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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 dareenka. 1,4-lagu khilaafay xeryahooda 1,2,3-triazole ayaa si guul leh loo farsameeyay oo loo hagaajiyay Cu-mediated Huisgen 1,3-dipolar cycloaddition reaction iyadoo la adeegsanayo 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 ee kooxaha raadinaya inay beddelaan qalabka muraayadaha dhaqameed ama qulqulka qalabka kiimikada ee wax-soo-saarka wax-soo-saarka wax-soo-saarka (AM) ee kiimikada "weelasha falcelinta"8. Naqshadeynta celceliska, wax soo saarka degdegga ah, iyo 3-cabbirka (3D) ee farsamooyinkan ayaa faa'iido u leh kuwa doonaya in ay qalabeeyaan qalabkooda si gaar ah oo loogu talagalay falcelinta, qalabka, farsamada ama shuruudaha shaqada ee 3 ayaa diiradda saaraya isticmaalka qalabka. sida stereolithography (SL) 9,10,11, fused deposition modeling (FDM) 8,12,13,14 iyo inkjet printing 7, 15, 16. La'aanta adkeyd iyo kartida qalabkan oo kale ah si ay u sameeyaan tiro balaadhan oo ah falcelin kiimikaad / falanqayn17, 18, 19, 20 ee baaxadda weyn AM 1, 1 ee baaxadda weyn ee AM, 1, 20 ee baaxadda weyn. 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 awood 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 ee AM ee farsamada hybri, kaas oo si toos ah loo garan karo in wax soo saarka kale ee AM-. situ periodic computer numerical control (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 haraaga ah ee kanaalka dareeraha yar yar, taas oo inta badan ah kiiska budada iyo dareeraha AM Systems26,27,28.Xriyadda naqshadeynta Tani waxay sidoo kale u fidisaa habka isku-dhafka ah ee UAM. doorashada isku-dhafka walxaha ka baxsan habka dhalaalidda macnaheedu waa in baahida farsamo iyo kiimikaad ee codsiyada gaarka ah si fiican loo dabooli karo.In marka lagu daro isku xidhka gobolka adag, ifafaale kale oo la kulmay inta lagu guda jiro isku xidhka ultrasonic waa socodka sare ee alaabta caag ah ee heerkulka xad hoose29,30,31,32,33.This feature gaar ah ee UAM fududayn kara cudad ee xubno farsamo / kulaylka u dhexeeya qalabka dareemaha ka mid ah lakabka waqtiga dhabta ah ee UAM fududayn karaa in la dhexgeliyo qalabka wax lagu dhejiyo ee qalabka waqtiga dhabta ah. tics
Shaqaaqadii hore ee qorayaashu32 waxay muujisay awooda habka UAM si ay u abuurto qaab dhismeedka 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 darida dareemayaasha kulaylka si toos ah inta u dhaxaysa durdurrada reagent ee saxda ah ee kormeerka heerkulka falcelinta iyo xakamaynta. Si loo muujiyo shaqeynta reactor, maktabadda 1,4-farmaceutically muhiim ah xeryahooda 1,2,3-triazole waxaa lagu falanqeeyay by copper-catalyzed Huisgen 1,3-dipolar-katalyized Huisgen 1,3-dipolar-ka-faa'iidaysiga fursadaha horumarinta sayniska iyo farsamada casriga ah. suurtagalnimada kimistari iyada oo loo marayo cilmi-baarisyo 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. CD3)
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 110 iyo Al 6061.Cu-110 waxay leedahay maaddo naxaas ah oo sarreeya (ugu yaraan 99.9% copper), taasoo ka dhigaysa musharax wanaagsan oo loogu talagalay falcelinta naxaasta-catalyzed, oo sidaas darteed loo isticmaalo sida "lakabka firfircoon ee microreactor.Al 6061 O waxaa loo isticmaalaa sida walxo "badan", sidoo kale lakabka dhejinta ee loo isticmaalo falanqaynta;Qaybta kaalmaynta Aloy ee ku-xidhka iyo xaalad la jeexjeexay oo lagu daray lakabka Cu-110.Al 6061 O waa walxo la muujiyey inay si heer sare ah ula jaan qaadayaan hababka UAM38, 39, 40, 41 oo la tijaabiyey lana ogaaday inay kiimiko ahaan degan yihiin reagen-yaasha loo isticmaalo shaqadan.Isku-darka Al 6061 O iyo Cu-110 ayaa sidoo kale loo arkaa inay yihiin walxo isku-dhafan oo loogu talagalay UAM oo markaa waa walxo ku habboon daraasaddan.38,42 Qalabkani waxa ay ku taxan yihiin shaxda 1 ee hoose.
Marxaladaha samaynta reactor (1) Al 6061 substrate (2) Samaynta kanaalka hoose oo loo dejiyay foornada naxaasta ah (3) Isku-xidhka heerkulbeegyada inta u dhaxaysa lakabyada (4) Kanaalka sare (5) Gelida iyo meelaha laga baxo (6) fal-celiyeyaasha monolithic.
Falsafada naqshadeynta ee dariiqa dareeraha waa in la isticmaalo dariiq isku dhafan si loo kordhiyo dareeraha masaafada u socdaalaya gudaha chip-ka, iyada oo la ilaalinayo jajabka cabbirka la maareyn karo. Kordhinta fogaantani waa mid la jecel yahay si loo kordhiyo wakhtiga isdhexgalka kicinta / reagent iyo bixinta wax soo saarka alaabta wanaagsan. taas oo lagu gaari karo, design reactor qoreysa laba reagent inlets oo la isku daray at Y-goyska ka hor inta aan la gelin qaybta isku dhafka serpentine. The saddexaad ee dhexda, kaas oo dhexda durdurka kala bar iyada oo ay degan tahay, waxaa lagu daray in design mustaqbalka falcelin multistep.
Dhammaan kanaalada waxay leeyihiin muuqaal labajibbaaran (aan lahayn xaglo qabyo ah), natiijada warshadaynta CNC ee xilliyeed loo isticmaalo si loo abuuro joomatari kanaalka. Cabbirka kanaalka ayaa la doortay si loo hubiyo wax soo saarka mugga sare (loogu talagalay microreactor), iyadoo yar oo ku filan si loo fududeeyo isdhexgalka dusha sare (catalysts) ee inta badan dareerayaasha ka kooban. µm iyo guud ahaan mugga reactor-ku wuxuu ahaa 1 ml. Isku-xidhaha isku-dhafan (1/4″—28 dun UNF) ayaa lagu soo daray naqshadaynta si loogu oggolaado is-dhexgalka 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 isticmaalayo gooyo labajibbaaran. Qaabka iyo cabbirka kanaalada waxaa lagu beddeli karaa mashiinnada CNC iyagoo isticmaalaya qalab kala duwan oo goyn ah si ay u helaan heerarka socodka iyo sifooyinka kala duwan. Tusaale ahaan abuurista kanaalka qaabka qalooca iyadoo la adeegsanayo qalabka 125 μm waxaa laga heli karaa shaqada Monaghan45. Marka lakabka foornada lagu dhejiyo in ka badan kanaalka shaqada, wuxuu ku dhammeeyaa kanaalka dabaqa ah. 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 soo saartaa shabagga kama dambaysta ah. Machining CNC waxaa loo isticmaalaa in lagu mishiinka contours dibadda iyo gudaha ee qalabka, taasoo keentay in dhammayn dusha sare ee qalabka iyo channels siman si ay u qalab la doortay iyo xuduudaha habka CNC (qiyaastii 1.6 μm Raashin tusaale ahaan this tusaale ahaan). Qaybta la dhammeeyey waxay la kulmi doontaa CNC dhammayn shiidista heerarka saxnaanta.Balac kanaalka loo isticmaalo qalabkani waa mid yar oo ku filan si loo hubiyo in walxaha foilku aanu "sageynin" kanaalka dareeraha, sidaas darteed kanaalka ayaa ilaalinaya qaybta isku-tallaabta ee labajibaaran.
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 a pre-calibrated 250 psi (1724 kPa) dib-u-habaynta 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. Heerkulbeegyada ku dhex jira reactor-ka iyo kuwa ku dhex jira saxanka kuleyliyaha FlowSyn chip. Tan waxaa lagu gaaraa iyadoo la beddelayo heerkulka kululaynta barnaamijka ee u dhexeeya 100 iyo 150 ° C ee 25 ° C kordhinta iyo in la ogaado wixii farqi ah ee u dhexeeya heerkulka barnaamijka iyo la duubay
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 buuxa oo heerkul ah oo tijaabo ah (DOE) iyadoo la adeegsanayo cabbirada heerkulka 1 ee tijaabooyinka (DOE) iyadoo la adeegsanayo cabbirada heerkulka 1 ee waqtiga. .
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 diyaariyey. waxaana lagu go'aamiyay chromatography dareeraha waxqabadka sare leh (HPLC)
Dhammaan shaybaarada waxaa lagu falanqeeyay iyadoo la isticmaalayo Chromaster HPLC nidaamka (VWR, PA, USA) oo ka kooban bam afargeesle ah, foornada column, variable wavelength UV detector iyo autosampler.Tiirku waxa uu ahaa Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 mm in size, 5 µm ol:biyo xadiga socodka 1.5 mL.min-1.Mugga cirbadadu waxa ay ahayd 5µL dhererka hirarka wax baadhana waxa uu ahaa 254nm
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 150. 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 nadiifiyay chromatography column on silica gel iyadoo la isticmaalayo ethyl acetate ka hor falanqaynta isku-darka HPLC,1H NMR,13C NMR iyo mass spectrometry mass HR).
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.
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-xidhka alaabta 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 / horay loo xoojiyay lakabka si loo xidho iyadoo la gariirayo walxaha. Wixii hawlgal joogto ah, sonotrode iyo gariirka dusha sare ee cylinka ayaa lagu dabaqaa xayndaabka. Cadaadiska joogtada ah iyo gariirku waxay sababi karaan asperities walxaha inay burburaanwaxa 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 dhalaalka ee qalabka birta ah ee isku dhafka ultrasonic oscillation iyo cadaadiska waxay keenaysaa heerar sare oo ka mid ah socdaalka xuduudka 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, phenomenon lakabka firfircoon ee u dhexeeya qaybaha birta ah ee phenomented, lakabka firfircoon ee u dhexeeya qaybaha birta ah ee phenomented ayaa dhaafi kara. Qaybaha lakabka. Qaybaha sida fiilooyinka indhaha 49, xoojinta 46, elektarooniga 50, iyo thermocouples (shaqadan) dhamaantood si guul leh ayaa loogu dhejiyay qaababka UAM si loo abuuro ururo isku dhafan oo 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 doorasho soo jiidasho leh warshadaha farsamaynta kiimikada Si fiican u maqnaanshaha ligands kale, Xirmooyinkani waxay inta badan yihiin qaab-dhismeed fudud oo aan qaali ahayn haddii la rabo, halka kuwa loo isticmaalo Pd chemistry ay inta badan yihiin kuwo adag, qaali ah, iyo hawada-xasaasi ah (iv) Cu, gaar ahaan loo yaqaan awoodda ay u leedahay in ay xirto alkynes in synthesis, Tusaale ahaan, bimetallic-catalyzed Sonogashira coupling with chemistry) sidoo kale waxay kor u qaadi kartaa isku-xirnaanta ee dhowr nucleophiles oo ku jira 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 xushay oo loogu talagalay isku-dhafka degdegga ah ee xeryahooda cusub iyo maktabadaha isku-dhafka ah iyada oo loo marayo isku xirka heteroatom (CXC) 1.
Huisgen 1,3-dipole cycloaddition ee classical 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 iyadoo ay joogaan Cu (I) marka la barbar dhigo 1,3-dipolar cycloaddition aan la hagaajin karin, kooxuhu waxay u baahan yihiin falcelin muhiim ah. ama xaaladaha falcelin adag iyo wax-soo-saar ku 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 falcelinta 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 ah oo lagu dhejiyay naxaas ah oo ay ku deeqeen shriyange proton qudhunka si ay u bixiso triazole alaabta iyo xidho 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 ku dhejinta (Jaantuska 1) heerkulbeegga 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 kala duwanaanshaha heerkulka ee kaliya dhowr darajo ayaa si weyn u beddeli kara heerka heerkulka sare usivity ee alaabta loo isticmaalo in habka wax soo saarka.Taasi kuleylku waa mid joogto ah oo sidaas daraaddeed loo xisaabin karaa in Mudanayaasha qalabka si loo hubiyo in heerkulka saxda ah waxaa la gaaray oo lagu qiyaaso inta lagu guda jiro reaction.Sidaas darteed, this qalab la socodka online fududeeyaa xakamaynta dhagan heerkulka falcelinta iyo fududeeyaa habayn sax ah oo dheeraad ah habaynta iyo horumarinta xaaladaha ugu fiicnayn.
Reactor-ka lagu soo bandhigay shaqadan ayaa ah tusaalaha ugu horreeya ee codsiga tignoolajiyada UAM ee soo saarista reactors kiimikaad waxayna wax ka qabataa 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 farsamaynta (ii) hagaajinta xalinta kanaalka gudaha marka la barbar dhigo isku-dhafka sariirta sariirta (PBF) farsamooyin kala duwan oo ka mid ah fayruuska sariirta sariirta (PBF) 6 farsamooyin dhalaalid leysarka 6 (SLM 6) heerkulka processing ducay, kaas oo fududeeyaa xidhidhka tooska ah ee dareemayaasha, taas oo aan suurto gal in technology sariirta budada, (v) ka adkaan sifooyinka farsamo liidata iyo dareenka qaybaha polymer-ku salaysan in noocyo kala duwan oo dareere organic caadiga ah17,19.
Shaqada ka-faa'iideysiga ayaa waxaa muujiyay taxane ah oo ah falcelin alkynne oo ka kooban alkynne oo ka kooban Cyclomdod oo ay ku jiraan xaaladaha socodka joogtada ah ee loo yaqaan 'Pip'. Alkakyl koontaallada ayaa ka goynaya jiritaanka sodium chloride (Jaantus 3) Lacetylne iyo Iodoethane) (eeg Jaantus 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 loo hagaajin karaa si dhakhso ah oo sax ah iyadoo la raacayo waqtiga ugu yar iyo isticmaalka alaabta. Ku shaqaynta hagaajinta ku dhex jirta iyada oo 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, kaas oo si dhow ula jaan qaadaya 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 u dhaxaysa phenylacetylene iyo iodoethane ayaa ka dibna lagu sameeyay mar kale hoos u dhigista ugu wanaagsan ee natiijada la arkay iyadoo la eegayo natiijada ugu wanaagsan ee la barbardhigay. Maaddada, taas oo lagu xisaabiyey inay tahay> 99% . Si kastaba ha ahaatee, la socodka HPLC ayaa muujisay in beddeliddani si weyn u yaraysay wakhtiga falcelinta aadka u dheer ee dheeraadka ah ilaa ku dhawaad ​​90 daqiiqo, ka dibna hawshu waxay u muuqatay inay la siman tahay oo ay gaarto "xaalad joogto ah" . Kormeerkani waxa uu soo jeedinayaa in isha dhaqdhaqaaqa catalytic laga helo oogada sare ee oksaydhka halkii ay eber-valent naxaas ah substrate-Cu si fudud u samaysan yahay lakabka cufan. Tani waxay meesha ka saaraysaa baahida loo qabo in lagu daro ilo naxaas ah (II) ee co-composition71.