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Ukukhiqiza okungeziwe kushintsha indlela abacwaningi nosozimboni abaklama futhi benze ngayo izinto zamakhemikhali ukuze zihlangabezane nezidingo zabo ezithile. Kulo msebenzi, sibika isibonelo sokuqala se-reactor egelezayo eyakhiwe yisu le-solid-state metal sheet lamination technique I-Ultrasonic Additive Manufacturing (UAM) enezingxenye ze-catalytic ezididiyelwe nezici zokuzwa. Akukhona nje kuphela ukuthi ubuchwepheshe be-UAM bunqoba imikhawulo eminingi okwamanje ehlotshaniswa nochungechunge lwamakhemikhali anjalo, futhi kwandisa ngokuphawulekayo uchungechunge lwamakhemikhali anjalo. Izakhi ezibalulekile ze-1,4-disubstituted 1,2,3-triazole zenziwe ngempumelelo futhi zalungiswa nge-Cu-mediated Huisgen 1,3-dipolar cycloaddition reaction kusetshenziswa ukusetha kwe-UAM chemistry.
Ngenxa yezinzuzo zayo eziphawulekayo ngaphezu komlingani wayo omningi, i-flow chemistry iyinkambu ebalulekile futhi ekhulayo kuzo zombili izilungiselelo zezemfundo nezimboni ngenxa yekhono layo lokwandisa ukukhetha nokusebenza kahle kwe-chemical synthesis.Lokhu kudlulela kusukela ekubunjweni kwe-organic molecule1 kuya kumakhemikhali emithi2,3 kanye nemikhiqizo yemvelo4,5,6.Ukusabela okungaphezulu kuka-50% ezimbonini ezinhle zamakhemikhali nezemithi kungazuza ekusebenziseni ukucubungula kokugeleza okuqhubekayo7.
Eminyakeni yamuva nje, kube nokuthambekela okukhulayo kwamaqembu afuna ukufaka esikhundleni se-glassware yendabuko noma imishini yamakhemikhali agelezayo nge-customizable additive manufacturing (AM) chemistry "reaction vessels"8.Umklamo ophindaphindayo, ukukhiqiza okusheshayo, namandla angu-3-dimensional (3D) alawa maqhinga anenzuzo kulabo abafisa ukwenza ngokwezifiso amadivayisi abo kusethi ethize yokusabela, idethi, ukusetshenziswa okusekelwe ku-polymer okusekelwe ku-3D kuphela kumibandela yokusebenza okusekelwe ku-3D kuphela. amasu okuphrinta afana ne-stereolithography (SL)9,10,11, i-fused deposition modeling (FDM)8,12,13,14 kanye nokuphrinta kwe-inkjet 7, 15, 16. Ukuntuleka kokuqina kanye nekhono lamathuluzi anjalo okwenza uhla olubanzi lokuphendula kwamakhemikhali/ukuhlaziya17, 18, 2018 mkhakha omkhulu, umkhawulo ongu-2018 womkhakha omkhulu 18, 18, 18, 2019 19, 20 .
Ngenxa yokwanda kokusetshenziswa kwekhemikhali yokugeleza kanye nezakhiwo ezithandekayo ezihlotshaniswa ne-AM, kunesidingo sokuhlola amasu athuthuke kakhulu avumela abasebenzisi ukuthi bakhe imikhumbi yokusabela kokugeleza ngamandla athuthukisiwe amakhemikhali nawokuhlaziya.Lawa masu kufanele avumele abasebenzisi ukuthi bakhethe ohlwini lwezinto eziqinile noma ezisebenzayo ezikwazi ukuphatha izimo ezihlukahlukene zokusabela, kuyilapho kusiza izinhlobo ezihlukahlukene zokulawula ukusabela okuvela kudivayisi nokulawula okuphumayo.
Inqubo eyodwa yokukhiqiza i-additive enamandla okuthuthukisa ama-reactors amakhemikhali angokwezifiso I-Ultrasonic Additive Manufacturing (UAM) .Le nqubo ye-solid state sheet lamination isebenzisa ama-oscillations e-ultrasonic kuma-foil ensimbi amancane ukuze uwahlanganise ndawonye ungqimba ngongqimba olunokushisa okuncane okuyinqwaba kanye nezinga eliphezulu lokugeleza kwe-plastic 21 , 22 , 23 .Ngokungafani nezinye izinhlobo ezihlanganisiwe ze-AM technologies, ngokungafani nezinye i-AM ekhiqizayo eyaziwayo njenge-subtechnic inqubo, lapho i-in-situ periodic computer numberal control (CNC) milling noma laser machining ichaza umumo wenetha weleya lezinto eziboshiwe 24, 25.Lokhu kusho ukuthi umsebenzisi akakhawulelwe ngezinkinga ezihambisana nokususa insalela yokwakha eluhlaza eziteshini ezincane eziwuketshezi, okuvame ukuba njalo ngempushana noketshezi oluwuketshezi lwezinhlelo ze-AM futhi zingakwazi ukwelula ukuklama okubalulekile kwe-AM futhi kungakwazi ukwelula ukuklama okubalulekile kwe-AM kanye ne-AM etholakalayo. ukuhlanganiswa kwezinto ezibonakalayo esinyathelweni esisodwa senqubo.Ukukhethwa kwezinhlanganisela zezinto ezidlula inqubo yokuncibilika kusho ukuthi izimfuno zemishini nezamakhemikhali zezinhlelo ezithile zokusebenza zingahlangatshezwana kangcono.Ngaphezu kokuhlanganiswa kombuso oqinile, enye into ehlangatshezwane nayo ngesikhathi sokuhlanganiswa kwe-ultrasonic ukugeleza okuphezulu kwezinto zepulasitiki emazingeni okushisa aphansi kakhulu29,30,31,32,33.Lesi sici esiyingqayizivele se-UAM sokufaka i-ethermal ingakwazi ukugxilisa izakhi zensimbi ngaphandle kwe-embedding. ukulethwa kolwazi lwesikhathi sangempela kusuka kudivayisi kuya kumsebenzisi ngezibalo ezihlanganisiwe.
Umsebenzi wangaphambili wababhali32 ubonise ikhono lenqubo ye-UAM yokudala izakhiwo ze-3D microfluidic metallic ezinamandla okuzwa okuhlanganisiwe.Lena iyithuluzi lokuqapha kuphela.Leli phepha lethula isibonelo sokuqala se-microfluidic chemical reactor eyakhiwe yi-UAM;idivayisi esebenzayo engaqapheli nje kuphela kodwa futhi idonsa ukuhlanganiswa kwamakhemikhali ngokusebenzisa izinto ezikhuthazayo ezihlanganisiwe ngokwesakhiwo.Idivayisi ihlanganisa izinzuzo ezimbalwa ezihambisana nobuchwepheshe be-UAM ekukhiqizeni idivayisi yamakhemikhali ye-3D, njengalezi: ikhono lokuguqula imiklamo egcwele ye-3D ngokuqondile kusuka kumamodeli we-computer-aid design (CAD) ibe yimikhiqizo;ukwakhiwa kwezinto eziningi ukuze kuhlanganiswe izinga eliphezulu le-thermal conductivity kanye nezinto ze-catalytic;kanye nokushumeka izinzwa ezishisayo ngokuqondile phakathi kokugeleza kwe-reagent ukuze kuhlolwe izinga lokushisa elinembile nokulawula.Ukubonisa ukusebenza kwe-reactor, umtapo wolwazi wezingxube ezibalulekile ze-1,4-disubstituted 1,2,3-triazole obalulekile ngokwemithi wahlanganiswa i-Huisgen 1,3-dipolar eyenziwe nge-copper-catalyzed. amathuba kanye namathuba ekhemistri ngocwaningo lwemikhakha eminingi.
Zonke izincibilikisi nama-reagents athengwe kwa-Sigma-Aldrich, Alfa Aesar, TCI noma i-Fischer Scientific futhi asetshenziswa ngaphandle kokuhlanzwa kwangaphambili.1H kanye ne-13C NMR spectra erekhodwe ku-400 MHz kanye no-100 MHz, ngokulandelana, atholwe kusetshenziswa i-JEOL ECS-400 400 400 MHz spectra ye-CD noma i-CD 400 MHz spectra noma i-CD 400 MHz I-l3 noma (CD3)2SO njenge-solvent.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 ngezinto ezishicilelwe ezilandelayo34,35,36,37.Idivayisi (Umfanekiso 1) yasetshenziswa kusetshenziswa amandla aphezulu kakhulu, i-9kW SonicLayer UAM 4000, isistimu yokugeleza kwe-U. idivayisi bekuyi-Cu-110 kanye ne-Al 6061.Cu-110 inokuqukethwe kwethusi okuphezulu (ubuncane obungu-99.9% bethusi), okuyenza ibe ikhandidethi elihle lokusabela okwenziwe ngethusi, futhi ngenxa yalokho isetshenziswa “njengesendlalelo esisebenzayo ngaphakathi kwe-microreactor.I-Al 6061 O isetshenziswa njengento “eyinqwaba”, futhi isendlalelo sokushumeka esisetshenziselwa ukuhlaziya;Ukushumeka kwengxenye ye-alloy kanye nesimo se-anneal kuhlanganiswe nesendlalelo se-Cu-110.I-Al 6061 O iyinto ekhonjiswe ukuthi ihambisana kakhulu nezinqubo ze-UAM38, 39, 40, 41 futhi ihloliwe futhi yatholakala izinzile ngokweKhemikhali nama-reagents asetshenziswa kulo msebenzi.Inhlanganisela ye-Al 6061 O ne-Cu-110 nayo ithathwa njengenhlanganisela yezinto ehambisanayo ye-UAM futhi ngenxa yalokho iwumsebenzi ofanele lolu cwaningo.38,42 Lezi zisetshenziswa zibalwe kuThebula 1 ngezansi.
Izigaba zokwenziwa kwe-reactor (1) I-Al 6061 substrate (2) Ukwenziwa kwesiteshi esingaphansi esisethwe ku-foil yethusi (3) Ukushumeka kwama-thermocouples phakathi kwezendlalelo (4) Ishaneli ephezulu (5) I-Inlet ne-outlet (6) i-Monolithic reactor.
Ifilosofi yedizayini yendlela yoketshezi iwukusebenzisa indlela ehlanganisiwe ukuze kwandiswe ibanga elihamba uketshezi ngaphakathi kwe-chip, kuyilapho ugcina i-chip ikusayizi olawulekayo.Lokhu kukhuphuka kwebanga kuyadingeka ukuze kukhuliswe isikhathi sokusebenzisana se-catalyst/reagent futhi kunikeze umkhiqizo omuhle kakhulu womkhiqizo. Ama-chips asebenzisa ukugoba okungu-90° ekugcineni kwendlela eqondile ukuze abangele uketshezi oluqhubekayo ngaphakathi kwe-4ta yokwandisa uketshezi ngaphakathi kwedivayisi (ukuze kukhuphule uketshezi oluqhubekayo phakathi nesikhathi sokuxhumana). ukuxuba okungafinyelelwa, umklamo we-reactor uhlanganisa ama-reagent inlets amabili ahlanganiswe ku-Y-junction ngaphambi kokungena esigabeni sokuxuba inyoka.I-inlet yesithathu, enqamula umfudlana phakathi nendawo yokuhlala kwayo, ifakiwe ekwakhiweni kwe-multistep reaction syntheses yesikhathi esizayo.
Wonke amashaneli anephrofayela eyisikwele (awekho ama-engeli asalungiswa), umphumela wokugaya ngezikhathi ezithile kwe-CNC okusetshenziselwa ukudala ijiyomethri yesiteshi. Ubukhulu besiteshi bukhethwa ukuze kuqinisekiswe ukuphuma kwevolumu ephezulu (ye-microreactor), kuyilapho buncane ngokwanele ukuze kube lula ukusebenzisana kwendawo (ama-catalyst) kuketshezi oluningi oluqukethwe. 750 µm kanye nesamba sevolumu ye-reactor bekungu-1 ml.Isixhumi esihlanganisiwe (1/4″—28 intambo ye-UNF) sifakiwe ekwakhiweni kokuvumela ukuhlobana okulula kwedivayisi nokokusebenza kwekhemistri egeleza ngokwentengiso.Usayizi wesiteshi unqunyelwe ubukhulu bezinto ze-foil, izakhiwo zayo zemishini, kanye nemingcele yokubopha esetshenziswa nama-ultrasonics.Ngobubanzi obuthile bento enikeziwe, okokusebenza "kuzocwila" kusiteshi esidaliwe.Okwamanje ayikho imodeli ethile yalesi sibalo, ngakho ububanzi besiteshi esiphezulu sento enikeziwe kanye nomklamo bunqunywa ngokuhlola;kulokhu, ububanzi be-750 μm ngeke bubangele i-sag.
Ukuma (isikwele) sesiteshi kunqunywa ngokusebenzisa i-square cutter.Umumo nobukhulu beziteshi kungashintshwa ngemishini ye-CNC kusetshenziswa amathuluzi okusika ahlukene ukuze kutholwe amazinga okugeleza ahlukene kanye nezici.Isibonelo sokwenza isiteshi somumo ogobile usebenzisa ithuluzi le-125 μm singatholakala emsebenzini we-Monaghan45.Lapho ungqimba lwe-foil lubekwe phezu kwe-fashion overlay, le nto izoba phezu kwepulani le-foil. umsebenzi, ukuze kugcinwe ukulinganisa kwesiteshi, kusetshenziswe uhlaka lwesikwele.
Ngesikhathi sokumisa okwesikhashana lapho kukhiqizwa, ama-thermocouple amazinga okushisa (Uhlobo K) ashumekwe ngokuqondile ngaphakathi kwedivayisi phakathi kwamaqembu amashaneli aphezulu naphansi (Umfanekiso 1 - Isiteji sesi-3). Lawa ma-thermocouples angakwazi ukuqapha izinguquko zokushisa ukusuka ku-−200 kuya ku-1350 °C.
Inqubo yokubeka insimbi yenziwa uphondo lwe-UAM lisebenzisa i-foil yensimbi engu-25.4 mm ububanzi, i-micron eyi-150 yensimbi.ubukhulu bezinto ezifakiwe zikhulu kunomkhiqizo wokugcina njengoba inqubo yokukhipha ikhiqiza isimo sokugcina senetha.Umshini we-CNC usetshenziselwa umshini ama-contours angaphandle nangaphakathi wemishini, okuholela ekuqedeni okungaphezulu kwemishini namashaneli alingana nethuluzi elikhethiwe kanye nemingcele yenqubo ye-CNC (cishe i-1.6 μm Ra kulesi sibonelo) . ukunemba kugcinwa futhi ingxenye eqediwe izohlangabezana namazinga okunemba wokuqeda ukugaya kwe-CNC.Ububanzi besiteshi obusetshenziselwa le divayisi buncane ngokwanele ukuze kuqinisekiswe ukuthi impahla ye-foil “ayicwilisi” esiteshini esiwuketshezi, ngakho-ke isiteshi sigcina isikwele esiphambanayo.Izikhala ezingaba khona ezintweni ze-foil kanye nemingcele yenqubo ye-UAM yanqunywa ngokuhlola uzakwethu wokukhiqiza (Fabrisonic LLC, USA).
Ucwaningo lubonise ukuthi ukusabalalisa okuncane kwe-elementi kwenzeka ku-UAM bonding interface 46, 47 ngaphandle kokwelashwa okushisayo okwengeziwe, ngakho-ke kumadivayisi akulo msebenzi, ungqimba lwe-Cu-110 luhlala luhlukile kungqimba lwe-Al 6061 futhi lushintsha kungazelelwe.
Faka isilawuli se-back pressure (BPR) esilinganiselwe ngaphambili esingu-250 (1724 kPa) esitokisini se-reactor bese umpompa amanzi nge-reactor ngenani elingu-0.1 ukuya ku-1 mL min-1. Ukucindezela kwereactor kwaqashwa kusetshenziswa inzwa ye-FlowSyn eyakhelwe ngaphakathi yesistimu yokucindezela ukuze kuqinisekiswe ukuthi isistimu ikwazi ukugcina noma iyiphi i-reactor egelezayo engaguquki phakathi kwe-reactor egelezayo engaguquki. ama-rmocouples ashumekwe ngaphakathi kwe-reactor kanye nalawo ashumekwe ngaphakathi kwepuleti lokushisa le-FlowSyn chip. Lokhu kufinyelelwa ngokushintsha izinga lokushisa le-hotplate elihlelekayo phakathi kuka-100 no-150 °C ekunyukeni okungu-25 °C nokuqaphela noma yimuphi umehluko phakathi kwamazinga okushisa ahleliwe narekhodiwe.Lokhu kufinyelelwe kusetshenziswa i-tc-08 isofthiwe ye-Pigcong.
Izimo zokusabela kwe-cycloaddition ze-phenylacetylene ne-iodoethane zathuthukiswa (I-Scheme 1- Cycloaddition of phenylacetylene kanye ne-iodoethane Scheme 1- Cycloaddition of phenylacetylene and iodoethane). Lokhu kulungiselelwa kwenziwa ngokuklanywa okuphelele kwe-factorial yokuhlola (i-DOE: i-residence ratio) ngesikhathi sokuhlola, kusetshenziswa i-parazine ratio ye-resided, kusetshenziswa i-parazine ratio ye-residence, kusetshenziswa i-residence ratio 1:2.
Izisombululo 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 elifiswayo lokugeleza kanye nezinga lokushisa njengoba imodeli ye-pelaty enqunyiwe yokuqala yomkhiqizo yathathwa imodeli ye-phezole yokuqala yomkhiqizo. nge-high performance liquid chromatography (HPLC).Ngokuvumelana kokuhlaziya, konke ukusabela kwathathwa isampula ngemva nje kokuba ingxube yokusabela ishiye i-reactor.Ububanzi bepharamitha obukhethelwe ukulungiselelwa buboniswa kuThebula 2.
Wonke amasampuli ahlaziywa kusetshenziswa isistimu ye-Chromaster HPLC (VWR, PA, USA) ehlanganisa iphampu ye-quaternary, i-oven yekholomu, umtshina we-UV oguquguqukayo we-wavelength kanye ne-autosampler.Ikholomu ibiyi-Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 × 100 mm ubukhulu be-isocratic, 5 000 mm i-isocra I-methanol engu-50:amanzi ngesilinganiso sokugeleza esingu-1.5 mL.min-1.Ivolumu yomjovo ibingu-5 µL futhi ubude bendawo yomtshina bebungu-254 nm.Indawo ephakeme engu-% yesampula ye-DOE ibalwe kusukela ezindaweni eziphakeme kakhulu zensalela ye-alkyne nemikhiqizo ye-triazole kuphela.
Ukuhlanganisa okukhiphayo kokuhlaziywa kwe-reactor kusofthiwe ye-MODDE DOE (i-Umetrics, i-Malmö, i-Sweden) kuvumele ukuhlaziya okuphelele kwamathrendi wemiphumela kanye nokunqunywa kwezimo ezilungile zokusabela zale cycloaddition.Ukusebenzisa isilungiseleli esakhelwe ngaphakathi nokukhetha yonke imibandela yemodeli ebalulekile kuveza isethi yezimo zokusabela eziklanyelwe ukukhulisa indawo ephakeme yomkhiqizo ngenkathi kunciphisa indawo ephakemeyo yokuqala yomkhiqizo ngenkathi kunciphisa inani eliphakeme lendawo yokuqala.
Ukufakwa kwe-oxidation yethusi engaphezulu ngaphakathi kwegumbi le-catalytic reaction kwafinyelelwa kusetshenziswa isixazululo se-hydrogen peroxide (36%) egeleza egumbini lokusabela (izinga lokugeleza = 0.4 mL min-1, isikhathi sokuhlala = 2.5 min) ngaphambi kokuhlanganiswa komtapo wezincwadi we-triazole ngamunye.
Lapho isethi yemibandela efanele ibonakalisiwe, isetshenziswe kuhlu lwe-acetylene kanye ne-haloalkane derivatives ukuvumela ukuhlanganiswa kokuhlanganiswa komtapo omncane, ngaleyo ndlela kusungulwe ikhono lokusebenzisa lezi zimo kuhlu olubanzi lwama-reagents angaba khona (Umfanekiso 1) .2).
Lungiselela izixazululo ezihlukene ze-sodium azide (0.25 M, 4:1 DMF:H2O), ama-haloalkanes (0.25 M, DMF) nama-alkynes (0.125 M, DMF). Ama-aliquots angu-3 mL esixazululo ngasinye axutshwe futhi ampontshwa nge-reactor ngo-75 µL.min-1 kanye no-150 °C eqoqwe ku-elutate yevolumu engu-100 °C ephelele. .Isixazululo sesampula sagezwa ngamanzi angu-3 × 10 mL. Izingqimba ezinamanzi zahlanganiswa futhi zakhishwa nge-10 mL ye-ethyl acetate;izingqimba zezinto eziphilayo zabe sezihlanganiswa, zagezwa nge-3 x 10 mL ye-brine, zomiswa phezu kwe-MgSO4 futhi zihlungiwe, bese i-solvent ikhishwa ku-vacuo.Amasampuli ahlanzwa ngekholomu ye-chromatography ku-silica gel kusetshenziswa i-ethyl acetate ngaphambi kokuhlaziywa ngenhlanganisela ye-HPLC, 1H NMR, 13C HR-spection ye-HR (i-high resolution mass NMR).
Wonke ama-spectra atholwe kusetshenziswa i-Thermofischer precision Orbitrap mass spectrometer ene-ESI njengomthombo we-ionization.Wonke amasampuli alungiswa kusetshenziswa i-acetonitrile njenge-solvent.
Ukuhlaziywa kwe-TLC kwenziwa kumapuleti e-silica ane-aluminium-backed.
Wonke amasampula ahlaziywa kusetshenziswa isistimu ye-VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) efakwe i-autosampler, ikholomu yephampu ye-oven kanambambili kanye nomtshina we-wavelength eyodwa.Ikholomu esetshenzisiwe kwakuyi-ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Ltd,Scotland Aberones).
Imijovo (5 µL) yenziwe ngokuqondile kusukela kungxube yokusabela okungcolile okuhlanjululiwe (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 mC noma ikholomu engu-4 igcinwe kukholomu engu-4m2 noma i-wangth engu-4m. .
Indawo ephakeme engu-% yesampula ibalwa kusukela endaweni ephakeme kakhulu ye-alkyne esele, umkhiqizo we-triazole kuphela, futhi umjovo wento yokuqala uvumele ukukhonjwa kweziqongo ezifanele.
Wonke amasampula ahlaziywa kusetshenziswa i-Thermo iCAP 6000 ICP-OES.Wonke amazinga okulinganisa alungiswa kusetshenziswa isisombululo esijwayelekile esingu-1000 ppm Cu ku-2% nitric acid (SPEX Certi Prep).Wonke amazinga alungiswe ngesixazululo esingu-5% DMF no-2% HNO3, futhi wonke amasampula ahlanjululwe isixazululo se-DMF esiphindwe ku-20-H3 kusixazululo esingu-20-H3.
I-UAM isebenzisa i-ultrasonic metal welding njengendlela yokubopha izinto ze-foil zensimbi ezisetshenziselwa ukwakha umhlangano wokugcina.I-Ultrasonic metal welding isebenzisa ithuluzi lensimbi elidlidlizayo (elibizwa ngokuthi uphondo noma uphondo lwe-ultrasonic) ukuze ifake ingcindezi kungqimba lwe-foil / ungqimba oluhlanganisiwe ngaphambili oluzohlanganiswa ngenkathi ludlidliza impahla. Uma ukucindezela nokudlidliza kusetshenziswa, ama-oxide aphezu kwempahla angaqhekeka.Ukucindezela okuqhubekayo nokudlidliza kungabangela ukuba i-asperities yezinto ezibonakalayo igoqe 36 .Ukuxhumana okuseduze nokushisa okudalwe endaweni kanye nokucindezela bese kuholela ekubopheni isimo esiqinile ezindaweni ezibonakalayo;kungasiza futhi ukunamathela ngokusebenzisa izinguquko zamandla angaphezulu48.Imvelo yendlela yokubopha inqoba izinkinga eziningi ezihambisana nokushisa okuguquguqukayo kokuncibilika kanye nokushisa okuphezulu ngemva kwemiphumela okukhulunywe ngayo kwamanye amasu okukhiqiza okungeziwe.Lokhu kuvumela ukubopha okuqondile (okungukuthi, ngaphandle kokuguqulwa kwendawo, ama-fillers noma ama-adhesives) wezingqimba eziningi zezinto ezihlukahlukene zibe isakhiwo esisodwa esihlanganisiwe.
Isici sesibili esivumayo se-UAM yizinga eliphakeme lokugeleza kwepulasitiki elibonwa ezintweni zensimbi, ngisho namazinga okushisa aphansi, okungukuthi ngaphansi kwendawo yokuncibilika yezinto zensimbi.Inhlanganisela ye-oscillation ye-ultrasonic kanye nokucindezela kubangela amazinga aphezulu okufuduka komngcele wokusanhlamvu wendawo kanye nokuvuselelwa kabusha ngaphandle kokukhuphuka okukhulu kwezinga lokushisa okuhlotshaniswa ngokujwayelekile nezinto eziningi.Ngesikhathi sokwakhiwa komhlangano wokugcina, lesi sigameko sokuqhuma kwensimbi singaqhuma futhi siqhume ungqimba lwensimbi oluqhumayo. ngesendlalelo.Izinto ezifana nama-optical fibers 49, ama-reinforcement 46, ama-electronics 50, kanye nama-thermocouples (lo msebenzi) wonke ashumekwe ngempumelelo ezakhiweni ze-UAM ukuze kwakheke imihlangano eyinhlanganisela esebenzayo nengenzi lutho.
Kulo msebenzi, kokubili okuhlukene okuhlanganisayo okuhlanganayo kanye namathuba okuxhumana e-UAM kusetshenziswe ukwakha i-microreactor yokugcina ebambe iqhaza yokuqapha izinga lokushisa.
Uma kuqhathaniswa ne-palladium (Pd) nezinye izinto ezisetshenziswayo zensimbi ezivame ukusetshenziswa, i-Cu catalysis inezinzuzo ezimbalwa: (i) Ngokomnotho, i-Cu ibiza kancane kunezinye izinsimbi eziningi ezisetshenziswa ku-catalysis ngakho-ke iyindlela ekhangayo embonini yokucubungula amakhemikhali (ii) Ububanzi be-Cu-catalyzed cross-coupling reactions buyanda futhi bubonakala buhambisana ne-Cu-catalyzed cross-coupling method (i-Cu-catalyzed cross-coupling) ukusabela kwe-zed kusebenza kahle lapho kungekho amanye ama-ligand, Lawa ma-ligand avame ukuhleleka kalula futhi angabizi uma efunwa, kuyilapho lawo asetshenziswa ku-Pd chemistry ngokuvamile ayinkimbinkimbi, ayabiza, futhi azwela emoyeni (iv) Cu, eyaziwa kakhulu ngekhono lawo lokubopha ama-alkynes ekuhlanganiseni, Ngokwesibonelo, i-bimetallic-catalyzed i-Sonogashides ikwazi ukukhuthaza i-Sonogashides ne-chemistry ikwazi ukuhlanganisa i-Cuba i-arylation yama-nucleophiles amaningana ekuphenduleni kohlobo lwe-Ullmann.
Izibonelo ze-heterogenization yazo zonke lezi zimo zisanda kuboniswa phambi kwe-Cu(0) .Lokhu kubangelwa kakhulu imboni yezemithi kanye nokugxila okukhulayo ekubuyiseleni i-metal catalyst kanye nokusetshenziswa kabusha55,56.
Iqalwe ngu-Huisgen ngeminyaka yawo-1960s57, ukusabela kwe-1,3-dipolar cycloaddition phakathi kwe-acetylene ne-azide kuya ku-1,2,3-triazole kuthathwa njengokusabela kokubonisa okuhambisanayo. Umphumela wezingxenye ze-triazole ezingu-1,2,3 zinentshisekelo ngokukhethekile njenge-ejenti ye-pharmacophore ekutholakaleni kwezidakamizwa ezihlukahlukene8 .
Lokhu kusabela kwagxila futhi lapho u-Sharpless nabanye bethula umqondo wokuthi "chofoza i-chemistry"59.Igama elithi "chofoza ikhemistri" lisetshenziselwa ukuchaza isethi eqinile, enokwethenjelwa futhi ekhethiwe yokusabela ekuhlanganiseni okusheshayo kwamakhompiyutha amasha nemitapo yolwazi ehlanganisiwe nge-heteroatom linkage (CXC)60 Ukwenziwa kokwenziwa kwalezi zimo zokusabela kuyizimo ezilula zokusabela, ukusabela kwamanzi okuhlobene nokuphikisana nomkhiqizo we-6, i-oksijini ehlobene nomkhiqizo wabo, i-oksijeni ephezulu ibangelwa ukusabela kwayo, i-oksijini etholakalayo kanye ne-oksijini. 1.
I-classical Huisgen 1,3-dipole cycloaddition ayiyona ingxenye yesigaba "sekhemistri yokuchofoza". Nokho, i-Medal kanye ne-Sharpless babonise ukuthi lo mcimbi wokuhlanganisa we-azide-alkyne wenza u-107 kuya ku-108 ebukhoneni be-Cu(I) uma kuqhathaniswa ne-uncatalyzed 1,3-dipolar chemistry ayidingi ukusabela okuthuthukisiwe kwe-cycload 62ing6. amaqembu noma izimo zokusabela ezinzima kanye nemikhiqizo eseduze nokuguqulwa okuphelele nokukhetha ku-1,4-disubstituted 1,2,3-triazoles (anti- 1,2,3-triazole) esikalini sesikhathi (Umfanekiso 3).
Imiphumela ye-Isometric ye-CycLoLDitions.Cu (I) -I-Huisgen Huisgen CycApplets kuphela isivuno 1,4-3,3-Triambezeles, kanti i-Huisgen-Triazoles, kanti i-Huisgen-Triazoles, kanti i-Huisgen-Triazoles, kanti i-Triazoles ye-Huisgen ngokuvamile ithela ama-1,4-5
Amaphrothokholi amaningi ahilela ukuncishiswa kwemithombo ezinzile ye-Cu(II), njengokuncishiswa kwezinhlobo ze-CuSO4 noma i-Cu(II)/Cu(0) ukuhlanganiswa nosawoti we-sodium.Uma kuqhathaniswa nokunye ukusabela okwenziwe ngensimbi, ukusetshenziswa kwe-Cu(I) kunezinzuzo ezinkulu zokungabizi futhi kulula ukuphatha.
Izifundo zokulebula ze-Kinetic ne-isotopic zika-Worrell et al.65 ibonise ukuthi, esimweni sama-alkynes esibulalayo, izinto ezilinganayo ezimbili zethusi ziyabandakanyeka ekwenzeni kusebenze ukusebenza kabusha kwe-molecule ngayinye ukuya ku-azide.Indlela ehlongozwayo iqhubeka ngendandatho yethusi enamalungu ayisithupha eyakhiwe ngokuxhumanisa kwe-azide ku-σ-bond acetylide yethusi ne-π-bonded copper eyakhiwe yi-copper donor eqinile. , okulandelwa ukubola kweproton ukuze kuhlinzekwe ngemikhiqizo ye-triazole nokuvala umjikelezo we-catalytic.
Nakuba izinzuzo zamadivayisi we-flow chemistry zibhalwe kahle, kube nesifiso sokuhlanganisa amathuluzi okuhlaziya kulezi zinhlelo ze-in-line, in-situ, ukuqapha inqubo66,67.UAM ibonakale iyindlela efanelekile yokuklama nokukhiqiza ama-flow reactors e-3D ayinkimbinkimbi kakhulu enziwe ngezinto ezisebenzayo, ezisebenza ngokushisa okushisayo ezinezinzwa ze-4 ezishumekiwe ngokuqondile ().
I-Aluminium-copper flow reactor eyakhiwe ukukhiqizwa kwe-ultrasonic additive (UAM) enesakhiwo sesiteshi sangaphakathi esiyinkimbinkimbi, ama-thermocouples ashumekiwe kanye ne-catalytic reaction chamber.
Ukuqinisekisa ukuthi ama-reactors akhelwe ukusabela kwe-organic esizayo, izincibilikisi zidinga ukushisisa ngokuphephile ngaphezu kwendawo yokubilisa;zivivinywa ukucindezela nokushisa.Ukuhlolwa kwengcindezi kubonise ukuthi uhlelo lugcina ukucindezela okuzinzile nokuqhubekayo ngisho nokucindezela kwesistimu okwenyuka (1.7 MPa) .Ukuhlolwa kwe-hydrostatic kwenziwa ekamelweni lokushisa kusetshenziswa i-H2O njengoketshezi.
Ukuxhuma i-thermocouple eshumekiwe (Umfanekiso 1) kumshini wokufaka idatha wezinga lokushisa kubonise ukuthi i-thermocouple ibipholile ngo-6 °C (± 1 °C) kunezinga lokushisa elihleliwe ohlelweni lwe-FlowSyn. Ngokuvamile, ukunyuka kwezinga lokushisa ngo-10 °C kubangela ukuphindaphindeka kwezinga lokusabela, ngakho-ke umehluko wezinga lokushisa wamadigri ambalwa nje ngenxa yomehluko ophezulu wezinga lokushisa lomzimba ungashintsha kakhulu izinga lokushisa lomzimba. i-ffusivity yezinto ezisetshenziswa enqubweni yokukhiqiza.Lokhu kudonsa okushisayo kuyahambisana futhi ngakho-ke kungabalwa ekusethweni kwemishini ukuqinisekisa ukuthi izinga lokushisa elinembile liyafinyelelwa futhi likalwe ngesikhathi sokusabela.Ngakho-ke, leli thuluzi lokuqapha eliku-inthanethi lisiza ukulawula okuqinile kokushisa okusabelayo futhi lenze inqubo enembe kakhudlwana kanye nokuthuthukiswa kwezimo ezifanele.Lezi zinzwa zingasetshenziswa futhi ukukhomba amasistimu wokuphendula ama-ruxona amakhulu.
I-reactor evezwe kulo msebenzi iyisibonelo sokuqala sokusetshenziswa kobuchwepheshe be-UAM ekwakhiweni kwama-reactors amakhemikhali futhi ibhekana nemikhawulo eminingana emikhulu okwamanje ehlotshaniswa nokuphrinta kwe-AM/3D kwalawa madivayisi, njengalokhu: (i) ukunqoba izinkinga ezibikiwe ezihlobene nokucutshungulwa kwe-alloy yethusi noma i-aluminium (ii) ukulungiswa kwesiteshi okuthuthukisiwe kwangaphakathi uma kuqhathaniswa ne-powder bed fusion (PBF) noma i-powder bed fusion (PBF) njengamasu okuthungwa okuqinile kwe-laser2 kanye nokukhetha ukuthungwa kwe-laser26 kanye nezindlela zokuthungatha kwe-laser2 ezikhethiwe 6 (SLM) ukuthungwa okunamandla2 (SLM) ukuthungwa okuqinile2 (iii) Ukushisa okuncishisiwe kokucubungula, okwenza kube lula ukuhlanganiswa okuqondile kwezinzwa, okungenakwenzeka kubuchwepheshe be-powder bed, (v) kunqoba izici ezimbi zemishini kanye nokuzwela kwezingxenye zezingxenye ezisekelwe ku-polymer ezinhlobonhlobo zezincibilikizi ezivamile ze-organic17,19.
Ukusebenza kwe-reactor kuboniswe uchungechunge lwe-alkyne azide cycloaddition reactions nge-copper-catalyzed alkyne azide cycloaddition ngaphansi kwezimo zokugeleza okuqhubekayo (Fig. 2) .I-reactor yethusi ephrintiwe nge-ultrasonic echazwe ku-Figure 4 ihlanganiswe nesistimu yokugeleza kwezohwebo futhi isetshenziselwa ukuhlanganiswa kwama-azides omtapo wezincwadi ezihlukahlukene ze-1,4-disubstituted i-3-alkoled-amaqembu okulawula izinga lokushisa kanye ne-alkeneyl reaction 1,4-disubstituted 1,4-disubstituted 3-tricealeled a-alkeneled a-alteraled-1,2. i-halides phambi kwe-sodium chloride (Umfanekiso 3) .Ukusetshenziswa kwendlela yokugeleza okuqhubekayo kunciphisa ukukhathazeka kokuphepha okungavela ezinqubweni ze-batch, njengoba lokhu kusabela kukhiqiza ama-aside intermediates asebenzayo kakhulu futhi ayingozi [317], [318]. kanye ne-iodoethane) (bheka uMdwebo 5).
(Phezulu kwesokunxele) Isikimu sokusetha okusetshenziselwa ukufaka i-reactor ye-3DP ohlelweni lokugeleza (phezulu kwesokudla) esitholwe kuhlelo olulungiselelwe (phansi) lohlelo lwe-Huisgen cycloaddition 57 phakathi kwe-phenylacetylene ne-iodoethane ukuze kuthuthukiswe futhi kuboniswe izinga lokuguqulwa kwamapharamitha athuthukisiwe.
Ngokulawula isikhathi sokuhlala kwama-reagents engxenyeni ye-catalytic ye-reactor kanye nokuqapha ngokucophelela izinga lokushisa lokusabela nge-thermocouple probe edidiyelwe ngokuqondile, izimo zokusabela zingathuthukiswa ngokushesha nangokunembile ngesikhathi esincane nokusetshenziswa kwezinto ezibonakalayo. kanye nezinga lokushisa lokusabela kuthathwa njengemigomo eyisibonelo ebalulekile.Ukusebenzisa isilungisisi esakhelwe ngaphakathi sisebenzisa la magama akhethiwe kukhiqiza isethi yezimo zokusabela eziklanyelwe ukukhulisa izindawo eziphakeme kakhulu zomkhiqizo ngenkathi kunciphisa izindawo eziphakeme kakhulu zokuqala.Lokhu kulungiselelwa kuveze ukuguqulwa okungama-53% komkhiqizo we-triazole, okufana eduze nesibikezelo esiyimodeli esingu-54%.
Ngokusekelwe ezincwadini ezibonisa ukuthi i-copper(I) oxide (Cu2O) ingasebenza njengezinhlobo ze-catalytic ezisebenzayo ezindaweni zethusi eziyiziro-valent kulokhu kusabela, ikhono lokwenza i-oxidize indawo ye-reactor ngaphambi kokwenza ukugeleza kokugeleza kwaphenywa70,71.Ukusabela phakathi kwe-phenylacetylene ne-iodoethane kwase kwenziwa futhi ngaphansi kwezimo ezingcono kakhulu zokulungiswa kwaphinde kwabonwa ukuthi umphumela waqhathaniswa nomphumela omuhle futhi waqhathaniswa nomphumela omuhle. kokokusebenza kokuqala, okubalwe ukuthi kube > 99%.Nokho, ukuqapha kwe-HPLC kubonise ukuthi lokhu kuguqulwa kunciphise kakhulu isikhathi sokusabela esinde ngokweqile kuze kube yimizuzu engaba ngu-90, lapho umsebenzi ubonakale wehla futhi ufinyelela "esimeni esizinzile".Lokhu kubheka kusikisela ukuthi umthombo womsebenzi we-catalytic utholakala endaweni ye-copper oxide engaphezulu kunefomu lensimbi elenziwe yi-zero-tooxilente kalula futhi i-Custrazed Cucuoxilent. akuzona izendlalelo ezizivikelayo.Lokhu kuqeda isidingo sokwengeza umthombo wethusi osizayo(II) wokuhlanganisa71.