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Ukwenziwa kwezinto ezongezelelekileyo kutshintsha indlela abaphandi kunye nabasebenzi bemizi-mveliso abayila kwaye benze ngayo izixhobo zeekhemikhali ukuhlangabezana neemfuno zabo ezithile. Kweli phepha, sixela umzekelo wokuqala we-flow reactor eyenziwe yi-ultrasonic additive manufacturing (UAM) lamination yeshiti yesinyithi eqinileyo eneenxalenye ze-catalytic ezihlanganisiweyo ngokuthe ngqo kunye nezinto zokuva. Itekhnoloji ye-UAM ayipheleli nje ekunqobeni uninzi lwemida enxulumene nokuveliswa kwezinto ezongezelelekileyo zee-chemical reactors, kodwa ikwakhulisa kakhulu amandla ezixhobo ezinjalo. Inani lee-compounds ze-1,2,3-triazole ezibalulekileyo zebhayoloji zenziwe ngempumelelo kwaye zalungiswa yi-Cu-mediated 1,3-dipolar Huisgen cycloaddition reaction esebenzisa i-UAM chemistry facility. Sisebenzisa iipropati ezizodwa ze-UAM kunye nokuqhubekeka kokucubungula ukuhamba, isixhobo siyakwazi ukuququzelela iimpendulo eziqhubekayo kunye nokubonelela ngempendulo yexesha langempela yokujonga nokuphucula iimpendulo.
Ngenxa yeenzuzo zayo ezibalulekileyo kune-bulk counterpart yayo, i-flow chemistry yintsimi ebalulekileyo nekhulayo kwiindawo zemfundo nakwimizi-mveliso ngenxa yokukwazi kwayo ukwandisa ukukhetha nokusebenza kakuhle kokwenziwa kweekhemikhali. Oku kususela ekudalweni kwee-molecule ezilula ze-organic1 ukuya kwiikhompawundi zamayeza2,3 kunye neemveliso zendalo4,5,6. Ngaphezulu kwe-50% yeempendulo kwimizi-mveliso yeekhemikhali ezintle kunye namayeza zinokungenelwa kukuhamba okuqhubekayo7.
Kwiminyaka yakutshanje, bekukho umkhwa okhulayo wamaqela afuna ukutshintsha izixhobo zeglasi zemveli okanye izixhobo zekhemistri yokuhamba ngezixhobo zekhemikhali eziguquguqukayo8. Uyilo oluphindaphindayo, ukwenziwa ngokukhawuleza, kunye nobuchule obunemilinganiselo emithathu (3D) yezi ndlela ziluncedo kwabo bafuna ukwenza ngokwezifiso izixhobo zabo zeseti ethile yeempendulo, izixhobo, okanye iimeko. Ukuza kuthi ga ngoku, lo msebenzi ugxile kakhulu ekusebenziseni iindlela zokuprinta ze-3D ezisekelwe kwi-polymer ezifana ne-sterolithography (SL)9,10,11, i-Fused Deposition Modeling (FDM)8,12,13,14 kunye ne-inkjet printing7,15. , 16. Ukungabikho kokuthembeka kunye nokukwazi kwezixhobo ezinjalo ukwenza uluhlu olubanzi lweempendulo/uhlalutyo lweekhemikhali17, 18, 19, 20 yinto ebalulekileyo ekuthinteleni ukusetyenziswa ngokubanzi kwe-AM kweli candelo17, 18, 19, 20.
Ngenxa yokusetyenziswa okwandayo kwekhemistri yokuhamba kunye neempawu ezilungileyo ezinxulumene ne-AM, kufuneka kuhlolwe iindlela ezingcono eziza kuvumela abasebenzisi ukuba benze imithambo yokusabela ukuhamba ngekhemistri ephuculweyo kunye nobuchule bokuhlalutya. Ezi ndlela kufuneka zivumele abasebenzisi ukuba bakhethe kuluhlu lwezinto ezinamandla aphezulu okanye ezisebenzayo ezikwaziyo ukusebenza phantsi kweemeko ezahlukeneyo zokusabela, kunye nokwenza lula iindlela ezahlukeneyo zokukhupha uhlalutyo kwisixhobo ukuze kuvunyelwe ukujonga nokulawula impendulo.
Enye inkqubo yokwenziwa kwezinto ezongeziweyo enokusetyenziselwa ukuphuhlisa ii-reactors zeekhemikhali ezenziwe ngokwezifiso yi-Ultrasonic Additive Manufacturing (UAM). Le ndlela ye-solid-state sheet lamination isebenzisa ii-ultrasonic vibrations kwi-thin metal foils ukuze zibotshelelwe kunye umaleko ngomaleko ngobushushu obuncinci kunye nenqanaba eliphezulu lokuhamba kweplastiki 21, 22, 23. Ngokungafaniyo nezinye iiteknoloji ze-AM, i-UAM inokudityaniswa ngokuthe ngqo nemveliso yokukhupha, eyaziwa ngokuba yinkqubo yokwenziwa kwe-hybrid, apho i-periodic in-situ numerical control (CNC) milling okanye i-laser processing imisela imo ye-net yomaleko wezinto ezibotshelelweyo 24, 25. Oku kuthetha ukuba umsebenzisi akapheleli kwiingxaki ezinxulumene nokususwa kwezinto zokwakha ezisele kwimijelo emincinci yolwelo, nto leyo edla ngokuba njalo kwiinkqubo zomgubo kunye nolwelo i-AM26,27,28. Le nkululeko yoyilo ikwafikelela ekukhetheni izinto ezikhoyo - i-UAM inokudibanisa iindibaniselwano zezinto ezifanayo ngobushushu nezingafaniyo kwinqanaba lenkqubo enye. Ukukhetha indibaniselwano yezinto ngaphaya kwenkqubo yokunyibilika kuthetha ukuba iimfuno zoomatshini kunye neekhemikhali zezicelo ezithile zinokufezekiswa ngcono. Ukongeza kwi-bonding eqinileyo, enye into eyenzekayo kwi-ultrasonic bonding kukugeleza okuphezulu kwezinto zeplastiki kumaqondo obushushu aphantsi kakhulu29,30,31,32,33. Olu phawu lukhethekileyo lwe-UAM luvumela izinto zoomatshini/zobushushu ukuba zibekwe phakathi kweengqimba zesinyithi ngaphandle komonakalo. Ii-UAM sensors ezifakiweyo zinokwenza kube lula ukuhanjiswa kolwazi lwexesha langempela oluvela kwisixhobo ukuya kumsebenzisi ngokusebenzisa uhlalutyo oludibeneyo.
Umsebenzi wangaphambili wababhali32 ubonise amandla enkqubo ye-UAM okudala izakhiwo ze-metallic 3D microfluidic ezinezakhono zokuva ezifakwe ngaphakathi. Esi sixhobo senzelwe iinjongo zokubeka esweni kuphela. Eli nqaku libonisa umzekelo wokuqala we-microfluidic chemical reactor eyenziwe yi-UAM, isixhobo esisebenzayo esingalawuli nje kuphela kodwa sikwakhuthaza ukuhlanganiswa kweekhemikhali ngezinto ezidityanisiweyo ngokwesakhiwo. Esi sixhobo sidibanisa iingenelo ezininzi ezinxulumene netekhnoloji ye-UAM ekwenzeni izixhobo zeekhemikhali ze-3D, ezinje: ukukwazi ukuguqula uyilo olupheleleyo lwe-3D ngqo kwimodeli yoyilo oluncediswa yikhompyutha (CAD) ibe yimveliso; ukwenziwa kwezinto ezininzi zokudibanisa ubushushu obuphezulu kunye nezinto ezifakelweyo, kunye neesensa zobushushu ezifakwe ngqo phakathi kwemilambo ye-reactant ukuze kulawulwe ngokuchanekileyo kwaye kulawulwe ubushushu be-reaction. Ukubonisa ukusebenza kwe-reactor, ithala leencwadi lee-compounds ze-1,2,3-triazole ezibalulekileyo ngamayeza zenziwe yi-1,3-dipolar Huisgen cycloaddition ye-copper-catalyzed 1,3-dipolar Huisgen cycloaddition. Lo msebenzi ugxininisa indlela ukusetyenziswa kwesayensi yezinto kunye noyilo oluncediswa yikhompyutha olunokuvula ngayo amathuba amatsha namathuba ekhemistri ngophando olubandakanya izifundo ezahlukeneyo.
Zonke izinyibilikisi kunye nee-reagents zithengwe kwiSigma-Aldrich, Alfa Aesar, TCI, okanye kwiFischer Scientific kwaye zasetyenziswa ngaphandle kokucocwa kwangaphambili. I-1H kunye ne-13C NMR spectra ezirekhodwe kwi-400 kunye ne-100 MHz, ngokulandelanayo, zifunyenwe kwi-spectrometer ye-JEOL ECS-400 400 MHz okanye kwi-spectrometer ye-Bruker Avance II 400 MHz ene-CDCl3 okanye (CD3)2SO njenge-solvent. Zonke ii-reaction zenziwe kusetyenziswa iqonga le-Uniqsis FlowSyn flow chemistry.
I-UAM yasetyenziswa ukwenza zonke izixhobo kolu phononongo. Le teknoloji yasungulwa ngo-1999 kwaye iinkcukacha zayo zobugcisa, iiparameter zokusebenza kunye nophuhliso ukusukela oko yasungulwa zinokufundwa kusetyenziswa ezi zinto zilandelayo zipapashiweyo34,35,36,37. Esi sixhobo (Umzobo 1) sasetyenziswa kusetyenziswa inkqubo ye-9 kW SonicLayer 4000® UAM enzima (Fabrisonic, Ohio, USA). Izinto ezikhethiweyo zesixhobo sokuhamba yayiyiCu-110 kunye neAl 6061. ICu-110 inomxholo ophezulu wobhedu (ubuncinci be-99.9% yobhedu), nto leyo eyenza ukuba ibe ngumviwa olungileyo weempendulo ze-copper catalyzed kwaye ke ngoko isetyenziswa njenge "maleko esebenzayo ngaphakathi kwi-microreactor. I-Al 6061 O isetyenziswa njengezinto "ezininzi". , kunye nomaleko wokudibanisa osetyenziselwa uhlalutyo; ukudibanisa izinto ze-alloy ezincedisayo kunye nemeko ye-annealed ngokudibeneyo nomaleko weCu-110. ifunyenwe izinzile ngokweekhemikhali kunye nee-reagents ezisetyenzisiweyo kulo msebenzi. I-Al 6061 O ngokudibeneyo neCu-110 ikwathathwa njengendibaniselwano yezinto ezihambelanayo ze-UAM kwaye ke ngoko zizinto ezifanelekileyo kolu phononongo38,42. Ezi zixhobo zidweliswe kwiTheyibhile 1 ngezantsi.
Amanyathelo okwenziwa kwe-reactor (1) 6061 i-aluminium alloy substrate (2) Ukwenziwa kwe-channel esezantsi kwi-copper foil (3) Ukufakwa kwe-thermocouples phakathi kwee-layers (4) I-channel ephezulu (5) Ukungena kunye ne-outlet (6) I-Monolithic reactor.
Ifilosofi yoyilo lwetshaneli yolwelo kukusebenzisa indlela erhabaxa ukwandisa umgama ohanjwa lulwelo ngaphakathi kwitshiphu ngelixa kugcinwa ubungakanani betshiphu obulawulekayo. Olu nyuko lomgama luyathandeka ukwandisa ixesha loqhagamshelwano lwe-catalyst kunye ne-reactant kunye nokubonelela ngemveliso emihle kakhulu. Iitshiphu zisebenzisa ii-90° bends eziphelweni zendlela ethe tye ukuze kubangele ukuxubana okuguquguqukayo ngaphakathi kwesixhobo44 kunye nokwandisa ixesha lokunxibelelana kolwelo nomphezulu (i-catalyst). Ukuphucula ngakumbi ukuxubana okunokufezekiswa, uyilo lwe-reactor luquka ii-inlets ezimbini ze-reactant ezidityaniswe kwi-Y-connection ngaphambi kokungena kwicandelo le-mixing coil. Umnyango wesithathu, onqumla ukuhamba phakathi kwe-residency yayo, ubandakanyiwe kwisicwangciso seempendulo ze-multi-stage synthesis ezizayo.
Zonke iitshaneli zineprofayili yesikwere (akukho zi-engile ezithambileyo), nto leyo ebangelwa kukugaya rhoqo kwe-CNC okusetyenziselwa ukwenza i-geometry yetshaneli. Ubukhulu betshaneli bukhethwa ukubonelela nge-volumetric yield ephezulu (ye-microreactor), kodwa incinci ngokwaneleyo ukwenza kube lula ukusebenzisana nomphezulu (ii-catalysts) uninzi lweziselo ezikuyo. Ubungakanani obufanelekileyo busekelwe kumava angaphambili ababhali ngezixhobo zokusabela zesinyithi-ulwelo. Ubukhulu bangaphakathi betshaneli yokugqibela yayiyi-750 µm x 750 µm kwaye umthamo we-reactor iyonke yayiyi-1 ml. Isixhumi esakhelwe ngaphakathi (1/4″-28 UNF thread) sifakiwe kuyilo ukuvumela ukudibana lula kwesixhobo nezixhobo zekhemistri yokuhamba kwemali. Ubungakanani betshaneli bunqunyelwe bubukhulu bezinto zefoyile, iimpawu zayo zoomatshini, kunye neeparamitha zokubopha ezisetyenziswa nge-ultrasonics. Kububanzi obuthile bezinto ezinikiweyo, izinto ziya "kugoba" kwitshaneli eyenziweyo. Okwangoku akukho modeli ithile yolu balo, ngoko ke ububanzi betshaneli obuphezulu bezinto kunye noyilo olunikiweyo bumiselwa ngovavanyo, apho ububanzi be-750 µm abuyi kubangela ukugoba.
Ubume (isikwere) setshaneli bumiselwa kusetyenziswa isixhobo sokusika isikwere. Ubume kunye nobukhulu betshaneli bunokutshintshwa koomatshini be-CNC kusetyenziswa izixhobo zokusika ezahlukeneyo ukuze kufunyanwe amazinga okuhamba kunye neempawu ezahlukeneyo. Umzekelo wokudala itshaneli egobileyo enesixhobo se-125 µm unokufumaneka kwi-Monaghan45. Xa umaleko wefoyile usetyenziswa ngokuthe tyaba, ukusetyenziswa kwezinto zefoyile kwitshaneli kuya kuba nomphezulu othe tyaba (isikwere). Kulo msebenzi, i-contour yesikwere yasetyenziswa ukugcina ulungelelwaniso lwetshaneli.
Ngexesha lokumiswa okucwangcisiweyo kwimveliso, izinzwa zobushushu ze-thermocouple (uhlobo K) zakhiwe ngqo kwisixhobo phakathi kwamaqela etshaneli ephezulu nesezantsi (Umzobo 1 - inqanaba lesi-3). Ezi thermocouples zinokulawula utshintsho lobushushu ukusuka kwi--200 ukuya kwi-1350 °C.
Inkqubo yokubeka isinyithi yenziwa yi-UAM horn isebenzisa i-metal foil 25.4 mm ububanzi kunye ne-150 microns ubukhulu. Ezi layers ze-foil ziqhagamshelwe kuluhlu lwemicu ekufutshane ukuze igubungele yonke indawo yokwakha; ubungakanani bezinto ezifakweyo bukhulu kunemveliso yokugqibela njengoko inkqubo yokukhupha idala imo yokugqibela ecocekileyo. I-CNC machining isetyenziselwa umatshini i-contours yangaphandle neyangaphakathi yesixhobo, nto leyo ebangela ukugqitywa komphezulu wesixhobo kunye nemijelo ehambelana nesixhobo esikhethiweyo kunye neeparameters zenkqubo ye-CNC (kulo mzekelo, malunga ne-1.6 µm Ra). Ukutshiza kunye nomatshini we-ultrasonic oqhubekayo, oqhubekayo, kusetyenziswa kuyo yonke inkqubo yokuvelisa yesixhobo ukuqinisekisa ukuchaneka kobukhulu kuyagcinwa kwaye inxalenye egqityiweyo ihlangabezana namanqanaba okuchaneka kwe-CNC fine milling. Ububanzi betshaneli esetyenziselwa esi sixhobo buncinci ngokwaneleyo ukuqinisekisa ukuba izinto ze-foil "azigobi" kwitshaneli yolwelo, ngoko ke itshaneli inecandelo elinqamlezileyo lesikwere. Izikhewu ezinokubakho kwi-foil material kunye neeparameters zenkqubo ye-UAM zichongiwe ngovavanyo liqabane lokuvelisa (Fabrisonic LLC, e-USA).
Izifundo zibonise ukuba kwi-interface 46, 47 ye-UAM compound akukho kusasazeka kuncinci kwezinto ngaphandle konyango olongezelelweyo lobushushu, ngoko ke kwizixhobo ezikulo msebenzi umaleko we-Cu-110 uhlala wahlukile kumaleko we-Al 6061 kwaye utshintsha kakhulu.
Faka i-pre-calibrated back pressure regulator (BPR) kwi-250 psi (1724 kPa) phantsi kwe-reactor uze upompe amanzi kwi-reactor ngesantya se-0.1 ukuya kwi-1 ml min-1. Uxinzelelo lwe-reactor lujongwe kusetyenziswa i-FlowSyn pressure transducer eyakhelwe kwinkqubo ukuqinisekisa ukuba inkqubo inokugcina uxinzelelo oluzinzileyo. Ii-gradients zobushushu ezinokubakho kwi-flow reactor zivavanyiwe ngokujonga nawuphi na umahluko phakathi kwee-thermocouples ezakhiwe kwi-reactor kunye nee-thermocouples ezakhiwe kwi-heating plate ye-FlowSyn chip. Oku kufezekiswa ngokutshintsha ubushushu be-hotplate obucwangcisiweyo phakathi kwe-100 kunye ne-150 °C kwii-25 °C increments kunye nokubeka esweni nawuphi na umahluko phakathi kobushushu obucwangcisiweyo kunye nobo burekhodiweyo. Oku kufezekisiwe kusetyenziswa i-tc-08 data logger (PicoTech, Cambridge, UK) kunye nesoftware yePicoLog ehamba nayo.
Iimeko zempendulo ye-cycloaddition ye-phenylacetylene kunye ne-iodoethane zilungiselelwe (iScheme 1-Cycloaddition ye-phenylacetylene kunye ne-iodoethane, iScheme 1-Cycloaddition ye-phenylacetylene kunye ne-iodoethane). Olu phuculo lwenziwe kusetyenziswa indlela epheleleyo yoyilo lwe-factorial of experiments (DOE), kusetyenziswa ubushushu kunye nexesha lokuhlala njengezinto eziguquguqukayo ngelixa kulungiswa umlinganiselo we-alkyne:azide kwi-1:2.
Izisombululo ezahlukeneyo ze-sodium azide (0.25 M, 4:1 DMF:H2O), iodoethane (0.25 M, DMF), kunye ne-phenylacetylene (0.125 M, DMF) zalungiswa. I-aliquot ye-1.5 ml yesisombululo ngasinye yaxutywa yaza yaphonswa kwi-reactor ngesantya sokuhamba kunye nobushushu obufunekayo. Impendulo yemodeli yathathwa njengomlinganiselo wendawo ephezulu yemveliso ye-triazole kwizinto zokuqala ze-phenylacetylene kwaye yamiselwa kusetyenziswa i-high performance liquid chromatography (HPLC). Ukuhambelana kohlalutyo, zonke iimpendulo zathathwa kwangoko emva kokuba umxube wempendulo ushiye i-reactor. Uluhlu lweeparameter ezikhethiweyo zokwenziwa ngcono ziboniswe kwiTheyibhile 2.
Zonke iisampulu zihlalutywe kusetyenziswa inkqubo yeChromaster HPLC (VWR, PA, USA) equlathe ipompo ye-quaternary, i-oven yekholamu, i-variable wavelength UV detector kunye ne-autosampler. Ikholamu yayiyi-Equivalence 5 C18 (VWR, PA, USA), 4.6 x 100 mm, 5 µm ubukhulu bamasuntswana, igcinwe kwi-40°C. I-solvent yayiyi-isocratic methanol:water 50:50 kwisantya sokuhamba se-1.5 ml·min-1. Umthamo wenaliti yayiyi-5 μl kwaye ubude bobude be-detector babuyi-254 nm. Indawo ye-% peak yesampulu ye-DOE ibalwe kwiindawo ze-peak zeemveliso ze-alkyne kunye ne-triazole ezisele kuphela. Ukungeniswa kwezinto zokuqala kwenza kube nokwenzeka ukuchonga iincochoyi ezifanelekileyo.
Ukudibanisa iziphumo zohlalutyo lwe-reactor kunye nesoftware ye-MODDE DOE (Umetrics, Malmö, Sweden) kuvumele uhlalutyo olupheleleyo lweziphumo kunye nokugqitywa kweemeko ezifanelekileyo zokuphendula kule cycloaddition. Ukusebenzisa i-optimizer eyakhelwe ngaphakathi kunye nokukhetha onke amagama abalulekileyo emodeli kudala iseti yeemeko zokuphendula ezenzelwe ukwandisa indawo ephezulu yemveliso ngelixa kunciphisa indawo ephezulu ye-acetylene feedstock.
Ukuxinana komphezulu wobhedu kwigumbi lokusabela kwe-catalytic kufezekisiwe kusetyenziswa isisombululo se-hydrogen peroxide (36%) esihamba kwigumbi lokusabela (isantya sokuhamba = 0.4 ml min-1, ixesha lokuhlala = 2.5 min) ngaphambi kokwenziwa kwethala leencwadi ngalinye le-triazole compound.
Nje ukuba iimeko ezifanelekileyo zichongiwe, zafakwa kuluhlu lwee-acetylene kunye ne-haloalkane derivatives ukuvumela ukuhlanganiswa kwethala leencwadi elincinci lokwenziwa kwezinto, ngaloo ndlela kumiselwa ithuba lokusebenzisa ezi meko kuluhlu olubanzi lwee-reagents ezinokubakho (Umzobo 1). 2).
Lungisa izisombululo ezahlukeneyo ze-sodium azide (0.25 M, 4:1 DMF:H2O), ii-haloalkanes (0.25 M, DMF), kunye nee-alkynes (0.125 M, DMF). Ii-aliquots ze-3 ml yesisombululo ngasinye zixutywe zaza zapontshwa kwi-reactor ngesantya se-75 µl/min kunye nobushushu be-150°C. Umthamo wonke waqokelelwa kwi-vial waza waxutywa ne-10 ml ye-ethyl acetate. Isisombululo sesampuli sahlanjwa nge-3 x 10 ml yamanzi. Iileya zamanzi zadityaniswa zaza zakhutshwa nge-10 ml ye-ethyl acetate, emva koko iileya ze-organic zadityaniswa, zahlanjwa nge-3 × 10 ml ye-brine, zomiswa phezu kwe-MgSO 4 zaza zahluzwa, emva koko i-solvent yasuswa kwi-vacuo. Iisampulu zacocwa yi-silica gel column chromatography kusetyenziswa i-ethyl acetate ngaphambi kohlalutyo ngokudibanisa i-HPLC, 1H NMR, 13C NMR kunye ne-high resolution mass spectrometry (HR-MS).
Zonke ii-spectra zifunyenwe kusetyenziswa i-Thermofischer Precision Orbitrap mass spectrometer ene-ESI njengomthombo we-ionization. Zonke iisampuli zilungiselelwe kusetyenziswa i-acetonitrile njenge-solvent.
Uhlalutyo lwe-TLC lwenziwe kwiipleyiti ze-silica ezine-substrate ye-aluminium. Iipleyiti ziboniswe ngokukhanya kwe-UV (254 nm) okanye i-vanillin staining kunye nokufudumeza.
Zonke iisampulu zihlalutywe kusetyenziswa inkqubo ye-VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) exhotyiswe nge-autosampler, i-binary pump ene-column oven kunye ne-single wavelength detector. Kusetyenziswe ikholamu ye-ACE Equivalence 5 C18 (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., e-Aberdeen, eScotland).
Iinaliti (5 µl) zenziwe ngokuthe ngqo kumxube we-diluted crude reaction (1:10 dilution) zaza zahlalutywa ngamanzi:methanol (50:50 okanye 70:30), ngaphandle kwezinye iisampuli ezisebenzisa inkqubo ye-solvent ye-70:30 (ebizwa ngokuba yi-star number ) kwisantya sokuhamba se-1.5 ml/min. Ikholamu igcinwe kwi-40°C. Ububanzi bomtshini wokuxilonga yi-254 nm.
Indawo yencochoyi yesampuli ibalwa ukusuka kwindawo yencochoyi ye-alkyne eseleyo, imveliso ye-triazole kuphela, kwaye ukungeniswa kwezinto zokuqala kwenze kwaba nokwenzeka ukuchonga iincochoyi ezifanelekileyo.
Zonke iisampulu zihlalutywe kusetyenziswa iThermo iCAP 6000 ICP-OES. Zonke imigangatho yokulinganisa ilungiselelwe kusetyenziswa isisombululo esiqhelekileyo se-1000 ppm Cu kwi-2% nitric acid (SPEX Certi Prep). Zonke imigangatho zilungiselelwe kwisisombululo se-5% DMF kunye ne-2% HNO3, kwaye zonke iisampulu zixutywe amaxesha angama-20 ngesisombululo sesampuli se-DMF-HNO3.
I-UAM isebenzisa i-ultrasonic metal welding njengendlela yokudibanisa i-metal foil esetyenziselwa ukwenza i-assembly yokugqibela. I-Ultrasonic metal welding isebenzisa isixhobo sesinyithi esingcangcazelayo (esibizwa ngokuba yi-horn okanye i-ultrasonic horn) ukufaka uxinzelelo kwi-foil/umaleko odibeneyo ngaphambili ukuze udityaniswe/udityaniswe ngaphambili ngokungcangcazela izinto. Ukuze kusebenze ngokuqhubekayo, i-sonotrode inomfanekiso we-cylindrical kwaye iqengqeleka phezu komphezulu wezinto, incamathisele yonke indawo. Xa kusetyenziswa uxinzelelo kunye nokungcangcazela, ii-oxides kumphezulu wezinto zinokuqhekeka. Uxinzelelo oluqhubekayo kunye nokungcangcazela kunokukhokelela ekutshatyalalisweni koburhabaxa bezinto 36. Ukudibana ngokusondeleyo nobushushu kunye noxinzelelo olukwindawo ethile emva koko kukhokelela kwi-solid phase bond kwiindawo zokudibana kwezinto; inokukhuthaza ukuhlangana ngokutshintsha amandla omphezulu48. Uhlobo lwendlela yokubopha luyoyisa iingxaki ezininzi ezinxulumene nobushushu obuguquguqukayo bokunyibilika kunye neziphumo zobushushu obuphezulu ezikhankanyiweyo kwezinye iiteknoloji zokuvelisa ezongeziweyo. Oku kuvumela uqhagamshelo oluthe ngqo (oko kukuthi ngaphandle kokuguqulwa komphezulu, izizalisi okanye izincamathelisi) zeeleya ezahlukeneyo zezinto ezahlukeneyo kwisakhiwo esinye esidibeneyo.
Into yesibini eluncedo kwi-CAM kukunyuka kokuhamba kweplastiki okubonwa kwizinto zesinyithi nokuba kubushushu obuphantsi, oko kukuthi, ngaphantsi kakhulu kwinqanaba lokunyibilika kwezinto zesinyithi. Ukudibana kokungcangcazela kwe-ultrasonic kunye noxinzelelo kubangela inqanaba eliphezulu lokufuduka kwemida yengqolowa yendawo kunye nokuphinda kusetyenziswe ngaphandle kokunyuka okukhulu kobushushu okuqhele ukunxulunyaniswa nezinto ezininzi. Ngexesha lokudalwa kwendibano yokugqibela, le nto ingasetyenziselwa ukufaka izinto ezisebenzayo nezingasebenziyo phakathi kweengqimba zefoyile yesinyithi, umaleko ngomaleko. Izinto ezifana ne-optical fiber 49, ukuqinisa 46, i-electronics 50 kunye ne-thermocouples (lo msebenzi) zihlanganiswe ngempumelelo kwizakhiwo ze-UAM ukudala iindibano ezisebenzayo nezingasebenziyo.
Kulo msebenzi, zombini iindlela ezahlukeneyo zokubopha izinto kunye neendlela zokudibanisa i-UAM zisetyenzisiwe ukudala i-microreactor efanelekileyo yokulawula ubushushu be-catalytic.
Xa kuthelekiswa ne-palladium (Pd) kunye nezinye ii-catalysts zesinyithi ezisetyenziswa rhoqo, i-Cu catalysis ineengenelo ezininzi: (i) Ngokwezoqoqosho, i-Cu ixabisa kancinci kunezinye iintsimbi ezininzi ezisetyenziswa kwi-catalysis kwaye ke ngoko lukhetho olunomtsalane kushishino lweekhemikhali (ii) uluhlu lwee-Cu-catalyzed cross-coupling reactions luyanda kwaye lubonakala luhambelana kancinci neendlela ezisekwe kwi-Pd51, 52, 53 (iii) Ii-Cu-catalyzed reactions zisebenza kakuhle xa kungekho ezinye ii-ligands. Ezi ligands zihlala zilula ngokwesakhiwo kwaye azibizi kakhulu. ukuba ziyafunwa, ngelixa ezo zisetyenziswa kwi-Pd chemistry zihlala ziyinkimbinkimbi, zibiza kakhulu, kwaye zinomoya obuthathaka (iv) I-Cu, eyaziwa kakhulu ngokukwazi kwayo ukudibanisa ii-alkynes kwi-synthesis, njenge-Sonogashira's bimetallic catalyzed coupling kunye ne-cycloaddition kunye ne-azides (click chemistry) (v) I-Cu inokukhuthaza i-arylation yezinye ii-nucleophiles kwi-Ullmann-type reactions.
Kutshanje, imizekelo yokwahluka kwazo zonke ezi mpendulo xa kukho i-Cu(0) ibonakalisiwe. Oku kungenxa kakhulu kushishino lwamayeza kunye nokugxila okukhulayo ekubuyiseleni nasekusebenziseni kwakhona ii-catalysts zesinyithi55,56.
I-1,3-dipolar cycloaddition reaction phakathi kwe-acetylene kunye ne-azide kwi-1,2,3-triazole, eyaqala ukucetywa nguHuisgen ngeminyaka yoo-196057, ithathwa njenge-synergistic demonstration reaction. Iziqwenga ze-1,2,3 triazole eziphumayo zinomdla kakhulu njenge-pharmacophore ekufumaneni amayeza ngenxa yezicelo zazo zebhayoloji kunye nokusetyenziswa kwazo kwiiarhente ezahlukeneyo zonyango58.
Le mpendulo yafumana ingqwalasela entsha xa uSharpless nabanye bazisa ingcamango "yekhemistri yokucofa"59. Igama elithi "ikhemistri yokucofa" lisetyenziselwa ukuchaza iseti eqinileyo nekhethiweyo yeempendulo zokwenziwa ngokukhawuleza kweekhompawundi ezintsha kunye neelayibrari ezidibeneyo kusetyenziswa i-heteroatomic bonding (CXC)60. Ukutsala okwenziwa kwezi mpendulo kungenxa yemveliso ephezulu enxulumene nazo. iimeko zilula, ukumelana neoksijini namanzi, kwaye ukwahlulwa kwemveliso kulula61.
I-cycloaddition yeklasikhi ye-1,3-dipole Huisgen ayiweli kudidi lwe-"click chemistry". Nangona kunjalo, iMedal kunye neSharpless zibonise ukuba esi siganeko sokudibanisa i-azide-alkyne sidlula kwi-107-108 phambi kwe-Cu(I) xa kuthelekiswa nokukhawuleziswa okukhulu kwisantya se-cycloaddition ye-1,3-dipolar 62,63 engeyiyo i-catalytic. Le ndlela yokusabela ephucukileyo ayifuni ukukhusela amaqela okanye iimeko zokusabela ezinzima kwaye ibonelela ngokuguqulwa okupheleleyo kunye nokukhetha kwi-1,4-dissubstituted 1,2,3-triazoles (anti-1,2,3-triazoles) ngokuhamba kwexesha (Umzobo 3).
Iziphumo ze-Isometric ze-cycloadditions ze-Huisgen zesiqhelo kunye ne-copper-catalyzed. Ii-cycloadditions ze-Huisgen ze-Cu(I)-catalyzed Huisgen zinika kuphela i-1,4-dissubstituted 1,2,3-triazoles, ngelixa ii-cycloadditions ze-Huisgen ezibangelwa ngubushushu zihlala zinika i-1,4- kunye ne-1,5-triazoles umxube we-1:1 we-azole stereoisomers.
Uninzi lweenkqubo zibandakanya ukunciphisa imithombo ezinzileyo yeCu(II), njengokunciphisa iCuSO4 okanye iCu(II)/Cu(0) compound xa idibene nesodium salts. Xa kuthelekiswa nezinye ii-metal catalyzed reactions, ukusetyenziswa kweCu(I) kuneenzuzo eziphambili zokuba ayibizi kakhulu kwaye kulula ukuyiphatha.
Izifundo zeKinetic kunye ne-isotopic ezenziwe nguWorrell et al. 65 zibonise ukuba kwimeko ye-terminal alkynes, ii-equivalents ezimbini ze-copper ziyabandakanyeka ekuvuseleleni i-reactivity ye-molecule nganye malunga ne-azide. Le ndlela icetywayo iqhubeka ngendandatho yesinyithi yobhedu enamalungu amathandathu eyenziwe ngokudityaniswa kwe-azide kwi-acetylide yobhedu ene-σ-bonded kunye ne-π-bonded copper njenge-ligand ezinzileyo yomnikelo. Ii-derivatives ze-copper triazolyl zenziwa ngenxa yokucuthwa kwendandatho kulandelwa kukuqhekeka kwe-proton ukwenza iimveliso ze-triazole kunye nokuvala umjikelo we-catalytic.
Nangona iingenelo zezixhobo zekhemistri yokuhamba zibhalwe kakuhle, bekukho umnqweno wokudibanisa izixhobo zohlalutyo kwezi nkqubo ukuze kujongwe inkqubo ngexesha langempela kwi-situ66,67. I-UAM ibonakalise ukuba yindlela efanelekileyo yokuyila nokuvelisa ii-reactors ze-3D flow ezintsonkothileyo kakhulu ezivela kwizinto ezisebenzayo neziqhuba ubushushu ezine-sensor efakwe ngqo (Umzobo 4).
I-aluminiyam-copper flow reactor eyenziwe yi-ultrasonic additive manufacturing (UAM) enesakhiwo se-internal channel esintsonkothileyo, ii-thermocouples ezakhelwe ngaphakathi kunye negumbi le-catalytic reaction. Ukuze ubone iindlela zangaphakathi zolwelo, iprototype ecacileyo eyenziwe kusetyenziswa i-stereolithography nayo iyaboniswa.
Ukuqinisekisa ukuba ii-reactors zenzelwe ii-organic reactions zexesha elizayo, izinyibilikisi kufuneka zifudunyezwe ngokukhuselekileyo ngaphezu kweqondo lazo lokubila; ziyavavanywa uxinzelelo kunye nobushushu. Uvavanyo loxinzelelo lubonise ukuba inkqubo igcina uxinzelelo oluzinzileyo noluqhubekayo nokuba kuxinzelelo oluphezulu kwinkqubo (1.7 MPa). Uvavanyo lwe-hydrostatic lwenziwe kubushushu begumbi kusetyenziswa i-H2O njengolwelo.
Ukuqhagamshela i-thermocouple eyakhelwe ngaphakathi (uMfanekiso 1) kwi-logger yedatha yobushushu kubonise ukuba ubushushu be-thermocouple babuyi-6 °C (± 1 °C) ngaphantsi kobushushu obucwangcisiweyo kwinkqubo ye-FlowSyn. Ngokwesiqhelo, ukunyuka kobushushu nge-10°C kuphinda kabini izinga lokuphendula, ngoko ke umahluko wobushushu weedigri ezimbalwa nje unokutshintsha izinga lokuphendula kakhulu. Lo mahluko ubangelwa kukulahleka kobushushu kuyo yonke i-RPV ngenxa yokwanda kobushushu okuphezulu kwezinto ezisetyenziswa kwinkqubo yokuvelisa. Olu tshintsho lobushushu luhlala luhleli kwaye ke ngoko lunokuthathelwa ingqalelo xa kusetwa izixhobo ukuqinisekisa ukuba ubushushu obuchanekileyo bufikelelwa kwaye bulinganiswa ngexesha lokuphendula. Ke ngoko, esi sixhobo sokujonga kwi-intanethi senza kube lula ukulawula ubushushu bokuphendula kwaye sinegalelo ekwenzeni ngcono inkqubo kunye nophuhliso lweemeko ezifanelekileyo. Ezi sensors zinokusetyenziswa ukubona iimpendulo ezingaqhelekanga kunye nokuthintela iimpendulo ezibalekayo kwiinkqubo ezinkulu.
I-reactor evezwe kweli phepha ngumzekelo wokuqala wokusetyenziswa kwetekhnoloji ye-UAM ekwenziweni kwee-reactors zeekhemikhali kwaye ijongana nemida emininzi emikhulu enxulumene nokuprintwa kwe-AM/3D kwezi zixhobo, ezinje: (i) Ukoyisa iingxaki eziphawulweyo ezinxulumene nokucutshungulwa kobhedu okanye i-aluminium alloy (ii) ukuphucuka kwesisombululo setshaneli yangaphakathi xa kuthelekiswa neendlela zokunyibilikisa i-powder bed (PBF) ezifana nokunyibilikisa i-laser selective (SLM)25,69 Ukuhamba kakubi kwezinto kunye nokuthungwa komphezulu orhabaxa26 (iii) ubushushu obuphantsi bokucubungula, okunceda izinzwa zokudibanisa ngqo, into engenakwenzeka kwitekhnoloji ye-powder bed, (v) ukoyisa iipropati ezimbi zoomatshini kunye novakalelo lwezinto ezisekwe kwi-polymer kwiisombululi ezahlukeneyo ze-organic eziqhelekileyo17,19.
Ukusebenza kwe-reactor kuboniswe luluhlu lwee-alkinazide cycloaddition reactions ze-copper-catalyzed phantsi kweemeko zokuhamba okuqhubekayo (Umzobo 2). I-reactor ye-copper eprintiweyo ye-ultrasonic eboniswe kumzobo 4 yadibaniswa nenkqubo yokuhamba kwemali kwaye yasetyenziswa ukwenza ilayibrari ye-azide ye-1,4-dissubstituted 1,2,3-triazoles ezahlukeneyo kusetyenziswa i-reaction elawulwa bubushushu ye-acetylene kunye ne-alkyl group halides phambi kwe-sodium chloride (Umzobo 3). Ukusetyenziswa kwendlela yokuhamba rhoqo kunciphisa imiba yokhuseleko enokuvela kwiinkqubo ze-batch, kuba le reaction ivelisa i-azide intermediates esabela kakhulu kwaye inobungozi [317], [318]. Ekuqaleni, i-reaction yayilungiselelwe i-cycloaddition ye-phenylacetylene kunye ne-iodoethane (Iskimu 1 - I-Cycloaddition ye-phenylacetylene kunye ne-iodoethane) (jonga uMfanekiso 5).
(Phezulu ekhohlo) Isicwangciso sokuseta esisetyenzisiweyo ukufaka i-reactor ye-3DP kwinkqubo yokuhamba (phezulu ekunene) efunyenwe kwisicwangciso esilungiselelweyo (esisezantsi) se-Huisgen 57 cycloaddition scheme phakathi kwe-phenylacetylene kunye ne-iodoethane ukuze kuphuculwe kwaye kuboniswe iiparameter zezinga lokuguqulwa elilungiselelweyo lempendulo.
Ngokulawula ixesha lokuhlala kwee-reactants kwicandelo le-catalytic le-reactor kunye nokujonga ngononophelo ubushushu be-reaction nge-sensor ye-thermocouple edityaniswe ngqo, iimeko ze-reaction zinokulungiswa ngokukhawuleza nangokuchanekileyo ngexesha elincinci kunye nezixhobo. Kwafunyaniswa ngokukhawuleza ukuba ukuguqulwa okuphezulu kufezekisiwe kusetyenziswa ixesha lokuhlala lemizuzu eli-15 kunye nobushushu be-reaction obuyi-150°C. Kunokubonwa kwi-coefficient plot yesoftware ye-MODDE ukuba zombini ixesha lokuhlala kunye nobushushu be-reaction zithathwa njengeemeko ezibalulekileyo zemodeli. Ukusebenzisa i-optimizer eyakhelwe ngaphakathi usebenzisa ezi meko zikhethiweyo kudala iseti yeemeko ze-reaction ezenzelwe ukwandisa iindawo ze-peak zemveliso ngelixa kunciphisa iindawo ze-peak zezixhobo zokuqala. Olu phuculo luvelise ukuguqulwa kwe-53% yemveliso ye-triazole, ehambelana ngqo noqikelelo lwemodeli lwama-54%.