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Ukukhiqiza okungeziwe kushintsha indlela abacwaningi nosozimboni abaklama futhi benze ngayo izinto zamakhemikhali ukuze zihlangabezane nezidingo zabo ezithile.Kuleli phepha, sibika isibonelo sokuqala se-reactor egelezayo eyenziwe yi-ultrasonic additive manufacturer (UAM) lamination yeshidi lensimbi eliqinile elinezingxenye ze-catalytic ezididiyelwe nezici zokuzwa.Ubuchwepheshe be-UAM abudluli nje kuphela imikhawulo eminingi okwamanje ehlobene nokukhiqizwa okungeziwe kwama-reactor amakhemikhali, kodwa futhi bakhulisa kakhulu amandla anjalo madivayisi.Inani lezinhlanganisela ezibalulekile zebhayoloji ze-1,4-disubstituted 1,2,3-triazole zenziwe ngempumelelo futhi zalungiswa nge-Cu-mediated 1,3-dipolar Huisgen cycloaddition reaction kusetshenziswa indawo yekhemistri ye-UAM.Isebenzisa izici ezihlukile ze-UAM nokucubungula ukugeleza okuqhubekayo, idivayisi iyakwazi ukugqugquzela ukusabela okuqhubekayo futhi inikeze impendulo yesikhathi sangempela ukuze igade futhi ilungiselele ukusabela.
Ngenxa yezinzuzo zayo ezibalulekile ngaphezu kozakwabo abayinqwaba, ikhemistri egelezayo iyinkambu ebalulekile nekhulayo kuzo zombili izilungiselelo zezemfundo nezimboni ngenxa yekhono layo lokukhulisa ukukhetha nokusebenza kahle kokuhlanganiswa kwamakhemikhali.Lokhu kusuka ekwakhekeni kwama- molecule ezinto eziphilayo alula1 kuye kwezinhlanganisela zemithi2,3 kanye nemikhiqizo yemvelo4,5,6.Ngaphezulu kwamaphesenti angama-50 wokusabela ezimbonini ezinhle zamakhemikhali nezemithi zingazuza ekugelezeni okuqhubekayo7.
Eminyakeni yamuva nje, kuye kwaba nomkhuba okhulayo wamaqembu afuna ukufaka esikhundleni sezinto zengilazi zendabuko noma imishini yamakhemikhali agelezayo ngamakhemikhali “amareactor”8 aguquguqukayo.Idizayini ephindaphindayo, ukukhiqiza okusheshayo, namandla-ntathu (3D) walezi zindlela awusizo kulabo abafuna ukwenza ngendlela oyifisayo amadivayisi abo ngesethi ethile yokusabela, amadivayisi, noma izimo.Kuze kube manje, lo msebenzi ugxile cishe ngokukhethekile ekusetshenzisweni kwezindlela zokuphrinta ze-3D ezisekelwe ku-polymer njenge-stereolithography (SL)9,10,11, i-Fused Deposition Modeling (FDM)8,12,13,14 kanye ne-inkjet printing7,15., 16. Ukuntuleka kokwethenjelwa kanye nekhono lamathuluzi anjalo okwenza uhla olubanzi lokusabela/ukuhlaziya amakhemikhali17, 18, 19, 20 kuyisici esikhulu esikhawulela ukusetshenziswa okubanzi kwe-AM kulo mkhakha17, 18, 19, 20.
Ngenxa yokusetshenziswa okwandayo kwekhemikhali yokugeleza kanye nezakhiwo ezithandekayo ezihlobene ne-AM, izindlela ezingcono kakhulu zidinga ukucutshungulwa ezizovumela abasebenzisi ukuthi bakhe imikhumbi yokusabela kokugeleza ngamandla athuthukisiwe wekhemistri namandla okuhlaziya.Lezi zindlela kufanele zivumele abasebenzisi ukuthi bakhethe kubange lamandla aphezulu noma izinto ezisebenzayo ezikwazi ukusebenza ngaphansi kwezimo ezibanzi zokusabela, kanye nokwenza kube lula izinhlobo ezihlukahlukene zokuphuma kokuhlaziya kusukela kudivayisi ukuze kunikwe amandla ukuqapha nokulawula ukusabela.
Inqubo eyodwa yokukhiqiza engezayo engasetshenziswa ukuthuthukisa ama-reactor amakhemikhali angokwezifiso i-Ultrasonic Additive Manufacturing (UAM).Le ndlela ye-solid-state lamination yeshidi isebenzisa ukudlidliza kwe-ultrasonic kumafoil ensimbi amancane ukuze ahlanganiswe ndawonye ungqimba ngongqimba olunokushisa okuncane kwevolumu kanye nezinga eliphakeme lokugeleza kwepulasitiki 21, 22, 23. Ngokungafani nobunye ubuchwepheshe obuningi be-AM, i-UAM ingahlanganiswa ngokuqondile nokukhiqizwa okuncishisiwe, okwaziwa ngokuthi inqubo yokukhiqiza eyingxube, lapho ngezikhathi ezithile endaweni endaweni inquma ukulawulwa kwezinombolo ze-net2, ungqimba oluhlanganisiwe lwe-CNC) 25. Lokhu kusho ukuthi umsebenzisi akakhawulelwe ezinkingeni ezihambisana nokususwa kwezinto zokwakha eziyinsalela eziteshini ezincane eziwuketshezi, okuvamise ukuba njalo ezinhlelweni eziyimpuphu neziwuketshezi AM26,27,28.Le nkululeko yokuklama iphinde idlulele ekukhethweni kwezinto ezitholakalayo - i-UAM ingahlanganisa inhlanganisela yezinto ezifanayo ezishisayo nezingafani esinyathelweni esisodwa senqubo.Ukukhethwa kwenhlanganisela yezinto ezibonakalayo ngale kwenqubo yokuncibilika kusho ukuthi izidingo zemishini nezamakhemikhali zezicelo ezithile zingahlangatshezwana kangcono.Ngaphezu kokuhlanganiswa okuqinile, enye into eyenzekayo nge-ultrasonic bonding i-fluidity ephezulu yezinto zepulasitiki emazingeni okushisa aphansi kakhulu29,30,31,32,33.Lesi sici esiyingqayizivele se-UAM sivumela izakhi zemishini/ezishisayo ukuthi zibekwe phakathi kwezingqimba zensimbi ngaphandle kokulimala.Izinzwa ze-UAM ezishumekiwe zingasiza ukulethwa kolwazi lwesikhathi sangempela kusuka kudivayisi kuya kumsebenzisi ngezibalo ezihlanganisiwe.
Umsebenzi wangaphambilini wababhali32 ubonise ikhono lenqubo ye-UAM yokwakha izakhiwo ze-3D microfluidic metallic ezinamandla okuzwa ashumekiwe.Le divayisi ngeyezinjongo zokuqapha kuphela.Lesi sihloko sethula isibonelo sokuqala se-microfluidic chemical reactor ekhiqizwa i-UAM, idivayisi esebenzayo engagcini nje ngokulawula kodwa futhi engenisa ukuhlanganiswa kwamakhemikhali ngezinto ezikhuthazayo ezididiyelwe.Idivayisi ihlanganisa izinzuzo eziningana ezihlotshaniswa nobuchwepheshe be-UAM ekwenziweni kwamadivayisi amakhemikhali e-3D, njengalokhu: ikhono lokuguqula umklamo ophelele we-3D ngokuqondile usuka kumodeli osizwa yikhompyutha (CAD) ube umkhiqizo;ukwakhiwa kwezinto eziningi ngenhlanganisela ye-thermal conductivity ephezulu kanye nezinto ze-catalytic, kanye nezinzwa ezishisayo ezishumekwe ngokuqondile phakathi kwemifudlana esabelayo ukuze kulawulwe ngokuqondile nokuphathwa kwezinga lokushisa lokusabela.Ukubonisa ukusebenza kwe-reactor, umtapo wolwazi wezinhlanganisela ezibaluleke ngokwemithi ze-1,4-disubstituted 1,2,3-triazole zahlanganiswa yi-copper-catalyzed 1,3-dipolar Huisgen cycloaddition.Lo msebenzi ugqamisa ukuthi ukusetshenziswa kwesayensi yezinto zokwakha kanye nomklamo osizwa ngekhompiyutha kungavula kanjani amathuba amasha namathuba ekhemistri ngocwaningo lwemikhakha eyahlukene.
Wonke ama-solvents nama-reagents athengwe kwa-Sigma-Aldrich, Alfa Aesar, TCI, noma i-Fischer Scientific futhi asetshenziswa ngaphandle kokuhlanzwa kwangaphambili.I-spectra ye-1H ne-13C NMR erekhodwe ku-400 kanye no-100 MHz, ngokulandelanayo, itholwe ku-JEOL ECS-400 400 MHz spectrometer noma i-Bruker Avance II 400 MHz spectrometer ene-CDCl3 noma (CD3)2SO njengesixazululi.Konke ukusabela kwenziwa kusetshenziswa iplathifomu yekhemistri egelezayo ye-Uniqsis FlowSyn.
I-UAM yasetshenziswa ukwenza wonke amadivaysi kulolu cwaningo.Ubuchwepheshe basungulwa ngo-1999 futhi imininingwane yabo yobuchwepheshe, imingcele yokusebenza kanye nentuthuko kusukela yasungulwa ingacwaningwa kusetshenziswa izinto ezilandelayo ezishicilelwe34,35,36,37.Idivayisi (Umfanekiso 1) yasetshenziswa kusetshenziswa umsebenzi osindayo we-9 kW SonicLayer 4000® UAM system (Fabrisonic, Ohio, USA).Izinto ezikhethelwe idivayisi yokugeleza bekuyi-Cu-110 ne-Al 6061. I-Cu-110 inokuqukethwe kwethusi okuphezulu (ubuncane obungu-99.9% ithusi), okuyenza ibe ikhandidethi elihle lokusabela okwenziwe ngethusi futhi ngenxa yalokho isetshenziswa “njengesendlalelo esisebenzayo ngaphakathi kwe-microreactor.I-Al 6061 O isetshenziswa njengento “eyinqwaba”., kanye nesendlalelo sokuhlanganisa esisetshenziselwa ukuhlaziya;ukuxubana kwezingxenye zealloy eyisizayo kanye nesimo esihlanganisiwe kuhlanganiswe nongqimba lwe-Cu-110.kutholakale ukuthi azinzile kumakhemikhali nama-reagents asetshenziswa kulo msebenzi.I-Al 6061 O ihlanganiswe ne-Cu-110 nayo ithathwa njengenhlanganisela yezinto ehambisanayo ye-UAM futhi ngenxa yalokho iwumsebenzi ofanelekile walolu cwaningo38,42.Lezi zisetshenziswa zibalwe kuThebula 1 ngezansi.
Izinyathelo zokwenziwa kwe-reactor (1) 6061 i-aluminium alloy substrate (2) Ukwakhiwa kweshaneli ephansi nge-foil yethusi (3) Ukufakwa kwe-thermocouples phakathi kwezendlalelo (4) Ishaneli engaphezulu (5) I-Inlet ne-outlet (6) I-Monolithic reactor.
Ifilosofi yokuklama isiteshi esiwuketshezi ukusebenzisa indlela ehlukumezayo ukuze kwandiswe ibanga elihanjwa uketshezi olungaphakathi kwe-chip kuyilapho kugcinwa usayizi we-chip olawulekayo.Lokhu kunyuka kwebanga kuyafiseleka ukuze kwandiswe isikhathi sokuxhumana esisabelayo kanye nokuhlinzeka ngesivuno esihle kakhulu somkhiqizo.Ama-chips asebenzisa ukugoba okungu-90° ekugcineni kwendlela eqondile ukuze abangele ukuxubana okunesiyaluyalu ngaphakathi kwedivayisi44 futhi andise isikhathi sokuthintana koketshezi nendawo engaphezulu (i-catalyst).Ukuze kuqhutshekwe kuthuthukiswe ukuxutshwa okungafezwa, ukuklanywa kwe-reactor kuhlanganisa ama-inlet amabili asabelayo ahlanganiswe ku-Y-connection ngaphambi kokungena esigabeni sekhoyili yokuhlanganisa.Umnyango wesithathu, oweqa ukugeleza phakathi nendawo lapho uhlala khona, ufakiwe ohlelweni lokusabela kokuhlanganiswa kwezigaba eziningi kwesikhathi esizayo.
Wonke amashaneli anephrofayela eyisikwele (awekho ama-engeli e-taper), okuwumphumela wokugaya ngezikhathi ezithile kwe-CNC okusetshenziselwa ukudala ijiyomethri yesiteshi.Ubukhulu besiteshi bukhethwa ukuze bunikeze isivuno esiphezulu (se-microreactor) yevolumu, kodwa encane ngokwanele ukuze kube lula ukusebenzisana nendawo (ama-catalyst) oketshezi oluningi oluqukethwe.Usayizi ofanele usekelwe kulwazi lwangaphambili lwababhali ngamadivayisi okusabela oketshezi lwensimbi.Ubukhulu bangaphakathi besiteshi sokugcina bekungu-750 µm x 750 µm futhi isamba sevolumu ye-reactor bekungu-1 ml.Isixhumi esakhelwe ngaphakathi (1/4″-28 UNF thread) sifakiwe ekwakhiweni kokuvumela ukuxhumana okulula kwedivayisi nempahla yekhemistri egeleza ngokwezentengiso.Usayizi wesiteshi unqunyelwe ubukhulu bezinto ze-foil, izakhiwo zayo zemishini, kanye nemingcele yokubopha esetshenziswa nama-ultrasonics.Ngobubanzi obuthile bezinto ezinikeziwe, okokusebenza “kuzocwila” kusiteshi esidaliwe.Okwamanje ayikho imodeli ethile yalesi sibalo, ngakho-ke ububanzi besiteshi obukhulu bento enikeziwe kanye nomklamo bunqunywa ngokuhlola, lapho ububanzi obungu-750 µm bungeke bubangele ukuhlehla.
Ukuma (isikwele) sesiteshi kunqunywa kusetshenziswa i-square cutter.Ukuma nobukhulu beziteshi kungashintshwa emishinini ye-CNC kusetshenziswa amathuluzi okusika ahlukene ukuze kutholwe amazinga okugeleza ahlukene kanye nezici.Isibonelo sokudala isiteshi esigobile ngethuluzi le-125 µm singatholakala ku-Monaghan45.Lapho ungqimba lwe-foil lusetshenziswa flat, ukusetshenziswa kwe-foil material eziteshini kuzoba nendawo eyisicaba (isikwele).Kulo msebenzi, i-contour yesikwele isetshenziswe ukuze kulondolozwe ukulinganisa kwesiteshi.
Ngesikhathi sokuphumula okuhleliwe ekukhiqizeni, izinzwa zokushisa ze-thermocouple (uhlobo K) zakhiwe ngokuqondile kudivayisi phakathi kwamaqembu amashaneli aphezulu naphansi (Umfanekiso 1 - isigaba sesi-3).Lawa ma-thermocouples angakwazi ukulawula ukushintsha kwezinga lokushisa ukusuka ku -200 kuya ku-1350 °C.
Inqubo yokubeka insimbi yenziwa uphondo lwe-UAM kusetshenziswa i-foil yensimbi engu-25.4 mm ububanzi nama-microns angu-150 ubukhulu.Lezi zingqimba ze-foil zixhunywe ochungechungeni lwamapheshana aseduze ukumboza yonke indawo yokwakha;usayizi wempahla ediphozithiwe mkhulu kunomkhiqizo wokugcina njengoba inqubo yokukhipha idala isimo sokugcina esihlanzekile.Imishini ye-CNC isetshenziselwa umshini amakhonto angaphandle nangaphakathi ezinto zokusebenza, okuholela ekuqedeni kwendawo okokusebenza namashaneli ahambisana nethuluzi elikhethiwe kanye nemingcele yenqubo ye-CNC (kulesi sibonelo, cishe u-1.6 µm Ra).Okuqhubekayo, okuqhubekayo, okuqhubekayo kwe-ultrasonic impahla yokufafaza kanye nemijikelezo yomshini kusetshenziswa kuyo yonke inqubo yokukhiqiza idivayisi ukuze kuqinisekiswe ukunemba kobukhulu kugcinwa futhi ingxenye eqediwe ihlangabezana namazinga e-CNC wokunemba wokugaya.Ububanzi beshaneli esetshenziselwa le divayisi buncane ngokwanele ukuqinisekisa ukuthi impahla ye-foil "ayincibiliki" esiteshini samanzi, ngakho-ke isiteshi sinesigaba esiphambanayo esiyisikwele.Izikhala ezingaba khona ku-foil kanye nemingcele yenqubo ye-UAM kwanqunywa ngokuhlola uzakwethu wokukhiqiza (Fabrisonic LLC, USA).
Ucwaningo luye lwabonisa ukuthi ku-interface 46, i-47 yenhlanganisela ye-UAM kukhona ukusabalalisa okuncane kwezakhi ngaphandle kokwelashwa okungeziwe kokushisa, ngakho-ke kumadivayisi kulo msebenzi ungqimba lwe-Cu-110 luhlala luhlukile kungqimba lwe-Al 6061 futhi lushintsha kakhulu.
Faka isilawuli se-pre-calibrated back pressure regulator (BPR) ku-250 psi (1724 kPa) ezansi nomfula bese umpompa amanzi ngereactor ngesilinganiso esingu-0.1 kuya ku-1 ml min-1.Ingcindezi ye-reactor iqashwe kusetshenziswa i-FlowSyn pressure transducer eyakhelwe ohlelweni ukuze kuqinisekiswe ukuthi isistimu ingagcina ingcindezi engaguquki.Ama-gradients okushisa angaba khona ku-reactor yokugeleza ahlolwe ngokubheka noma yimuphi umehluko phakathi kwama-thermocouples akhelwe ku-reactor kanye nama-thermocouples akhelwe ku-heater plate ye-chip ye-FlowSyn.Lokhu kufinyelelwa ngokushintsha izinga lokushisa elihleliwe le-hotplate phakathi kuka-100 no-150 °C ekunyukeni okungu-25 °C nokuqapha noma yimuphi umehluko phakathi kwamazinga okushisa ahleliwe narekhodiwe.Lokhu kufinyelelwe kusetshenziswa i-tc-08 data logger (PicoTech, Cambridge, UK) kanye nesofthiwe ehambisana nayo ye-PicoLog.
Izimo zokusabela kwe-cycloaddition ye-phenylacetylene ne-iodoethane ziyathuthukiswa (I-Scheme 1-Cycloaddition ye-phenylacetylene ne-iodoethane, i-Scheme 1-Cycloaddition ye-phenylacetylene ne-iodoethane).Lokhu kulungiselelwa kwenziwa kusetshenziswa indlela ephelele ye-factorial design of experiments (DOE), kusetshenziswa izinga lokushisa nesikhathi sokuhlala njengokuguquguqukayo ngenkathi kulungiswa isilinganiso se-alkyne:azide ku-1:2.
Izixazululo ezihlukene ze-sodium azide (0.25 M, 4:1 DMF:H2O), iodoethane (0.25 M, DMF), ne-phenylacetylene (0.125 M, DMF) zalungiswa.I-aliquot engu-1.5 ml yesixazululo ngasinye yaxutshwa futhi yampontshwa nge-reactor ngezinga lokugeleza elifiselekayo kanye nezinga lokushisa.Impendulo yemodeli ithathwe njengesilinganiso sendawo ephakeme kakhulu yomkhiqizo we-triazole kwinto yokuqala ye-phenylacetylene futhi yanqunywa kusetshenziswa ukusebenza okuphezulu kwe-liquid chromatography (HPLC).Ukuze uthole ukuvumelana kokuhlaziywa, konke ukusabela kwathathwa ngokushesha ngemva kokuba ingxube yokusabela ishiye i-reactor.Ububanzi bepharamitha obukhethelwe ukuthuthukiswa buboniswa kuThebula 2.
Wonke amasampuli ahlaziywa kusetshenziswa isistimu ye-Chromaster HPLC (VWR, PA, USA) ehlanganisa iphampu ye-quaternary, i-oven yekholomu, umtshina we-UV we-wavelength oguquguqukayo kanye ne-autosampler.Ikholomu ibiyi-Equivalence 5 C18 (VWR, PA, USA), 4.6 x 100 mm, 5 µm usayizi wezinhlayiyana, egcinwe ku-40°C.I-solvent kwakuyi-isocratic methanol:amanzi 50:50 ngesilinganiso sokugeleza esingu-1.5 ml·min-1.Umthamo womjovo wawungu-5 μl kanti ubude begagasi lomtshina bungu-254 nm.Indawo ephakeme engu-% yesampula ye-DOE ibalwe kusukela ezindaweni eziphakeme kakhulu zensalela ye-alkyne nemikhiqizo ye-triazole kuphela.Ukwethulwa kwento yokuqala kwenza kube nokwenzeka ukuhlonza iziqongo ezihambisanayo.
Ukuhlanganisa imiphumela yokuhlaziywa kwe-reactor nesofthiwe ye-MODDE DOE (I-Umetrics, i-Malmö, i-Sweden) kuvumele ukuhlaziywa kwethrendi okuphelele kwemiphumela kanye nokunqunywa kwezimo zokusabela ezilungile zale cycloaddition.Ukusebenzisa isilungiseleli esakhelwe ngaphakathi nokukhetha yonke imigomo yemodeli ebalulekile kudala isethi yezimo zokusabela eziklanyelwe ukukhulisa indawo ephakeme kakhulu yomkhiqizo kuyilapho kunciphisa indawo ephakeme kakhulu yesitoko se-acetylene.
I-oxidation yendawo yethusi ekamelweni lokuphendula i-catalytic yafinyelelwa ngokusebenzisa isisombululo se-hydrogen peroxide (36%) egeleza ekamelweni lokuphendula (isilinganiso sokugeleza = 0.4 ml min-1, isikhathi sokuhlala = 2.5 min) ngaphambi kokuhlanganiswa kwe-triazole ngayinye.umtapo wolwazi.
Lapho isethi elungile yezimo isinqunyiwe, yasetshenziswa kuhlu lwe-acetylene kanye ne-haloalkane derivatives ukuze kuvunyelwe ukuhlanganiswa komtapo wezincwadi omncane wokuhlanganiswa, ngaleyo ndlela kutholwe ukuthi kungenzeka yini ukusebenzisa lezi zimo kuhlu olubanzi lwama-reagents angaba khona (Fig. 1).2).
Lungiselela izixazululo ezihlukene ze-sodium azide (0.25 M, 4:1 DMF:H2O), haloalkanes (0.25 M, DMF), nama-alkynes (0.125 M, DMF).Ama-aliquots ka-3 ml wesixazululo ngasinye axutshwe futhi ampontshwa ku-reactor ngenani elingu-75 µl/min kanye nezinga lokushisa elingu-150°C.Ivolumu yonke iqoqwe ku-vial futhi ihlanjululwe nge-10 ml ye-ethyl acetate.Isixazululo sesampula sagezwa ngo-3 x 10 ml wamanzi.Izendlalelo ezinamanzi zahlanganiswa futhi zikhishwe nge-10 ml ethyl acetate, khona-ke izingqimba eziphilayo zihlanganiswa, zigezwe nge-3 × 10 ml brine, zomiswe phezu kwe-MgSO 4 futhi zihlungwe, bese i-solvent ikhishwa ku-vacuo.Amasampuli ahlanzwa ngekholomu ye-silica gel chromatography kusetshenziswa i-ethyl acetate ngaphambi kokuhlaziywa ngenhlanganisela ye-HPLC, 1H NMR, 13C NMR kanye ne-high resolution mass spectrometry (HR-MS).
Zonke izibukeli zitholwe kusetshenziswa i-Thermofischer Precision Orbitrap mass spectrometer ene-ESI njengomthombo we-ionization.Wonke amasampula alungiswa kusetshenziswa i-acetonitrile njenge-solvent.
Ukuhlaziywa kwe-TLC kwenziwa kumapuleti e-silica ane-aluminium substrate.Amapuleti aboniswe ngokukhanya kwe-UV (254 nm) noma amabala nokushisisa kwe-vanillin.
Wonke amasampula ahlaziywa kusetshenziswa isistimu ye-VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) efakwe i-autosampler, iphampu kanambambili ene-oven yekholomu kanye nomtshina owodwa wamaza amaza.Ikholomu ye-ACE Equivalence 5 C18 (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland) isetshenzisiwe.
Imijovo (5 µl) yenziwe ngokuqondile ngengxube ehlanjululiwe yokusabela okungcolile (i-1:10 dilution) futhi yahlaziywa ngamanzi:i-methanol (50:50 noma 70:30), ngaphandle kwamasampuli athile kusetshenziswa isistimu ye-solvent engu-70:30 (echazwa njengenombolo yenkanyezi) ngenani lokugeleza elingu-1.5 ml/min.Ikholomu yayigcinwe ku-40°C.Ubude begagasi bomtshina bungama-254 nm.
Indawo ephakeme engu-% yesampula ibalwa kusukela endaweni ephakeme ye-alkyne esele, umkhiqizo we-triazole kuphela, futhi ukwethulwa kwezinto zokuqala kwenze kwaba nokwenzeka ukuhlonza iziqongo ezihambisanayo.
Wonke amasampuli ahlaziywa kusetshenziswa i-Thermo iCAP 6000 ICP-OES.Wonke amazinga okulinganisa alungiswa kusetshenziswa isixazululo esijwayelekile esingu-1000 ppm Cu ku-2% we-nitric acid (SPEX Certi Prep).Wonke amazinga alungiswa ngesisombululo sika-5% DMF no-2% HNO3, futhi wonke amasampula ahlanjululwe izikhathi ezingu-20 ngesixazululo sesampula se-DMF-HNO3.
I-UAM isebenzisa i-ultrasonic metal welding njengendlela yokuhlanganisa i-foil yensimbi esetshenziselwa ukwakha umhlangano wokugcina.I-Ultrasonic metal welding isebenzisa ithuluzi lensimbi elidlidlizayo (elibizwa ngokuthi uphondo noma uphondo lwe-ultrasonic) ukuze kufakwe ingcindezi ku-foil/ungqimba olwaluqinisiwe ngaphambili ukuze luboshwe/luhlanganiswe ngaphambilini ngokudlidliza.Ngokusebenza okuqhubekayo, i-sonotrode inomumo we-cylindrical futhi igoqa phezu kwendawo yezinto ezibonakalayo, ihlanganisa yonke indawo.Lapho kusetshenziswa ingcindezi nokudlidliza, ama-oxide angaphezulu kwezinto angaqhekeka.Ukucindezela njalo nokudlidliza kungaholela ekubhujisweni kobunzima bento engu-36.Ukuthintana eduze nokushisa kwendawo kanye nokucindezela bese kuholela kubhondi yesigaba esiqinile ezindaweni ezibonakalayo;ingabuye ikhuthaze ukubumbana ngokushintsha amandla angaphezulu48.Imvelo yendlela yokuhlanganisa inqoba izinkinga eziningi ezihlobene nezinga lokushisa eliguquguqukayo lokuncibilika kanye nemiphumela yokushisa ephezulu okukhulunywe ngayo kobunye ubuchwepheshe bokukhiqiza okungeziwe.Lokhu kuvumela ukuxhumana okuqondile (okungukuthi ngaphandle kokuguqulwa kwendawo, ama-fillers noma ama-adhesives) kwezingqimba eziningana zezinto ezihlukahlukene zibe isakhiwo esisodwa esihlanganisiwe.
Isici sesibili esivumayo se-CAM yizinga eliphezulu lokugeleza kwepulasitiki okubonwa ezintweni zensimbi ngisho namazinga okushisa aphansi, okungukuthi ngaphansi kwendawo encibilika yezinto zensimbi.Ukuhlanganiswa kokudlidliza kwe-ultrasonic kanye nokucindezela kubangela izinga eliphezulu lokufuduka komngcele wendawo wokusanhlamvu kanye nokuvuselelwa kabusha ngaphandle kokukhuphuka okuphawulekayo kwezinga lokushisa okuvame ukuhlotshaniswa nezinto eziningi.Ngesikhathi sokwakhiwa komhlangano wokugcina, lesi simo singasetshenziselwa ukushumeka izingxenye ezisebenzayo nezingenzi lutho phakathi kwezingqimba ze-foil yensimbi, ungqimba ngongqimba.Izinto ezinjenge-fiber optical 49, i-reinforcement 46, i-electronics 50 kanye nama-thermocouples (lo msebenzi) ahlanganiswe ngempumelelo ezakhiweni ze-UAM ukuze kwakhiwe imihlangano eyinhlanganisela esebenzayo nengenzi lutho.
Kulo msebenzi, kokubili amakhono ahlukene okubopha izinto ezibonakalayo kanye nekhono lokuxhumanisa le-UAM asetshenziselwa ukwakha i-microreactor efanelekile yokulawula izinga lokushisa le-catalytic.
Uma kuqhathaniswa ne-palladium (Pd) nezinye izinto ezisetshenziswayo zensimbi ezivame ukusetshenziswa, i-Cu catalysis inezinzuzo ezimbalwa: (i) Ngokomnotho, i-Cu ishibhile kunezinye izinsimbi eziningi ezisetshenziswa ku-catalysis ngakho-ke iyindlela ekhangayo embonini yamakhemikhali (ii) uhla lwe-Cu-catalyzed cross-coupling reactions luyakhula futhi lubonakala lusekelwe ku-Pd2,5calogies -3,51,51,31,51,51,31,51,51,51,51,51,51,51,51,3,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,51,5,3,5,3,51,51,5,3,51,51,5,51,5,3,51,5,3,51,5,5,51. ukusabela kwe-talyzed kusebenza kahle uma ingekho eminye imigqa.Lawa ma-ligand ngokuvamile alula ngokwesakhiwo futhi awabizi.uma kuthanda, kuyilapho lawo asetshenziswa ku-Pd chemistry ngokuvamile eyinkimbinkimbi, ebiza, futhi ezwela emoyeni (iv) Cu, eyaziwa kakhulu ngekhono layo lokuhlanganisa ama-alkynes ekuhlanganiseni, njengokuhlanganisa kwe-bimetallic catalyzed ka-Sonogashira kanye ne-cycloaddition nge-azides (chofoza i-chemistry) (v) I-Cu ingase futhi ikhuthaze i-arylation ye-nucleotype ethile yokusabela kwe-nullmann.
Muva nje, izibonelo ze-heterogenization yakho konke lokhu kusabela phambi kwe-Cu(0) zibonisiwe.Lokhu kubangelwa kakhulu imboni yezemithi kanye nokugxila okukhulayo ekubuyiseleni nasekusebenziseni kabusha ama-catalysts ensimbi55,56.
Ukusabela kwe-1,3-dipolar cycloaddition phakathi kwe-acetylene ne-azide kuya ku-1,2,3-triazole, eyahlongozwa okokuqala ngu-Huisgen ngeminyaka yo-1960s57, kuthathwa njengokusabela kokubonisana kwe-synergistic.Izingcezu ezingu-1,2,3 ze-triazole eziwumphumela zinesithakazelo esikhulu njenge-pharmacophore ekutholweni kwezidakamizwa ngenxa yezicelo zazo zebhayoloji kanye nokusetshenziswa kuma-ejenti okwelapha ahlukahlukene 58.
Lokhu kusabela kuthole ukunakwa okuvuselelwe lapho u-Sharpless nabanye bethula umqondo “wokuchofoza ikhemistri”59.Igama elithi "chofoza ikhemistri" lisetshenziselwa ukuchaza isethi eqinile nekhethiwe yokusabela kokuhlanganiswa okusheshayo kwezinhlanganisela ezintsha nemitapo yolwazi ehlanganisiwe esebenzisa i-heteroatomic bonding (CXC)60.Ukukhanga kokwenziwa kwalokhu kusabela kungenxa yesivuno esiphezulu esihambisana nakho.izimo zilula, ukumelana nomoya-mpilo namanzi, futhi ukuhlukaniswa komkhiqizo kulula61.
I-classical 1,3-dipole Huisgen cycloaddition ayiweli esigabeni esithi "chofoza ikhemistri".Kodwa-ke, i-Medal ne-Sharpless ibonise ukuthi lo mcimbi wokuhlanganisa i-azide-alkyne udlula i-107-108 phambi kwe-Cu(I) uma kuqhathaniswa nokusheshisa okuphawulekayo kwesilinganiso se-non-catalytic 1,3-dipolar cycloaddition 62,63.Le ndlela yokusabela ethuthukisiwe ayidingi ukuvikela amaqembu noma izimo zokusabela ezinzima futhi inikeza cishe ukuguqulwa okuphelele nokukhetha ku-1,4-disubstituted 1,2,3-triazoles (anti-1,2,3-triazoles) ngokuhamba kwesikhathi (Fig. 3).
Imiphumela ye-Isometric ye-Huisgen cycloadditions evamile kanye ne-copper-catalyzed.I-Cu(I)-catalyzed Huisgen cycloadditions inikeza kuphela i-1,4-distituted 1,2,3-triazoles, kuyilapho ama-cycloadditions e-Huisgen enziwa ngokushisa ngokuvamile anikeza i-1,4- kanye ne-1,5-triazoles ingxube engu-1:1 yama-azole stereoisomers.
Izivumelwano eziningi zibandakanya ukuncishiswa kwemithombo ezinzile ye-Cu(II), njengokuncishiswa kwe-CuSO4 noma inhlanganisela ye-Cu(II)/Cu(0) kuhlanganiswe nosawoti we-sodium.Uma kuqhathaniswa nokunye ukusabela okwenziwe ngensimbi, ukusetshenziswa kwe-Cu(I) kunezinzuzo eziyinhloko zokungabizi futhi kulula ukuyiphatha.
Izifundo ze-Kinetic ne-isotopic ngu-Worrell et al.65 baye babonisa ukuthi esimweni se-alkynes yokugcina, okulinganayo kokubili kwethusi kuyabandakanyeka ekwenzeni kusebenze ukusebenza kabusha kwe-molecule ngayinye ngokuphathelene ne-azide.Indlela ehlongozwayo iqhubeka ngendandatho yethusi enamalungu ayisithupha eyakhiwe ukuxhumanisa kwe-azide ku-σ-bond acetylide yethusi enethusi eliboshwe u-π njenge-ligand donor ezinzile.Okuphuma kokuphuma kwe-Copper triazolyl kwakheka ngenxa yokufinyela kwendandatho okulandelwa ukubola kweproton ukuze kwakhe imikhiqizo ye-triazole futhi kuvalwe umjikelezo we-catalytic.
Nakuba izinzuzo zamadivayisi we-flow chemistry zibhalwe kahle, kube nesifiso sokuhlanganisa amathuluzi okuhlaziya kulezi zinhlelo zokuqapha inqubo yesikhathi sangempela ku-situ66,67.I-UAM ifakazele ukuthi iyindlela efanelekile yokuklama nokwenza izinto ezigeleza ze-3D eziyinkimbinkimbi kakhulu ezivela ezintweni ezisebenzayo, ezisebenza ngokushisa okushisayo ezinezakhi zokuzwa ezishunyekiwe ngokuqondile (Umfanekiso 4).
I-Aluminium-copper flow reactor ekhiqizwa ukukhiqizwa kwe-ultrasonic additive (UAM) enesakhiwo sesiteshi sangaphakathi esiyinkimbinkimbi, ama-thermocouples akhelwe ngaphakathi kanye ne-catalytic reaction chamber.Ukuze ubone ngeso lengqondo izindlela zoketshezi lwangaphakathi, i-prototype esobala eyenziwe kusetshenziswa i-stereolithography nayo iyaboniswa.
Ukuqinisekisa ukuthi ama-reactors enzelwe ukusabela kwe-organic okuzayo, izincibilikisi kufanele zishiswe ngokuphephile ngaphezu kwendawo yazo yokubilisa;zivivinywa ingcindezi nezinga lokushisa.Ukuhlolwa kwengcindezi kubonise ukuthi uhlelo lugcina ingcindezi ezinzile futhi eqhubekayo ngisho nasekucindezelweni okuphezulu ohlelweni (1.7 MPa).Ukuhlolwa kwe-Hydrostatic kwenziwa ekamelweni lokushisa kusetshenziswa i-H2O njengoketshezi.
Ukuxhuma i-thermocouple eyakhelwe ngaphakathi (Umfanekiso 1) kusilondolozi sedatha yezinga lokushisa kubonise ukuthi izinga lokushisa le-thermocouple lalingu-6 °C (± 1 °C) ngaphansi kwezinga lokushisa elihleliwe ohlelweni lwe-FlowSyn.Ngokuvamile, ukunyuka kwezinga lokushisa ngo-10°C kuliphinda kabili izinga lokusabela, ngakho umehluko wezinga lokushisa wamadigri ambalwa nje ungashintsha izinga lokusabela ngokuphawulekayo.Lo mehluko ungenxa yokulahleka kwezinga lokushisa kuyo yonke i-RPV ngenxa yokuhluka okuphezulu kokushisa kwezinto ezisetshenziswa enqubweni yokukhiqiza.Lokhu kukhukhuleka okushisayo kuhlala njalo ngakho-ke kungacatshangelwa lapho kusethwa okokusebenza ukuze kuqinisekiswe ukuthi izinga lokushisa elinembile liyafinyelelwa futhi likalwe phakathi nokusabela.Ngakho-ke, leli thuluzi lokuqapha eliku-inthanethi lisiza ukulawula okuqinile kwezinga lokushisa lokusabela futhi linomthelela ekwenzeni inqubo enembe kakhudlwana nasekuthuthukisweni kwezimo ezifanele.Lezi zinzwa zingasetshenziswa futhi ukuthola ukusabela kwe-exothermic nokuvimbela ukusabela kokubaleka kumasistimu amakhulu.
I-reactor evezwe kuleli phepha iyisibonelo sokuqala sokusetshenziswa kobuchwepheshe be-UAM ekwenziweni kwama-reactors amakhemikhali futhi ibhekana nemikhawulo eminingana emikhulu okwamanje ehlotshaniswa nokuphrinta kwe-AM/3D kwalawa madivayisi, njengalokhu: (i) Ukunqoba izinkinga eziphawuliwe ezihlobene nokucutshungulwa kwethusi noma ingxubevange ye-aluminium (ii) ukulungiswa kwesiteshi okuthuthukisiwe kwangaphakathi uma kuqhathaniswa nezindlela zokuncibilika kombhede oyimpuphu (PBive6M2) njengezindlela zokuncibilika kombhede oyimpushana (i-PBive6M2) indlela yokuncibilika kwe-SLF 5 nezindlela zokuncibilika kombhede (i-PPB9M)2 26 (iii) izinga lokushisa eliphansi lokucubungula, okusiza izinzwa zokuxhuma ngokuqondile, okungenakwenzeka kubuchwepheshe be-powder bed, (v) ukunqoba izici ezimbi zemishini kanye nokuzwela kwezingxenye ezisekelwe ku-polymer ku-solvents evamile ye-organic17,19.
Ukusebenza kwe-reactor kuboniswe uchungechunge lwe-alkinazide cycloaddition reactions ye-copper-catalyzed ngaphansi kwezimo zokugeleza okuqhubekayo (Fig. 2).I-reactor yethusi ephrintiwe ye-ultrasonic eboniswe emkhiwaneni.I-4 ihlanganiswe nesistimu yokugeleza kwezentengiselwano futhi isetshenziselwe ukuhlanganiswa komtapo we-azide we-1,4-disubstituted 1,2,3-triazoles ehlukahlukene usebenzisa ukusabela okulawulwa kwezinga lokushisa kwe-acetylene ne-alkyl group halides phambi kwe-sodium chloride (Fig. 3).Ukusetshenziswa kwendlela yokugeleza okuqhubekayo kunciphisa izinkinga zokuphepha ezingase ziphakame ezinqubweni ze-batch, njengoba lokhu kusabela kukhiqiza ama-aside intermediates asebenzayo kakhulu futhi ayingozi [317], [318].Ekuqaleni, ukusabela kwalungiselelwa i-cycloaddition ye-phenylacetylene ne-iodoethane (I-Scheme 1 - i-Cycloaddition ye-phenylacetylene ne-iodoethane) (bheka i-Fig. 5).
(Phezulu kwesokunxele) Uhlelo lokusetha olusetshenziselwa ukufaka i-reactor ye-3DP ohlelweni lokugeleza (ngaphezulu kwesokudla) etholwe kusikimu esilungiselelwe (esiphansi) sohlelo lwe-Huisgen 57 cycloaddition phakathi kwe-phenylacetylene ne-iodoethane ukuze kuthuthukiswe futhi kuboniswe imingcele yezinga lokuguqulwa elilungiselelwe lokusabela.
Ngokulawula isikhathi sokuhlala sama-reactants esigabeni se-catalytic se-reactor nokuqapha ngokucophelela izinga lokushisa lokusabela ngenzwa edidiyelwe ngokuqondile ye-thermocouple, izimo zokusabela zingenziwa ngokushesha nangokunembile ngobuncane besikhathi nezinto zokwakha.Ngokushesha kwatholakala ukuthi ukuguqulwa okuphezulu kakhulu kwafinyelelwa kusetshenziswa isikhathi sokuhlala semizuzu engu-15 kanye nezinga lokushisa lokusabela elingu-150°C.Kungabonakala kusakhiwo se-coefficient yesofthiwe ye-MODDE ukuthi kokubili isikhathi sokuhlala kanye nezinga lokushisa lokusabela kubhekwa njengezimo ezibalulekile zemodeli.Ukusebenzisa isilungiseleli esakhelwe ngaphakathi kusetshenziswa lezi zimo ezikhethiwe kudala isethi yezimo zokusabela ezidizayinelwe ukukhulisa izindawo eziphakeme kakhulu zomkhiqizo ngenkathi kuncipha ukuqala kwezindawo eziphakeme kakhulu.Lokhu kulungiselelwa kuveze ukuguqulwa okungu-53% komkhiqizo we-triazole, okufana ncamashi nokubikezela kwemodeli okungama-54%.