Supramolecular chemistry yog ib thaj chaw ntawm kev tshawb fawb uas dhau mus dhau cov khoom uas tsom mus rau cov kev tshawb fawb uas tsim los ntawm cov lej sib cais ntawm cov subunits los yog cov khoom sib txuas. Lub zog lub luag haujlwm rau lub koom haum spatial tuaj yeem muaj los ntawm cov tsis muaj zog (electrostatic lossis hydrogen bonds) mus rau muaj zog (covalent bonds) muab tias qhov kev sib raug zoo ntawm hluav taws xob ntawm cov molecular Cheebtsam tseem me me nyob rau hauv kev sib raug zoo rau lub zog tsis sib xws ntawm cov khoom.
ntsiab lus tseem ceeb
Thaum cov tshuaj chemistry ib txwm tsom mus rau covalent daim ntawv cog lus, supramolecular chemistry tshawb nrhiav qhov tsis muaj zog thiab thim rov qab tsis yog cov kev sib cuam tshuam ntawm cov molecules. Cov rog no suav nrog kev sib koom ua ke hydrogen, kev sib koom tes hlau, hydrophobic van der Waals teeb, thiab cov teebmeem electrostatic.
Cov ntsiab lus tseem ceeb uas tau qhia siv qhov noCov kev qhuab qhia muaj xws li ib feem ntawm nws tus kheej sib sau ua ke, folding, kev lees paub, tus tswv tsev qhua, kev sib koom ua ke ntawm kev sib koom ua ke, thiab dynamic covalent science. Txoj kev kawm ntawm cov tsis-covalent hom kev sib cuam tshuam hauv supramolecular chemistry yog qhov tseem ceeb rau kev nkag siab txog ntau yam kev lom neeg los ntawm cov qauv ntawm tes mus rau lub zeem muag uas vam khom rau cov rog no. Biological systems feem ntau yog qhov kev tshoov siab rau kev tshawb fawb. Supermolecules yog rau molecules thiab intermolecular bonds, raws li hais tias yog rau atoms, thiab covalent tangency.
History
Lub neej ntawm cov rog sib txuas yog thawj zaug los ntawm Johannes Diederik van der Waals hauv 1873. Txawm li cas los xij, Nobel laureate Hermann Emil Fischer tau tsim cov hauv paus ntsiab lus ntawm supramolecular chemistry. Xyoo 1894, Fisher tau qhia tias kev sib cuam tshuam ntawm enzyme-substrate siv rau hauv "xauv thiab qhov tseem ceeb", cov ntsiab lus tseem ceeb ntawm kev paub txog molecular thiab tus tswv tsev chemistry. Nyob rau hauv lub xyoo pua 20th thaum ntxov, cov nyiaj tsis-covalent tau kawm ntau yam ntxiv, nrog rau cov nyiaj hydrogen tau piav qhia los ntawm Latimer thiab Rodebush hauv xyoo 1920.
Kev siv cov ntsiab cai no tau ua rau nkag siab tob txog cov qauv protein thiab lwm cov txheej txheem lom neeg. Piv txwv li, ib qho tseem ceeb ntawm kev ua txhaum uas ua rau muaj kev nthuav dav ntawm ob lub helix qauv los ntawm DNA tshwm sim thaum nws tau pom tseeb tias muaj ob qhov sib cais ntawm nucleotides txuas nrog ntawm hydrogen bonds. Kev siv cov kev sib raug zoo uas tsis yog-covalent yog qhov tseem ceeb rau kev rov ua dua vim tias lawv tso cai rau cov strands sib cais thiab siv los ua tus qauv rau ib qho tshiab. DNA muab ob npaug rau. Nyob rau tib lub sijhawm, chemists pib paub thiab kawm cov qauv hluavtaws raws li kev sib cuam tshuam uas tsis yog-covalent, xws li micelles thiab microemulsions.
Thaum kawg, cov kws tshuaj muaj peev xwm coj tau cov ntsiab lus no thiab siv rau cov tshuab hluavtaws. Ib qho kev tawg tshwm sim hauv xyoo 1960 - kev sib txuas ntawm cov yas (ethers raws li Charles Pedersen). Ua raws li txoj haujlwm no, lwm tus kws tshawb fawb xws li Donald J. Crum, Jean-Marie Lehn, thiab Fritz Vogtl tau ua haujlwm nyob rau hauv kev sib txuas ntawm daim ntawv-ion-selective receptors, thiab thaum xyoo 1980, kev tshawb fawb hauv cheeb tsam no tau txais lub zog. Cov kws tshawb fawb tau ua haujlwm nrog cov ntsiab lus xws li kev sib cuam tshuam ntawm cov tshuab molecular.
Nyob rau xyoo 90s, supramolecular chemistry tau dhau los ua teeb meem ntau dua. Cov kws tshawb fawb xws li James Fraser Stoddart tau tsim cov txheej txheem molecular thiab cov txheej txheem sib koom ua ke ntawm tus kheej, thaum Itamar Wilner tau kawm thiab tsim cov sensors thiab cov hau kev rau kev sib cuam tshuam hauv hluav taws xob thiab lom. Thaum lub sij hawm no, photochemical motifs tau koom ua ke rau hauv supramolecular systems kom muaj nuj nqis, kev tshawb fawb pib ntawm kev sib txuas lus ntawm tus kheej-replicating, thiab ua hauj lwm txuas ntxiv ntawm cov khoom siv rau kev ua cov ntaub ntawv molecular. Kev hloov pauv ntawm kev tshawb fawb ntawm nanotechnology kuj tseem muaj kev cuam tshuam rau lub ntsiab lus no, tsim cov tsev blocks xws li fullerenes (supramolecular chemistry), nanoparticles, thiab dendrimers. Lawv koom nrog hauv cov tshuab hluavtaws.
Control
Supramolecular chemistry cuam tshuam nrog kev sib cuam tshuam me me, thiab yog li tswj hwm cov txheej txheem koom nrogtej zaum yuav xav tau zoo precision. Tshwj xeeb, cov nyiaj tsis yog covalent muaj lub zog qis, thiab feem ntau tsis muaj lub zog txaus rau kev ua kom muaj zog, tsim. Raws li Arrhenius kab zauv qhia tau hais tias, qhov no txhais tau hais tias, tsis zoo li covalent daim ntawv cog lus ua chemistry, tus nqi ntawm creation tsis nce nyob rau hauv siab dua. Qhov tseeb, cov tshuaj sib npaug sib npaug qhia tau tias tsis muaj zog ua rau muaj kev hloov pauv mus rau kev puas tsuaj ntawm supramolecular complexes ntawm qhov kub siab dua.
Txawm li cas los xij, qib qis kuj tuaj yeem tsim teeb meem rau cov txheej txheem zoo li no. Supramolecular chemistry (UDC 541-544) yuav xav tau cov molecules kom hloov mus rau hauv cov thermodynamically unfavorable conformations (piv txwv li, thaum lub sij hawm "synthesis" ntawm rotaxanes nrog plam). Thiab nws yuav suav nrog qee qhov kev tshawb fawb sib txawv uas zoo ib yam nrog cov saum toj no. Tsis tas li ntawd, qhov dynamic xwm ntawm supramolecular chemistry yog siv nyob rau hauv ntau mechanics. Thiab tsuas yog qhov txias txias yuav ua rau cov txheej txheem no qeeb.
Yog li, thermodynamics yog ib qho cuab yeej tseem ceeb rau kev tsim, tswj thiab kawm supramolecular chemistry hauv kev ua neej nyob. Tej zaum qhov piv txwv zoo tshaj plaws yog cov kab mob ntshav qab zib, uas tsis ua haujlwm sab nraum qhov ntsuas qhov nqaim heev.
Environmental sphere
Qhov ib puag ncig molecular nyob ib puag ncig cov kab ke supramolecular kuj tseem ceeb heev rau nws txoj haujlwm thiab kev ruaj ntseg. Ntau cov kuab tshuaj muaj zog hydrogen bonds, electrostaticcov khoom thiab lub peev xwm los hloov cov nqi, thiab yog li ntawd lawv tuaj yeem nkag mus rau hauv txoj kev sib npaug nrog lub kaw lus, txawm tias tag nrho cov complexes. Vim li no, kev xaiv cov kuab tshuaj tuaj yeem yog qhov tseem ceeb.
Molecular self-assembly
Qhov no yog lub tsev tsis muaj kev taw qhia lossis kev tswj hwm los ntawm qhov chaw sab nraud (tsis yog los muab qhov chaw zoo). Molecules raug coj mus rau sau los ntawm kev sib cuam tshuam uas tsis yog-covalent. Self-assembly yuav subdivided rau hauv intermolecular thiab intramolecular. Qhov kev txiav txim no tseem tso cai rau kev tsim cov qauv loj xws li micelles, membranes, vesicles, kua muaju. Qhov no yog ib qho tseem ceeb rau siv lead ua engineering.
MP thiab complex
Molecular lees paub yog qhov tshwj xeeb khi ntawm tus qhua particle rau tus tswv tsev ntxiv. Feem ntau lub ntsiab txhais ntawm hom twg yog nws thiab qhov twg yog "tus qhua" zoo li yog arbitrary. Molecules tuaj yeem txheeb xyuas ib leeg siv cov kev sib cuam tshuam uas tsis yog-covalent. Cov ntawv thov tseem ceeb hauv cheeb tsam no yog tus qauv tsim thiab catalysis.
Template Directed Synthesis
Molecular lees paub thiab kev sib sau ua tus kheej tuaj yeem siv nrog cov tshuaj reactive los npaj ua ntej cov tshuaj tiv thaiv kab mob (kom tsim ib lossis ntau dua cov nyiaj cog lus). Qhov no tuaj yeem suav hais tias yog qhov tshwj xeeb ntawm supramolecular catalysis.
Tsis yog-covalent daim ntawv cog lus ntawm cov reactants thiab "matrix" ua kom cov chaw tshuaj tiv thaiv nyob ze ua ke, txhawb cov chemistry xav tau. Txoj kev notshwj xeeb tshaj yog muaj txiaj ntsig zoo nyob rau hauv cov xwm txheej uas qhov kev xav tau kev sib haum xeeb yog thermodynamically lossis kinetically tsis zoo li, xws li hauv kev tsim cov macrocycles loj. Lub koom haum ua ntej nws tus kheej hauv supramolecular chemistry tseem ua haujlwm rau lub hom phiaj xws li txo qis kev cuam tshuam sab nraud, txo qis lub zog ua kom muaj zog, thiab tau txais qhov xav tau stereochemistry.
Tom qab cov txheej txheem dhau los, tus qauv yuav nyob twj ywm, raug tshem tawm, lossis "automatically" decomplexed vim muaj ntau yam khoom paub txog cov khoom. Cov qauv tuaj yeem yooj yim li ib qho hlau ion lossis nyuaj heev.
Mechanically interconnected molecular architectures
Lawv yog tsim los ntawm cov khoom uas tsuas yog txuas nrog rau qhov tshwm sim ntawm lawv cov topology. Qee qhov kev sib cuam tshuam uas tsis yog-covalent tuaj yeem tshwm sim ntawm cov khoom sib txawv (feem ntau cov siv hauv kev tsim kho), tab sis covalent bonds tsis muaj nyob. Kev tshawb fawb - supramolecular chemistry, tshwj xeeb yog matrix-directed synthesis, yog tus yuam sij rau kev sib xyaw ua haujlwm zoo. Piv txwv ntawm mechanically interconnected molecular architectures muaj xws li catenanes, rotaxanes, knots, Borromean rings, thiab ravels.
Dynamic Covalent Chemistry
Nyob rau hauv nws daim ntawv cog lus raug puas tsuaj thiab tsim nyob rau hauv ib tug reversible cov tshuaj tiv thaiv nyob rau hauv thermodynamic tswj. Thaum covalent daim ntawv cog lus yog tus yuam sij rau cov txheej txheem, lub kaw lus tau tsav los ntawm cov tsis yog covalent rog los tsim cov qauv hluav taws xob qis tshaj plaws.
YBiomimetics
Ntau yam hluavtaws supramolecularsystems yog tsim los luam cov dej num ntawm biological spheres. Cov qauv biomimetic no tuaj yeem siv los kawm ob qho tib si qauv thiab kev siv hluavtaws. Piv txwv xws li photoelectrochemical, catalytic systems, protein engineering, thiab tus kheej-replication.
Molecular Engineering
Cov no yog ib feem ntawm cov rooj sib txoos uas tuaj yeem ua haujlwm xws li tawm los yog kev sib hloov, hloov thiab tuav. Cov khoom siv no muaj nyob rau hauv pem hauv ntej ntawm supramolecular chemistry thiab nanotechnology, thiab cov qauv tsim tau pom siv cov ntsiab lus zoo sib xws. Jean-Pierre Sauvage, Sir J. Fraser Stoddart thiab Bernard L. Feringa tau qhia txog 2016 Nobel nqi zog hauv Chemistry rau kev tsim thiab kev sib txuas ntawm cov tshuab molecular.
YMacrocycles
Macrocycles muaj txiaj ntsig zoo hauv supramolecular chemistry vim tias lawv muab tag nrho cov kab noj hniav uas tuaj yeem nyob ib puag ncig cov qhua tuaj noj mov thiab raug hloov kho tshuaj los kho lawv cov khoom zoo.
Cyclodextrins, calixarenes, cucurbiturils thiab yas ethers tau yooj yim ua ke hauv ntau qhov ntau thiab yog li yooj yim rau siv hauv supramolecular systems. Ntau dua cyclophanes thiab cryptands tuaj yeem ua ke los muab cov khoom paub txog tus kheej.
Supramolecular metallocycles yog macrocyclic aggregates nrog hlau ions nyob rau hauv lub nplhaib, feem ntau tsim los ntawm angular thiab linear modules. Cov duab metallocycle feem ntau nyob rau hauv hom kev siv no muaj xws li daim duab peb sab, squares, thiabpentagons, txhua tus nrog cov pab pawg ua haujlwm uas txuas cov khoom los ntawm "kev sib dhos tus kheej".
Metallacrowns yog metallomacrocycles tsim los siv txoj hauv kev zoo sib xws nrog fused chelate rings.
Supramolecular chemistry: khoom
Ntau lub tshuab zoo li no xav tau lawv cov khoom kom muaj qhov sib txawv thiab kev sib haum xeeb ntawm ib leeg, thiab yog li yuav tsum tau siv cov txheej txheem yooj yim.
Feem ntau, spacers thiab txuas cov pab pawg muaj xws li polyester, biphenyls thiab triphenyls thiab yooj yim alkyl chains. Chemistry los tsim thiab muab cov cuab yeej no nkag siab zoo heev.
Nto tuaj yeem siv los ua scaffolding los xaj cov tshuab nyuaj, thiab cuam tshuam cov tshuaj electrochemical nrog electrodes. Cov chaw tsis tu ncua tuaj yeem siv los tsim cov monolayers thiab multilayer self-assemblies.
Kev nkag siab ntawm kev sib cuam tshuam ntawm cov khoom sib txuas hauv cov khoom khib nyiab tau dhau los ua qhov tseem ceeb vim muaj kev koom tes ntawm ntau yam kev sim thiab kev suav hauv kaum xyoo dhau los. Qhov no suav nrog kev kawm siab hauv cov khib nyiab thiab hauv qhov chaw crystallization ntawm cov tebchaw uas yog cov kua hauv chav tsev kub, nrog rau kev siv cov electron ceev tsom xam, siv lead ua qauv kwv yees, thiab cov khoom hauv lub xeev DFT suav kom muaj kev nkag siab ntau ntawm cov xwm txheej, muaj zog, thiab topology.
Photo-electrochemically active units
Porphyrins thiab phthalocyanines muaj kev tswj hwm zoophotochemical zog, nrog rau lub peev xwm rau txoj kev tsim.
Photochromic thiab photoisomerizable pawg muaj peev xwm hloov lawv cov duab thiab cov khoom thaum raug lub teeb.
TTF thiab quinones muaj ntau dua ib lub xeev oxidation ruaj khov thiab yog li ntawd tuaj yeem hloov tau los ntawm kev txo cov chemistry lossis electron science. Lwm cov chav xws li benzidine derivatives, viologen pawg, thiab fullerenes kuj tau siv rau hauv cov khoom siv supramolecular.
Biologically derived units
Cov complexion muaj zog heev ntawm avidin thiab biotin txhawb cov ntshav txhaws thiab siv los ua ib qho kev lees paub los tsim cov tshuab hluavtaws.
Kev khi ntawm cov enzymes rau lawv cov cofactors tau siv los ua txoj hauv kev kom tau txais kev hloov kho, hluav taws xob tiv tauj thiab txawm tias cov duab hloov pauv tau. DNA yog siv los ua cov qauv thiab kev ua haujlwm hauv cov tshuab hluavtaws supramolecular.
Material Technology
Supramolecular chemistry tau pom ntau daim ntawv thov, tshwj xeeb, cov txheej txheem molecular self-assembly tau tsim los tsim cov ntaub ntawv tshiab. Cov qauv loj tuaj yeem nkag mus tau yooj yim siv cov txheej txheem hauv qab, vim lawv tau tsim los ntawm cov khoom me me uas yuav tsum tau ua kom tsawg dua los ua ke. Yog li, feem ntau txoj hauv kev rau nanotechnology yog raws li supramolecular chemistry.
Catalysis
Nws yog lawv txoj kev loj hlob thiab kev nkag siab uas yog qhov tseem ceeb ntawm kev siv tshuaj supramolecular. Kev tsis sib haum xeeb yog qhov tseem ceeb heev hauvcatalysis los ntawm binding reactants nyob rau hauv conformations haum rau cov tshuaj tiv thaiv thiab txo lub zog nyob rau hauv lub hloov lub xeev. Template directed synthesis yog ib qho xwm txheej ntawm cov txheej txheem supramolecular. Cov tshuab encapsulation xws li micelles, dendrimers, thiab cavitands kuj tseem siv rau hauv catalysis los tsim microenvironment tsim nyog rau kev tshwm sim rau qhov chaw uas tsis tuaj yeem siv rau ntawm qhov ntsuas macroscopic.
Tshuaj
Txoj kev raws li supramolecular chemistry tau coj mus rau ntau daim ntawv thov hauv kev tsim cov khoom siv biomaterials thiab kho. Lawv muab ntau yam ntawm modular thiab generalizable platforms nrog customizable mechanical, tshuaj thiab lom zog. Cov no suav nrog cov tshuab ua raws li kev sib dhos peptide, tus tswv macrocycles, kev sib raug zoo hydrogen siab, thiab kev sib cuam tshuam hlau-ligand.
Txoj hauv kev supramolecular tau siv dav los tsim cov khoom siv dag zog los thauj cov sodium thiab potassium hauv thiab tawm ntawm cov hlwb.
Cov tshuaj chemistry no tseem ceeb heev rau kev txhim kho cov tshuaj kho tshiab los ntawm kev nkag siab txog kev sib txuas ntawm cov tshuaj hauv qhov chaw. Kev lag luam ntawm kev xa tshuaj kuj tseem ua rau muaj kev cuam tshuam loj heev los ntawm kev siv tshuaj supramolecular. Nws muab encapsulation thiab phiaj tso tawm mechanisms. Tsis tas li ntawd, cov txheej txheem no tau tsim los cuam tshuam cov protein-rau-protein kev sib cuam tshuam uas tseem ceeb rau kev ua haujlwm ntawm tes.
Tseeb nyhuv thiab supramolecular chemistry
Hauv kev tshawb fawb, cov qauv tshuaj tiv thaiv yog ib chav kawm ntawm ligand raws li kev ua. Lawv tshwm sim ntawm ob lossis ntau qhov chaw sib koom ua ke ntawm qhov chaw hlau. Cov ntsiab lus "cov nyhuv template" thiab "self-assembly" nyob rau hauv supramolecular chemistry yog siv nyob rau hauv kev sib koom tes science. Tab sis thaum tsis muaj ion, tib cov organic reagents muab cov khoom sib txawv. Qhov no yog cov nyhuv template hauv supramolecular chemistry.
