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Wax-soo-saarka wax-soo-saarka wax-soo-saarka ayaa beddelaya habka cilmi-baarayaasha iyo warshad-yaqaannada ay u naqshadeeyaan oo ay u soo saaraan qalabyada kiimikada si ay u daboolaan baahidooda gaarka ah. Shaqadan, waxaan ku soo gudbineynaa tusaalaha ugu horreeya ee fal-celinta qulqulka ee ay sameeyeen farsamada-soo-saarka birta ee adag ee wax-soo-saarka Ultrasonic Additive Manufacturing (UAM) oo leh qaybo toos ah oo isku dhafan iyo walxaha dareemayaasha. Bayooloji ahaan 1,4-ku-daran 1,2,3-triazole xeryahooda ayaa si guul leh loo farsameeyay oo lagu hagaajiyay Cu-dhexdhexaadiyay Huisgen 1,3-dipolar cycloaddition reaction iyadoo la isticmaalayo kimistari UAM
Sababtoo ah faa'iidooyinka muhiimka ah ee ka badan dhiggiisa bulk, chemistry socodka waa mid muhiim ah oo sii kordhaya goobaha tacliinta iyo warshadaha labadaba sababtoo ah awoodda ay u leedahay in ay kordhiso xulashada iyo waxtarka kiimikada kiimikada. In ka badan 50% falcelinta kiimikada wanaagsan iyo warshadaha dawooyinka ayaa ka faa'iideysan kara isticmaalka socodsiinta socodka joogtada ah7.
Sanadihii la soo dhaafay, waxaa jiray isbeddello sii kordhaya oo kooxo raadinaya inay beddelaan qalabka muraayadaha dhaqameed ama qulqulka qalabka kiimikada ee wax soo saarka wax-soo-saarka (AM) ee kiimikada "weelasha falcelinta"8. Naqshadeynta celceliska, wax soo saarka degdega ah, iyo 3-cabbirka (3D) awoodaha farsamooyinkan ayaa faa'iido u leh kuwa doonaya in ay qalabeeyaan qalabkooda si gaar ah oo loogu talagalay falcelinta, qalabka, ama xaaladaha shaqada ayaa ku dhawaad ​​​​isticmaalka falcelinta, qalabyada, ama xaaladaha shaqada. Farsamooyinka daabacaadda 3D sida stereolithography (SL) 9,10,11, fused deposition modeling (FDM) 8,12,13,14 iyo inkjet printing 7, 15, 16 beerta17, 18, 19, 20.
Sababo la xiriira isticmaalka sii kordhaya ee kiimikada socodka iyo guryaha wanaagsan ee la xidhiidha AM, waxaa jira baahi loo qabo in la sahamiyo farsamooyin aad u horumarsan oo awood u isticmaala si ay u abuuraan weelasha falcelinta qulqulka awood kiimiko iyo falanqaynta.These waa in ay awood dadka isticmaala si ay u doortaan tiro ka mid ah qalabka aadka u adag ama functional awood u leh in ay wax ka qabtaan kala duwan oo ka mid ah xaaladaha falcelinta, halka sidoo kale fududaynta noocyada kala duwan ee falcelinta ee qalabka si ay u oggolaadaan noocyada kala duwan ee falcelinta falanqeynta.
Mid ka mid ah habka wax soo saarka wax lagu daro in uu leeyahay awoodda si ay u horumariyaan reactors kiimikada caadadii waa Ultrasonic wax-soo-saarka wax-soo-saarka (UAM) .Tani farsamo lamination xaashida adag-state khuseysaa ultrasonic oscillations in foils biraha dhuuban si ay ugu biiraan iyaga si wadajir ah lakabka by lakabka kulaylka bulk ugu yar iyo heerka sare ee socodka caag ah 21 , 22 , 23 .Unlike inta badan wax soo saarka AM ee teknoolajiyada hoose ee si toos ah loo garan karo sida wax soo saarka hybri oo kale. habka, kaas oo goobta-ku-meel-gaadhka ah ee kontoroolka nambarada kombuyuutarka (CNC) milling ama laser machining qeexaya qaabka saafiga ah ee lakabka alaabta bonded 24, 25.Tani waxay ka dhigan tahay in isticmaaluhu aanu ku xaddidnayn dhibaatooyinka la xidhiidha ka saarista alaabta dhismaha ee cayriin ee ka soo baxa dareeraha dareeraha yar yar, taas oo inta badan ah kiiska budada iyo dareeraha AM Systems26,27,28. Isku-dhafka walxaha kala duwan ee hal-abuurka ah ee habka hal-abuurka ah ee hal-abuurka ah ee ka baxsan habka dhalaalidda waxay ka dhigan tahay in baahida farsamada iyo kiimikada ee codsiyada gaarka ah ay si fiican u dabooli karaan.In dheer in isku-xidhka adag ee gobolka, dhacdo kale oo la kulantay inta lagu jiro xidhitaanka ultrasonic waa socodka sare ee alaabta caagga ah ee heerkulka hooseeya29,30,31,32,33. Tani waxay si gaar ah u leedahay UAM waxay fududeyn kartaa iyada oo aan la daboolin lakabka lakabka ee UAM. waxay fududeyn kartaa gaarsiinta macluumaadka waqtiga-dhabta ah ee aaladda isticmaalaha iyada oo loo marayo falanqayn isku dhafan.
Shaqadii hore ee qorayaashu32 waxay muujisay awooda habka UAM si ay u abuurto dhismooyin microfluidic 3D macdan ah oo leh awoodo dareen isku dhafan. qalab firfircoon oo aan kaliya kormeerin, laakiin sidoo kale soo jiidaya isku-dhafka kiimikada iyada oo loo marayo qalab isku-dhafan oo qaab-dhismeed ah. Qalabku wuxuu isku daraa dhowr faa'iidooyin oo la xidhiidha tignoolajiyada UAM ee soo saarista qalabka kiimikada ee 3D, sida: awoodda si toos ah loogu beddelo naqshadaha 3D ee buuxa ee naqshadaynta kombuyuutarka (CAD) ee alaabta; wax-soo-saarka alaabada badan si loo isku daro kuleylka kuleylka sare iyo walxaha kicinta; iyo ku dhejinta dareemayaasha kulaylka si toos ah inta u dhaxaysa durdurrada reagent ee saxda ah ee kormeerka heerkulka falcelinta iyo xakamaynta. Si loo muujiyo shaqeynta reactor-ka, maktabadda dawooyinka muhiimka ah ee 1,4-lagu khilaafay 1,2,3-triazole xeryahooda waxaa lagu farsameeyey Huisgen 1,3-dipolar-katalyzed Huisgen 1,3-dipolar cycloadition-ka naqshadaynta qalabka kombiyuutarka kor u qaadida fursadaha cusub iyo fursadaha kimisteriga iyada oo loo marayo cilmi-baadhisyo kala duwan.
Dhammaan dareerayaasha iyo reagen-yaasha waxa laga soo iibiyay Sigma-Aldrich, Alfa Aesar, TCI ama Fischer Scientific waxaana la isticmaalay iyada oo aan la nadiifin ka hor. CDCl3 ama (CD3)2SO sida dareere ah.Dhammaan falcelinta waxaa la sameeyay iyadoo la isticmaalayo Uniqsis FlowSyn flow chemistry platform.
UAM waxaa loo isticmaalay in lagu sameeyo dhammaan qalabka daraasaddan. Tiknoolajiyada waxaa la abuuray 1999, iyo faahfaahinteeda farsamada, xuduudaha hawlgalka iyo horumarinta tan iyo markii la abuuray waxaa lagu baran karaa iyada oo loo marayo agabyada daabacan ee soo socda qalabka socodka ahaayeen Cu-110 iyo Al 6061.Cu-110 uu leeyahay content naxaas sare (ugu yaraan 99.9% copper), taasoo ka dhigaysa musharax wanaagsan ee falcelinta copper-catalyzed, oo sidaas daraaddeed waxaa loo isticmaalaa sida "lakabka firfircoon gudahood microreactor ah. Al 6061 O waxaa loo isticmaalaa sida a "bulk" wax, sidoo kale Embedding lakabka ah oo isku dhafan oo la isku daray qayb ka mid ah qaybaha falanqaynta; Lakabka Cu-110 Al 6061 O waa walxo la muujiyay in ay si heer sare ah ula jaan qaadayaan hababka UAM38, 39, 40, 41 waxaana la tijaabiyay oo la helay kiimikaad deggan oo leh reagents-yada loo isticmaalo shaqadan hoose
Marxaladaha samaynta reactor (1) Al 6061 substrate (2) Samaynta kanaalka hoose oo loo dejiyay foornada naxaasta ah (3) Ku-xidhka heerkulbeegyada inta u dhaxaysa lakabyada (4) Kanaalka sare (5) Gelida iyo meelaha laga baxo (6) Reactor Monolithic.
Falsafada naqshadeynta ee dariiqa dareeraha waa in la isticmaalo waddo isku dhafan si loo kordhiyo dareeraha masaafada u socdaalaya gudaha chip-ka, iyada oo la ilaalinayo jajabka cabbirka la maareyn karo. Kororka fogaantan waa mid la jecel yahay in la kordhiyo wakhtiga isdhexgalka kicinta / reagent iyo bixinta wax soo saarka alaabta wanaagsan. sii kordhinta isku dhafka ah ee lagu gaari karo, naqshadeynta reactor-ka waxay ka kooban tahay laba godad reagent oo la isku daray oo ku yaala isgoyska Y ka hor inta aan la gelin qaybta isku dhafka serpentine. Meesha saddexaad, oo dhexda qulqulka nuska iyada oo loo marayo degenaanshaha, ayaa lagu daraa naqshadeynta mustaqbalka falcelinta falcelinta-tallaabada badan.
Dhammaan kanaalada waxay leeyihiin muuqaal labajibbaaran (aan lahayn xaglo qabyo ah), natiijada warshadaynta CNC ee xilliyeed ee loo isticmaalo abuuritaanka joomatari kanaalka. Cabirrada kanaalka waxaa loo doortaa si loo hubiyo wax soo saarka sare ee (microreactor), iyadoo yar oo ku filan si loo fududeeyo isdhexgalka dusha sare (catalysts) ee inta badan dareerayaasha ka kooban. x 750 µm iyo guud ahaan mugga reactor-ka wuxuu ahaa 1 ml. Xidhiidhiyaha isku dhafan (1/4″—28 dun UNF) ayaa lagu soo daray naqshadeynta si loogu oggolaado isdhexgalka fudud ee aaladda qalabka kimistari socodka ganacsiga. Cabbirka kanaalka ayaa xaddidaya dhumucda walxaha foil-ka, sifooyinka farsamada, iyo xuduudaha isku-xidhka ee loo isticmaalo ultrasonics. Ballaar gaar ah oo loogu talagalay shay la bixiyay, maaddadu waxay "sagi doontaa" kanaalka la abuuray. Hadda ma jiro nooc gaar ah oo xisaabintan ah, sidaas darteed ballaca kanaalka ugu sarreeya ee walxaha iyo naqshadeynta waxaa lagu go'aamiyaa si tijaabo ah; Xaaladdan oo kale, ballac 750 μm ma keeni doono sag.
Qaabka (square) ee kanaalka waxaa lagu go'aamiyaa iyadoo la adeegsanayo gooyo labajibbaaran. Qaabka iyo cabbirka kanaalada waxaa lagu beddeli karaa mashiinnada CNC iyagoo isticmaalaya qalab goyn oo kala duwan si ay u helaan heerarka socodka iyo sifooyinka kala duwan. Tusaale ahaan abuurista kanaalka qaabka qalloocan iyadoo la adeegsanayo qalabka 125 μm waxaa laga heli karaa shaqada Monaghan45. Marka lakabka foornada lagu dhejiyo ee dusha sare ee kanaalka ayaa yeelan doona dusha sare ee moodada. dhammayn.Shaqadan, si loo ilaaliyo summaynta kanaalka, dulmar labajibbaaran ayaa la isticmaalay.
Inta lagu jiro hakad horay loo sii qorsheeyay ee soo saarista, heerkulka heerkulbeegga (Nooca K) ayaa si toos ah ugu dhexjira aaladda u dhaxaysa kooxaha kanaalka sare iyo kan hoose (Jaantuska 1 - Marxaladda 3) Heerkulbeegyadani waxay la socon karaan isbeddelada heerkulka -200 ilaa 1350 °C.
Habka dhigista birta waxaa sameeya gees UAM ah iyadoo la isticmaalayo balac 25.4 mm ah, bir dhumucdiisuna tahay 150 micron. Lakabyadan birta ah waxay ku xidhan yihiin taxane isku xiga si ay u daboolaan dhammaan aagga dhismaha; cabbirka alaabta la shubay waa ka weyn yahay wax soo saarka kama dambaysta ah sida geeddi-socodka kala-goynta waxay soo saartaa shabagga kama dambaysta ah. Machining CNC waxaa loo isticmaalaa in lagu mashiinnada wareegga dibadda iyo gudaha ee qalabka, taasoo keentay in dhamaystirka dusha sare ee qalabka iyo kanaalada siman si ay u qalab la doortay iyo xuduudaha habka CNC (qiyaastii 1.6 μm Raashin in tusaale ahaan this). waa la ilaaliyaa oo qaybta la dhammeeyey waxay la kulmi doontaa CNC dhammayn shiidista heerarka saxnaanta.Balacda kanaalka loo isticmaalo qalabkani waa mid yar oo ku filan si loo hubiyo in walxaha foilku aanu "sageynin" kanaalka dareeraha, sidaas darteed kanaalka wuxuu ilaaliyaa qaybta wareega wareega.
Cilmi-baaristu waxay muujisay in faafitaan yar oo asal ah ay ka dhacdo UAM bonding interface 46, 47 iyada oo aan lahayn daaweyn kuleyl ah oo dheeraad ah, markaa qalabka ku jira shaqadan, lakabka Cu-110 ayaa weli ka duwan lakabka Al 6061 oo isbeddelo lama filaan ah.
Ku rakib 250 psi pre-calibrated (1724 kPa) dib u habeynta cadaadiska (BPR) ee ka soo baxa reactor-ka oo ku shub biyo iyada oo loo marayo reactor-ka heerka 0.1 ilaa 1 mL min-1. Aqoonsiga wixii farqi ah ee u dhexeeya thermocouples ee ku dhex jira reactor-ka iyo kuwa ku dhex jira saxanka kuleyliyaha FlowSyn chip.Tani waxaa lagu gaaraa iyadoo la bedelayo heerkulka barnaamijka ee u dhexeeya 100 iyo 150 °C ee 25 °C kordhinta iyo in la ogaado farqiga u dhexeeya heerkulka barnaamijka iyo diiwaanka PicoLog software.
Shuruudaha falcelinta cycloaddition ee phenylacetylene iyo iodoethane ayaa la hagaajiyay (Scheme 1- Cycloaddition of phenylacetylene iyo iodoethane Scheme 1- Cycloaddition of phenylacetylene iyo iodoethane) . hagaajintan waxaa lagu sameeyay qaab-dhismeed buuxa oo heerkul ah oo tijaabo ah (DOE) iyadoo la adeegsanayo cabbirada heerkulka waqtiga iyo qaabaynta heerkulka waqtiga. at 1:2.
Xalalka kala duwan ee sodium azide (0.25 M, 4: 1 DMF: H2O), iodoethane (0.25 M, DMF), iyo phenylacetylene (0.125 M, DMF) ayaa la diyaariyay. Maaddada bilawga ah ee phenylacetylene oo lagu go'aamiyay waxqabadka sare ee chromatography dareeraha ah (HPLC) . Si joogto ah falanqaynta, dhammaan falcelinta ayaa la qaaday wax yar ka dib markii isku-darka falcelinta ay ka tagtay reactor.
Dhammaan shaybaarrada waxaa lagu falanqeeyay iyadoo la adeegsanayo nidaamka Chromaster HPLC (VWR, PA, USA) oo ka kooban bamka afargeeska ah, foornada tiirarka, hirarka hirarka UV ee baaraha iyo autosampler. Tiirka wuxuu ahaa Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 mm ee cabbirka, 5 µm qayb ka mid ah xallinta waa 4 ° C 50:50 methanol: biyaha heerka socodka 1.5 mL.min-1.Mugga cirbaddu waxay ahayd 5 µL dhererka hirarka wax baadhana wuxuu ahaa 254 nm. The % meesha ugu sarreysa ee muunada DOE waxaa laga soo xisaabiyay meelaha ugu sarreeya ee alkyne haraaga ah iyo alaabada triazole ee la isku duro oo keliya.
Isku-dubbaridka wax soo saarka falanqaynta reactor ee software-ka MODDE DOE (Umetrics, Malmö, Sweden) waxay oggolaatay falanqayn qotodheer oo ku saabsan isbeddellada natiijooyinka iyo go'aaminta xaaladaha falcelinta ugu fiican ee cycloaddition.
oksaydhka naxaasta dusha sare ee qolka falcelinta catalytic ayaa lagu gaadhay iyadoo la adeegsanayo xal hydrogen peroxide (36%) oo ku qulqulaya qolka falcelinta (heerka socodka = 0.4 mL min-1, wakhtiga degenaanshaha = 2.5 min) ka hor inta aan la isku dhejin maktabad kasta oo ka kooban triazole.
Marka la ogaado xaaladaha ugu fiican, waxaa lagu dabaqay noocyo kala duwan oo acetylene iyo haloalkane ah si ay u oggolaadaan isku-dubarid isku-darka maktabadda yar, taas oo lagu dhisayo awoodda lagu dabaqi karo shuruudahan tiro balaadhan oo ah reagents suurtagal ah (Jaantus 1).2).
Diyaarso xalal gaar ah oo sodium azide ah (0.25 M, 4: 1 DMF: H2O), haloalkanes (0.25 M, DMF) iyo alkynes (0.125 M, DMF) .3 mL aliquots ee xal kasta ayaa la isku daray oo lagu shubay iyada oo loo marayo reactor at 75 µL.min-1 iyo 150 digrii mugga la ururiyey. mL of ethyl acetate.Xalka muunada waxaa lagu dhaqay 3 × 10 mL oo biyo ah. Lakabyada aqueous ayaa la isku daray oo laga soo saaray 10 mL ee ethyl acetate; lakabyada dabiiciga ah ayaa markaa la isku daray, lagu dhaqay 3 x 10 mL oo brine ah, la qalajiyey MgSO4 oo la sifeeyay, ka dibna dareeraha ayaa laga saaray vacuo. Shaybaarada waxaa lagu nadiifiyey chromatography column on silica gel iyadoo la isticmaalayo ethyl acetate ka hor falanqaynta isku-darka HPLC,1H NMR,13C NMR iyo mass spectrometry mass.
Dhammaan spectra-yada waxaa lagu helay iyadoo la adeegsanayo cabirka cabbirka qiyaasta Thermofischer saxda ah ee Orbitrap oo leh ESI oo ah isha ionization. Dhammaan muunadaha waxaa la diyaariyey iyadoo la isticmaalayo acetonitrile ahaan dareere ahaan.
Falanqaynta TLC waxaa lagu sameeyay taarikada silica ee aluminium-taageertay. Taarikada waxaa lagu sawiray iftiinka UV (254 nm) ama midabaynta vanillin iyo kuleylka.
Dhammaan shaybaarada waxaa lagu falanqeeyay iyadoo la adeegsanayo nidaamka VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) oo ku qalabaysan autosampler, foornada tiirarka binary bamka iyo hal mawjadda dhererka.
Cirbadaha (5 µL) ayaa si toos ah looga sameeyay isku darka falcelinta cayriin ee la qasi jiray (1:10 qasitaan) waxaana lagu falanqeeyay biyo: methanol (50:50 ama 70:30), marka laga reebo muunado qaar iyadoo la isticmaalayo 70:30 nidaamka dareeraha (oo lagu tilmaamay lambarka xiddigga) heerka socodka 1.5 mL/min. nm.
Aagga % ugu sarreeya ee muunadda waxaa laga soo xisaabiyay aagga ugu sarreeya ee alkyne haraaga, kaliya sheyga triazole, iyo duritaanka walxaha bilawga ah ayaa oggolaaday aqoonsiga meelaha ugu sarreeya.
Dhammaan shaybaarrada waxaa lagu falanqeeyay iyadoo la adeegsanayo Thermo iCAP 6000 ICP-OES. Dhammaan heerarka cabbirka ayaa la diyaariyey iyadoo la adeegsanayo 1000 ppm Cu heerka caadiga ah ee 2% nitric acid (SPEX Certi Prep).
UAM waxay isticmaashaa alxanka birta ultrasonic sida farsamada isku dhafka ah ee walxaha birta ah ee loo isticmaalo in lagu dhiso shirka ugu dambeeya. Alxanka birta Ultrasonic waxay isticmaashaa qalab bir ah oo gariiraya (oo loo yaqaan gees ama gees ultrasonic) si loo cadaadiyo lakabka bireed / hore loo xoojiyay si loogu xiro iyadoo la gariirayo walxaha. Wixii qalliin joogto ah, sonotrode iyo aagga cylin-ka ee dulsaarka ayaa ka sarreeya. iyo gariirka ayaa la mariyaa, oksaydhyada dusha sare ee maaddadu way dillaaci kartaa. Cadaadiska joogtada ah iyo gariirku waxay sababi karaan asperities walxaha si ay u burburaan 36. waxa kale oo ay ka caawin kartaa adhesion iyada oo loo marayo isbeddel ku yimaada tamarta dusha sare48.Dabeecadda habka isku-xidhka ayaa ka soo kabanaya dhibaatooyin badan oo la xidhiidha heerkulka dhalaalka doorsooma iyo heerkulka sare ee saamaynta ka dib ee lagu xusay farsamooyinka kale ee wax-soo-saarka.
Qodobka labaad ee wanaagsan ee UAM waa heerka sare ee qulqulka caagga ah ee lagu arkay qalabka macdan, xitaa heerkulka hooseeya, ie si fiican uga hooseeya barta dhalaalaysa ee alaabta macdan ah. Isku-dhafka ultrasonic oscillation iyo cadaadiska waxay keenaysaa heerar sare oo ka mid ah socdaalka xadka hadhuudhka maxalliga ah iyo recrystallization iyada oo aan korodhka heerkulka ballaaran ee dhaqan ahaan la xidhiidha qalabka bulk.Inta lagu jiro dhismaha shirka kama dambaysta ah, taas oo ka dhigaysa lakabka firfircoon ee u dhexeeya qaybaha ugu dambeeya iyo walxaha qarxa. biraha birta ah, lakabka lakabka. Qaybaha sida fiilooyinka indhaha 49, xoojinta 46, elektaroonigga 50, iyo thermocouples (shaqadan) ayaa dhamaantood si guul leh loogu dhejiyay qaababka UAM si loo abuuro ururo firfircoon oo firfircoon.
Shaqadan, labada isku xidhka walxaha kala duwan iyo fursadaha isdhexgalka ee UAM ayaa loo isticmaalay si loo abuuro microreactor-ka ilaalinta heerkulka ugu dambeeya.
Marka la barbardhigo palladium (Pd) iyo biraha kale ee sida caadiga ah loo isticmaalo, Cu-catalysis waxay leedahay faa'iidooyin dhowr ah: (i) Dhaqaale ahaan, Cu wuu ka qaalisan yahay biraha kale ee badan ee loo isticmaalo catalysis sidaas darteedna waa ikhtiyaar soo jiidasho leh warshadaha farsamaynta kiimikada Dareen-celinta Cu-catalyzed waxay si fiican u shaqeysaa maqnaanshaha ligands kale, Isku-dhafkan ayaa badanaa qaab-dhismeed ahaan fudud oo aan qaali ahayn haddii la rabo, halka kuwa loo isticmaalo Pd chemistry ay inta badan yihiin kuwo adag, qaali ah, iyo hawo-xasaasi ah (iv) Cu, gaar ahaan loo yaqaan awoodda ay ku xirto alkynes in synthesis, Tusaale ahaan, bimetallic-catalyzed Sonogazirazid. (v)Cu waxa kale oo uu awoodaa in uu kor u qaado xuubka dhawrka nucleophiles ee falcelinta nooca Ullmann.
Tusaalooyinka heterogenization ee dhammaan falcelintan ayaa dhawaan lagu muujiyay joogitaanka Cu (0) Tani waxay inta badan sabab u tahay warshadaha dawooyinka iyo diiradda sii kordheysa ee soo kabashada birta birta iyo dib u isticmaalida55,56.
Horudhac by Huisgen ee 1960s57, falcelinta 1,3-dipolar cycloaddition u dhexeeya acetylene iyo azide in 1,2,3-triazole waxaa loo arkaa falcelinta synergistic.
Dareen-celintani waxay soo gashay mar kale markii Sharpless iyo kuwa kale ay soo bandhigeen fikradda "click chemistry" 59. Ereyga "click chemistry" waxaa loo isticmaalaa in lagu qeexo falcelin adag, la isku halleyn karo oo la doortay oo loogu talagalay isku dhafka degdegga ah ee xeryahooda cusub iyo maktabadaha isku-dhafka ah iyada oo loo marayo heteroatom linkage (CXC) kala goyntu waa sahal61.
Huisgen 1,3-dipole cycloaddition qadiimiga ah kama mid aha qaybta "click chemistry" Si kastaba ha ahaatee, Medal iyo Sharpless ayaa muujiyay in dhacdadan azide-alkyne ee isku dhafka ah ay ku socoto 107 ilaa 108 iyada oo ay joogaan Cu (I) marka la barbar dhigo 1,3-dipolar cycloaddition, falcelinta 6-aad ee muhiimka ah. Uma baahna kooxaha ilaalinta ama xaaladaha falcelinta qallafsan iyo wax-soo-saarka u dhow beddelaad dhammaystiran iyo xulashada 1,4-lagu khilaafay 1,2,3-triazoles (anti- 1,2,3-triazole) ee qiyaasta wakhtiga (Jaantuska 3).
Natiijooyinka isometric ee huisgen cycloadditions ee caadiga ah iyo copper-catalyzed Huisgen.
Nidaamyada intooda badani waxay ku lug leeyihiin hoos u dhigista ilaha Cu(II), sida hoos u dhigista noocyada CuSO4 ama Cu(II)/Cu(0) oo la isku darayo cusbada sodium.
Kinetic iyo daraasadaha calaamadaynta isotopic ee Worrell et al. 65 waxay muujisay in, marka laga hadlayo alkynes terminal, laba u dhigma oo naxaas ah ayaa ku lug leh kicinta reactivity ee molecule kasta oo ku wajahan azide. Habka la soo jeediyay wuxuu ka soo baxaa giraan bir ah oo lix xubnood ah oo ay sameeyeen iskudubarid azide ilaa σ-bonded copper acetylide oo leh π-bonded copper iyo naxaas la sameeyay sida ku-deeqaha naxaas ah hoos u dhac, oo ay ku xigto proton-ka-soo-noqoshada si loo bixiyo alaabada triazole oo loo xiro wareegga catalytic.
Iyadoo faa'iidooyinka qalabka kiimikada socodka si fiican loo diiwaangeliyay, waxaa jiray rabitaan ah in lagu dhex daro qalabka falanqaynta ee nidaamyadan loogu talagalay in-line, goobta, kormeerka habka66,67.UAM waxay caddeeyeen in ay tahay hab ku habboon naqshadeynta iyo soo saarista qulqulo qulqulaya 3D oo aad u adag oo ka samaysan qalab firfircoon oo firfircoon, qalab kuleyl leh oo leh walxo dareemeed oo toos ah.
Aluminium-naxaasta qulqulka dareeraha ee ay farsamaysay soo-saarka wax-soo-saarka ultrasonic (UAM) oo leh qaab-dhismeedka kanaalka gudaha ee kakan, heerkulbeegyo-ku-xidhan iyo qolka falcelinta kicinta.
Si loo hubiyo in reactors-ku loo sameeyay fal-celinta dabiiciga ah ee mustaqbalka, dareerayaasha waxay u baahan yihiin in si badbaado leh loogu kululeeyo meel ka sarreysa barta karkarinta; waxay yihiin cadaadis iyo heerkul la tijaabiyey. Tijaabada cadaadiska ayaa muujisay in nidaamku uu hayo cadaadis joogto ah oo joogto ah xitaa iyadoo la kordhinayo cadaadiska nidaamka (1.7 MPa) . Tijaabada hydrostatic waxaa lagu sameeyay heerkulka qolka iyadoo la adeegsanayo H2O sida dareeraha.
Isku xirka heerkulbeegga ku dhex jira (Jaantuska 1) heerkulbeegga xogta heerkulka ayaa muujisay in heerkulbeeggu uu ahaa 6 °C (± 1 ° C) qabow marka loo eego heerkulka barnaamijka ee nidaamka FlowSyn. Caadi ahaan, kororka 10 ° C ee heerkulka natiijada labanlaabida heerka falcelinta, markaa farqiga heerkulka ee kaliya dhowr darajo ayaa si weyn u beddeli kara heerka celceliska heerkulka sare ee heerka celceliska heerkulka sare. diffusivity kulaylka ee alaabta loo isticmaalo in habka wax soo saarka.Tani kulaylku waa joogto ah oo sidaas daraaddeed waxaa lagu xisaabin karaa in Mudanayaasha qalabka si loo hubiyo in heerkulka saxda ah la gaarey oo lagu qiyaaso inta lagu guda jiro reaction.Sidaas darteed, this qalab la socodka online fududeeyaa xakamaynta adag ee heerkulka falcelinta iyo fududeeyo hab sax ah u habaynta iyo horumarinta xaaladaha ugu fiicnayn.These dareemayaal ayaa sidoo kale loo isticmaali karaa si ay u aqoonsadaan in reactions ka baxsan.
Reactor-ka lagu soo bandhigay shaqadan ayaa ah tusaalaha ugu horreeya ee codsiga tikniyoolajiyada UAM ee soo saarista reactors kiimikaad iyo wax ka qabashada dhowr xaddidaad oo waaweyn oo hadda la xidhiidha daabacaadda AM / 3D ee qalabkan, sida: (i) ka gudubka dhibaatooyinka la soo sheegay ee la xidhiidha naxaasta ama aluminiumka aluminiumka (ii) hagaajinta xalinta kanaalka gudaha marka la barbar dhigo isku-dhafka sariirta sariirta (PBF) farsamooyin kala duwan oo ka mid ah muraayadda sariirta sariirta (PBF) 6 farsamooyin dhalaalid ah oo dusha sare ah, 6, farsamada PoLM 2 iyo 6. (iii) Heerkulka habaynta oo la dhimay, kaas oo fududeeya isku xidhka tooska ah ee dareemayaasha, taas oo aan suurtagal ahayn tignoolajiyada sariirta budada ah, (v) waxay ka adkaataa sifooyinka farsamaysan ee liita iyo dareenka qaybaha polymer-ku-salaysan ee noocyo kala duwan oo dareeraha dabiiciga ah ee caadiga ah17,19.
shaqeynta reactor waxaa lagu muujiyay taxane ah naxaas-catalyzed alkyne azide cycloaddition reactions hoos xaaladaha socodka joogtada ah (Jaantus. 2) .The ultrasonic-daabacan naxaasta naxaas tafatiran ee Jaantuska 4 ayaa la dhexgaliyay nidaamka socodka ganacsiga oo loo isticmaalo in synthesize azides maktabadda kala duwan 1,4-disubstituted 1,2,3-lenides heerkulka falcelinta ee 1,2,3-leenedes heerkulka a joogitaanka sodium chloride (Jaantus 3) .Isticmaalka habka socodka joogtada ah wuxuu yareeyaa welwelka nabdoonaanta ee ka dhalan kara hababka dufcada, maaddaama falcelintani ay soo saarto dhexdhexaadin azide ah oo aad u firfircoon oo khatar ah [317], [318] . Markii hore, falcelinta waxaa loo hagaajiyay cycloaddition ee phenylacetylene iyo iodoethnyloadition of phenylacetylene iyo chromeloadition -Chylene iodoethane) (fiiri sawirka 5).
(Bidix sare) Jadwalka habaynta loo isticmaalo in lagu daro reactor 3DP nidaamka socodka (midig sare) ee laga helay nidaamka la wanaajiyey (hoose) ee nidaamka Huisgen cycloaddition 57 ee u dhexeeya phenylacetylene iyo iodoethane si kor loogu qaado loona muujiyo cabbirada la wanaajiyey heerka beddelka falcelinta.
Iyada oo la xakameynayo wakhtiga degenaanshaha reagents ee qaybta kicinta ee reactor iyo si dhow loola socdo heerkulka falcelinta oo leh baaritaan heerkulbeeg toos ah oo isku dhafan, xaaladaha falcelinta waxaa lagu hagaajin karaa si dhakhso ah oo sax ah iyadoo la raacayo waqtiga ugu yar iyo isticmaalka alaabta. Waxaa loo tixgeliyaa shuruudaha moodeelka ah ee muhiimka ah. Ku socodsiinta hagaajinta ku dhex jirta iyadoo la adeegsanayo ereyadan la doortay waxay soo saartaa shuruudo falcelin ah oo loogu talagalay in lagu kordhiyo aagagga ugu sarreeya ee alaabta iyada oo la dhimayo bilawga aagagga ugu sarreeya ee alaabta. Hagaajintani waxay keentay beddelka 53% ee badeecada triazole, taas oo si dhow ula mid ah saadaasha moodeelka ee 54%.
Iyada oo ku saleysan suugaanta muujinaysa in copper (I) oxide (Cu2O) u dhaqmi karaa sida nooc katalytic wax ku ool ah on eber-valent copper dusha falcelin kuwan, awoodda pre-oxidize dusha reactor ka hor inta fulinta falcelinta ee socodka ayaa la baadhay70,71. Falcelinta ka dhexeeya phenylacetylene iyo iodoethane ayaa ka dibna la sameeyey mar kale hoos u diyaarin xaaladaha wanaagsan iyo waxa la arkay in natiijada la barbar dhigo heerka ugu fiican. Beddelka alaabta bilawga ah, taas oo loo xisaabiyay inay noqoto> 99% . Si kastaba ha ahaatee, la socodka HPLC ayaa muujisay in isbeddelkani uu si weyn u yareeyey wakhtiga falcelinta aadka u dheer ee dheeraadka ah ilaa qiyaastii 90 daqiiqo, halkaas oo hawshu u muuqatay inay la siman tahay oo ay gaarto "xaalad joogto ah" . Kormeerkan ayaa soo jeedinaya in isha dhaqdhaqaaqa catalytic laga helo oksaydhka dusha sare ee naxaasta halkii ay ka ahaan lahayd eber-valent ee heerkulka qolka Cusbooneysii kuwaas oo aan ahayn lakabyo is ilaalinaya