10.1021/ja057664z|pmid=16551115|bibcode=2006JAChS.128.4058C }}

|File:Molecular shuttle illustration commons.png

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|Molecular switch

|A molecule that can be reversibly shifted between two or more stable states in response to certain stimuli. This change of states influences the properties of the molecule according to the state it occupies at the moment. Unlike a molecular motor, any mechanical work done due to the motion in a switch is generally undone once the molecule returns to its original state unless it is part of a larger motor-like system. The image on the right shows a hydrazone-based switch that switches in response to pH changes.{{cite journal |last1=Kassem |first1=S. |last2=van Leeuwen |first2=T. |last3=Lubbe |first3=A. S. |last4=Wilson |first4=M. R. |last5=Feringa |first5=B. L. |last6=Leigh |first6=D. A. |title=Artificial molecular motors |journal=Chemical Society Reviews |date=2017 |volume=46 |issue=9 |pages=2592–2621 |doi=10.1039/C7CS00245A|pmid=28426052 |url=https://www.research.manchester.ac.uk/portal/en/publications/artificial-molecular-motors(0335f428-84f0-4f4f-b09a-65c37db984e0).html }}

|File:Molecular switch example.png

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|Molecular tweezers

|Host molecules capable of holding items between their two arms.{{cite journal |last1=Chen |first1=C. W. |last2=Whitlock |first2=H. W. |title=Molecular tweezers: a simple model of bifunctional intercalation |journal=Journal of the American Chemical Society |date=July 1978 |volume=100 |issue=15 |pages=4921–4922 |doi=10.1021/ja00483a063|bibcode=1978JAChS.100.4921C }} The open cavity of the molecular tweezers binds items using non-covalent bonding including hydrogen bonding, metal coordination, hydrophobic forces, van der Waals forces, π interactions, or electrostatic effects.{{cite journal |last1=Klärner |first1=Frank-Gerrit |last2=Kahlert |first2=Björn |title=Molecular Tweezers and Clips as Synthetic Receptors. Molecular Recognition and Dynamics in Receptor−Substrate Complexes |journal=Accounts of Chemical Research |date=December 2003 |volume=36 |issue=12 |pages=919–932 |doi=10.1021/ar0200448|pmid=14674783 }} For instance, the image on the right depicts tweezers formed by corannulene pincers clasping a C60 fullerene molecule, termed "buckycatcher".{{cite journal |last1=Sygula |first1=A. |last2=Fronczek |first2=F. R. |last3=Sygula |first3=R. |last4=Rabideau |first4=P. W. |last5=Olmstead |first5=M. M. |title=A Double Concave Hydrocarbon Buckycatcher |journal=Journal of the American Chemical Society |date=2007 |volume=129 |issue=13 |pages=3842–3843 |doi=10.1021/ja070616p|pmid=17348661 |bibcode=2007JAChS.129.3842S |s2cid=25154754 }} Examples of molecular tweezers have been reported that are constructed from DNA and are considered DNA machines.{{cite journal |last1=Yurke |first1=Bernard |last2=Turberfield |first2=Andrew J. |last3=Mills |first3=Allen P. |last4=Simmel |first4=Friedrich C. |last5=Neumann |first5=Jennifer L. |title=A DNA-fuelled molecular machine made of DNA |journal=Nature |date=10 August 2000 |volume=406 |issue=6796 |pages=605–608 |doi=10.1038/35020524|pmid=10949296 |bibcode=2000Natur.406..605Y |s2cid=2064216 }}

|File:Buckycatcher JACS 2007 V129 p3843.jpg

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|Nanocar

|Single-molecule vehicles that resemble macroscopic automobiles and are important for understanding how to control molecular diffusion on surfaces. The image on the right shows an example with wheels made of fullerene molecules. The first nanocars were synthesized by James M. Tour in 2005. They had an H-shaped chassis and 4 molecular wheels (fullerenes) attached to the four corners.{{cite journal |last1=Shirai |first1=Yasuhiro |last2=Osgood |first2=Andrew J. |last3=Zhao |first3=Yuming |last4=Kelly |first4=Kevin F. |last5=Tour |first5=James M. |title=Directional Control in Thermally Driven Single-Molecule Nanocars |journal=Nano Letters |date=November 2005 |volume=5 |issue=11 |pages=2330–2334 |doi=10.1021/nl051915k|pmid=16277478 |bibcode=2005NanoL...5.2330S }} In 2011, Feringa and co-workers synthesized the first motorized nanocar which had molecular motors attached to the chassis as rotating wheels.{{cite journal |last1=Kudernac |first1=Tibor |last2=Ruangsupapichat |first2=Nopporn |last3=Parschau |first3=Manfred |last4=Maciá |first4=Beatriz |last5=Katsonis |first5=Nathalie |last6=Harutyunyan |first6=Syuzanna R. |last7=Ernst |first7=Karl-Heinz |last8=Feringa |first8=Ben L. |title=Electrically driven directional motion of a four-wheeled molecule on a metal surface |journal=Nature |date=10 November 2011 |volume=479 |issue=7372 |pages=208–211 |doi=10.1038/nature10587|pmid=22071765 |bibcode=2011Natur.479..208K |s2cid=6175720 }} The authors were able to demonstrate directional motion of the nanocar on a copper surface by providing energy from a scanning tunneling microscope tip. Later, in 2017, the world's first-ever nanocar race took place in Toulouse.{{cite web|url=https://www.ladepeche.fr/article/2015/11/30/2227726-nanocar-race-la-course-de-petites-voitures-pour-grands-savants.html| title=NanoCar Race : la course de petites voitures pour grands savants|trans-title=NanoCar Race: the race of small cars for great scientists|language=French|date=November 30, 2017|newspaper=La Dépêche du Midi|accessdate=December 2, 2018}}

|File:Nanocar2.png

Biological molecular machines

Image:Protein translation.gif and membrane targeting stages of protein translation. The ribosome is green and yellow, the tRNAs are dark blue, and the other proteins involved are light blue. The produced peptide is released into the endoplasmic reticulum.]]

Many macromolecular machines are found within cells, often in the form of multi-protein complexes.{{Cite book|title=Biochemistry|last=Donald|first=Voet|date=2011|publisher=John Wiley & Sons|others=Voet, Judith G.|isbn=9780470570951|edition= 4th|location=Hoboken, NJ|oclc=690489261}} Examples of biological machines include motor proteins such as myosin, which is responsible for muscle contraction, kinesin, which moves cargo inside cells away from the nucleus along microtubules, and dynein, which moves cargo inside cells towards the nucleus and produces the axonemal beating of motile cilia and flagella. "[I]n effect, the [motile cilium] is a nanomachine composed of perhaps over 600 proteins in molecular complexes, many of which also function independently as nanomachines ... Flexible linkers allow the mobile protein domains connected by them to recruit their binding partners and induce long-range allostery via protein domain dynamics."{{cite journal |last1=Satir |first1=P. |last2=Christensen |first2=S. T. |title=Structure and function of mammalian cilia |journal=Histochemistry and Cell Biology |date=2008 |volume=129 |issue=6 |pages=687–693 |doi=10.1007/s00418-008-0416-9|pmid=18365235 |pmc=2386530 }} Other biological machines are responsible for energy production, for example ATP synthase which harnesses energy from proton gradients across membranes to drive a turbine-like motion used to synthesise ATP, the energy currency of a cell.{{Cite journal|last1=Kinbara|first1=Kazushi|last2=Aida|first2=Takuzo|date=2005-04-01|title=Toward Intelligent Molecular Machines: Directed Motions of Biological and Artificial Molecules and Assemblies|journal=Chemical Reviews|volume=105|issue=4|pages=1377–1400|doi=10.1021/cr030071r|pmid=15826015|issn=0009-2665}} Still other machines are responsible for gene expression, including DNA polymerases for replicating DNA, RNA polymerases for producing mRNA, the spliceosome for removing introns, and the ribosome for synthesising proteins. These machines and their nanoscale dynamics are far more complex than any molecular machines that have yet been artificially constructed.{{cite book |vauthors=Bu Z, Callaway DJ |chapter=Proteins MOVE! Protein dynamics and long-range allostery in cell signaling |volume=83 |pages=163–221 |year=2011 |pmid=21570668 |doi=10.1016/B978-0-12-381262-9.00005-7 |chapter-url=http://linkinghub.elsevier.com/retrieve/pii/B978-0-12-381262-9.00005-7 |series=Advances in Protein Chemistry and Structural Biology |isbn=9780123812629|title=Protein Structure and Diseases |publisher=Academic Press }}

Biological machines have potential applications in nanomedicine.{{Cite journal | doi = 10.1002/ange.200905200| title = Targeted Optimization of a Protein Nanomachine for Operation in Biohybrid Devices| journal = Angewandte Chemie| volume = 122| issue = 2| pages = 322–326| year = 2010| last1 = Amrute-Nayak | first1 = M. | last2 = Diensthuber | first2 = R. P. | last3 = Steffen | first3 = W. | last4 = Kathmann | first4 = D. | last5 = Hartmann | first5 = F. K. | last6 = Fedorov | first6 = R. | last7 = Urbanke | first7 = C. | last8 = Manstein | first8 = D. J. | last9 = Brenner | first9 = B. | last10 = Tsiavaliaris | first10 = G. | pmid = 19921669| bibcode = 2010AngCh.122..322A}} For example, they could be used to identify and destroy cancer cells.{{Cite journal | doi = 10.1080/10611860600612862| title = Nanorobot: A versatile tool in nanomedicine| journal = Journal of Drug Targeting| volume = 14| issue = 2| pages = 63–7| year = 2006| last1 = Patel | first1 = G. M. | last2 = Patel | first2 = G. C. | last3 = Patel | first3 = R. B. | last4 = Patel | first4 = J. K. | last5 = Patel | first5 = M. | pmid=16608733| s2cid = 25551052}}{{Cite journal | doi = 10.1002/anie.201100115| title = Micromachine-Enabled Capture and Isolation of Cancer Cells in Complex Media| journal = Angewandte Chemie International Edition| volume = 50| issue = 18| pages = 4161–4164| year = 2011| last1 = Balasubramanian | first1 = S. | last2 = Kagan | first2 = D. | last3 = Jack Hu | first3 = C. M. | last4 = Campuzano | first4 = S. | last5 = Lobo-Castañon | first5 = M. J. | last6 = Lim | first6 = N. | last7 = Kang | first7 = D. Y. | last8 = Zimmerman | first8 = M. | last9 = Zhang | first9 = L. | last10 = Wang | first10 = J. | pmid=21472835 | pmc=3119711}} Molecular nanotechnology is a speculative subfield of nanotechnology regarding the possibility of engineering molecular assemblers, biological machines which could re-order matter at a molecular or atomic scale.{{cn|date=April 2025}} Nanomedicine would make use of these nanorobots, introduced into the body, to repair or detect damages and infections, but these are considered to be far beyond current capabilities.{{cite journal |journal=Journal of Computational and Theoretical Nanoscience |volume=2 |pages=471 |date=2005 |title=Current Status of Nanomedicine and Medical Nanorobotics |first1=Robert A. Jr. |last1=Freitas|doi=10.1166/jctn.2005.001 |first2=Ilkka |last2=Havukkala |url=http://www.nanomedicine.com/Papers/NMRevMar05.pdf |issue=4|bibcode=2005JCTN....2..471K }}

Research and applications

Advances in this area are inhibited by the lack of synthetic methods.{{Cite journal|last1=Golestanian|first1=Ramin|last2=Liverpool|first2=Tanniemola B.|last3=Ajdari|first3=Armand|date=2005-06-10|title=Propulsion of a Molecular Machine by Asymmetric Distribution of Reaction Products|journal=Physical Review Letters|volume=94|issue=22|pages=220801|doi=10.1103/PhysRevLett.94.220801|pmid=16090376|arxiv=cond-mat/0701169|bibcode=2005PhRvL..94v0801G|s2cid=18989399}} In this context, theoretical modeling has emerged as a pivotal tool to understand the self-assembly or -disassembly processes in these systems.{{Cite journal|last=Drexler|first=K. Eric|date=1999-01-01|title=Building molecular machine systems|url=https://www.cell.com/trends/biotechnology/abstract/S0167-7799(98)01278-5|journal=Trends in Biotechnology|language=en|volume=17|issue=1|pages=5–7|doi=10.1016/S0167-7799(98)01278-5|issn=0167-7799}}{{cite journal|author1=Tabacchi, G. |author2=Silvi, S. |author3=Venturi, M. |author4=Credi, A. |author5=Fois, E. |journal=ChemPhysChem |year=2016|doi=10.1002/cphc.201501160|pmid=26918775 |title=Dethreading of a Photoactive Azobenzene-Containing Molecular Axle from a Crown Ether Ring: A Computational Investigation |volume=17 |issue=12 |pages=1913–1919|hdl=11383/2057447 |s2cid=9660916 }}

Possible applications have been demonstrated for AMMs, including those integrated into polymeric,{{cite journal |last1=Ikejiri |first1=S. |last2=Takashima |first2=Y. |last3=Osaki |first3=M. |last4=Yamaguchi |first4=H. |last5=Harada |first5=A. |title=Solvent-Free Photoresponsive Artificial Muscles Rapidly Driven by Molecular Machines |journal=Journal of the American Chemical Society |date=2018 |volume=140 |issue=49 |pages=17308–17315 |doi=10.1021/jacs.8b11351|pmid=30415536 |bibcode=2018JAChS.14017308I |s2cid=207195871 }}{{cite journal |last1=Iwaso |first1=K. |last2=Takashima |first2=Y. |last3=Harada |first3=A. |title=Fast response dry-type artificial molecular muscles with [c2]daisy chains |journal=Nature Chemistry |date=2016 |volume=8 |issue=6 |pages=625–632 |doi=10.1038/nchem.2513|pmid=27219709 |bibcode=2016NatCh...8..625I }} liquid crystal,{{cite journal |last1=Orlova |first1=T. |last2=Lancia |first2=F. |last3=Loussert |first3=C. |last4=Iamsaard |first4=S. |last5=Katsonis |first5=N. |last6=Brasselet |first6=E. |title=Revolving supramolecular chiral structures powered by light in nanomotor-doped liquid crystals |journal=Nature Nanotechnology |date=2018 |volume=13 |issue=4 |pages=304–308 |doi=10.1038/s41565-017-0059-x|pmid=29434262 |bibcode=2018NatNa..13..304O |s2cid=3326300 |url=https://hal.archives-ouvertes.fr/hal-01803743/file/OrlovaNN2018_PostPrint.pdf }}{{cite journal |last1=Hou |first1=J. |last2=Long |first2=G. |last3=Zhao |first3=W. |last4=Zhou |first4=G. |last5=Liu |first5=D. |last6=Broer |first6=D. J. |last7=Feringa |first7=B. L. |last8=Chen |first8=J. |title=Phototriggered Complex Motion by Programmable Construction of Light-Driven Molecular Motors in Liquid Crystal Networks |journal=Journal of the American Chemical Society |date=2022 |volume=144 |issue=15 |pages=6851–6860 |doi=10.1021/jacs.2c01060|pmid=35380815 |pmc=9026258 |bibcode=2022JAChS.144.6851H }} and crystalline{{cite journal |last1=Terao |first1=F. |last2=Morimoto |first2=M. |last3=Irie |first3=M. |title=Light-Driven Molecular-Crystal Actuators: Rapid and Reversible Bending of Rodlike Mixed Crystals of Diarylethene Derivatives |journal=Angewandte Chemie International Edition |date=2012 |volume=51 |issue=4 |pages=901–904 |doi=10.1002/anie.201105585|pmid=22028196 }}{{cite journal |last1=Vogelsberg |first1=C. S. |last2=Garcia-Garibay |first2=M. A. |title=Crystalline molecular machines: function, phase order, dimensionality, and composition |journal=Chemical Society Reviews |date=2012 |volume=41 |issue=5 |pages=1892–1910 |doi=10.1039/c1cs15197e|pmid=22012174 }} systems for varied functions. Homogenous catalysis is a prominent example, especially in areas like asymmetric synthesis, utilizing noncovalent interactions and biomimetic allosteric catalysis.{{cite journal |last1=van Dijk |first1=L. |last2=Tilby |first2=M. J. |last3=Szpera |first3=R. |last4=Smith |first4=O. A. |last5=Bunce |first5=H. A. P. |last6=Fletcher |first6=S. P. |title=Molecular machines for catalysis |journal=Nature Reviews Chemistry |date=2018 |volume=2 |issue=3 |pages=0117 |doi=10.1038/s41570-018-0117|s2cid=139606220 |url=https://ora.ox.ac.uk/objects/uuid:3b300c32-b5c1-4415-beb5-53d3e819b71b }}{{cite journal |last1=Neal |first1=E. A. |last2=Goldup |first2=S. M. |title=Chemical consequences of mechanical bonding in catenanes and rotaxanes: isomerism, modification, catalysis and molecular machines for synthesis |journal=Chemical Communications |date=2014 |volume=50 |issue=40 |pages=5128–5142 |doi=10.1039/C3CC47842D|pmid=24434901 |doi-access=free }} AMMs have been pivotal in the design of several stimuli-responsive smart materials, such as 2D and 3D self-assembled materials and nanoparticle-based systems, for versatile applications ranging from 3D printing to drug delivery.{{cite journal |last1=Corra |first1=S. |last2=Curcio |first2=M. |last3=Baroncini |first3=M. |last4=Silvi |first4=S. |last5=Credi |first5=A. |title=Photoactivated Artificial Molecular Machines that Can Perform Tasks |journal=Advanced Materials |date=2020 |volume=32 |issue=20 |pages=1906064 |doi=10.1002/adma.201906064|pmid=31957172 |bibcode=2020AdM....3206064C |s2cid=210830979 |hdl=11585/718295 |hdl-access=free }}{{cite journal |last1=Moulin |first1=E. |last2=Faour |first2=L. |last3=Carmona-Vargas |first3=C. C. |last4=Giuseppone |first4=N. |title=From Molecular Machines to Stimuli-Responsive Materials |journal=Advanced Materials |date=2020 |volume=32 |issue=20 |pages=1906036 |doi=10.1002/adma.201906036|pmid=31833132 |bibcode=2020AdM....3206036M |s2cid=209343354 |url=https://hal.archives-ouvertes.fr/hal-03080467/file/AdvMat_Giuseppone.pdf }}

AMMs are gradually moving from the conventional solution-phase chemistry to surfaces and interfaces. For instance, AMM-immobilized surfaces (AMMISs) are a novel class of functional materials consisting of AMMs attached to inorganic surfaces forming features like self-assembled monolayers; this gives rise to tunable properties such as fluorescence, aggregation and drug-release activity.{{cite journal |last1=Zhang |first1=Q. |last2=Qu |first2=D.-H. |title=Artificial Molecular Machine Immobilized Surfaces: A New Platform To Construct Functional Materials |journal=ChemPhysChem |date=2016 |volume=17 |issue=12 |pages=1759–1768 |doi=10.1002/cphc.201501048|pmid=26717523 }}

Most of these "applications" remain at the proof-of-concept level. Challenges in streamlining macroscale applications include autonomous operation, the complexity of the machines, stability in the synthesis of the machines and the working conditions.{{cite journal |last1=Aprahamian |first1=I. |title=The Future of Molecular Machines |journal=ACS Central Science |date=2020 |volume=6 |issue=3 |pages=347–358 |doi=10.1021/acscentsci.0c00064|pmid=32232135 |pmc=7099591 }}

References

Category:Nanotechnology

Category:Supramolecular chemistry

Category:Molecular machines

Category:Nanomachines

Molecular machine#Biological

Terminology

History

Artificial molecular machines

= Types =

Biological molecular machines

Research and applications

See also

References