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Imveliso eyongezelelweyo iyayitshintsha indlela abaphandi kunye nosomashishini abayila kwaye benze izixhobo zeekhemikhali ukuhlangabezana neemfuno zabo ezithile. Kulo msebenzi, sinika ingxelo yomzekelo wokuqala we-reactor ehambayo eyenziwe yi-slid-state metal sheet lamination technique Ultrasonic Additive Manufacturing (UAM) enamalungu adityanisiweyo adityanisiweyo kunye nezinto ezizivayo. Ayipheleli nje ekubeni itekhnoloji ye-UAM yoyise uninzi lwemida kodwa ikwayanyaniswa nezixhobo zokongezwayo ngoku, kodwa iphinda inyuse kakhulu izixhobo zokwenziwa kweekhemikhali. uchungechunge lwezinto eziphilayo ezibalulekileyo ze-1,4-disubstituted 1,2,3-triazole iikhompawundi zenziwe ngempumelelo kwaye zalungiswa yi-Cu-mediated Huisgen 1,3-dipolar cycloaddition reaction usebenzisa i-UAM chemistry set-up.
Ngenxa yeenzuzo zayo ezibalulekileyo ngaphezu komlingani wayo obuninzi, ikhemistri ejikelezayo iyintsimi ebalulekileyo kwaye ikhula kwimimiselo yezemfundo kunye nezoshishino ngenxa yokukwazi ukunyusa ukukhetha kunye nokusebenza kakuhle kwe-chemical synthesis.Olu lusuka kwi-molecule elula ye-organic formation1 ukuya kwi-pharmaceutical compounds2,3 kunye neemveliso zendalo4,5,6. Ngaphezulu kwe-50% yeempendulo kwimichiza emihle kunye namashishini axuba amayeza anokuzuza ngokusetyenziswa kwenkqubo yokuhamba eqhubekayo7.
Kwiminyaka yakutshanje, kukho umkhwa okhulayo wamaqela afuna ukubuyisela izixhobo zeglasi okanye ukuhamba kwekhemistri kunye ne-customizable additive production (AM) chemistry "reaction vessels"8.Uyilo oluphindaphindayo, imveliso ekhawulezileyo, kunye ne-3-dimensional (3D) ubuchule bobu buchule buluncedo kwabo banqwenela ukwenza izixhobo zabo ngokwezifiso zabo kwiseti ethile yokusabela, umhla, izixhobo, okanye iimeko zokusebenza ezikhethekileyo. ubuchule boshicilelo be-polymer-based 3D njenge-stereolithography (SL)9,10,11, i-fused deposition modeling (FDM)8,12,13,14 kunye noshicilelo lwe-inkjet 7, 15, 16. Ukunqongophala kokuqina kunye nokukwazi kwezixhobo ezinjalo ukwenza uluhlu olubanzi lweekhemikhali zokusabela / ukuhlalutya okukhulu kwe-18207, ukuphunyezwa okukhulu kwe-182019, ye-AM kule ntsimi17, 18, 19, 20.
Ngenxa yokwanda kokusetyenziswa kwekhemistri kunye neempawu ezifanelekileyo ezinxulumene ne-AM, kukho imfuneko yokuphonononga iindlela eziphucukileyo ezivumela abasebenzisi ukuba benze iinqanawa zokusabela ukuhamba kunye nekhemikhali eyongeziweyo kunye nezakhono zokuhlalutya. Ezi ndlela kufuneka zenze abasebenzisi bakwazi ukukhetha kuluhlu lwezinto ezinamandla kakhulu okanye ezisebenzayo ezikwaziyo ukuphatha uluhlu olubanzi lweemeko zokusabela, ngelixa zikwaququzelela iindlela ezahlukeneyo zokujonga ukuphendulwa kwesixhobo kunye nokuvumela ukujongwa kwemveliso kunye nokulawula ukusabela kwisixhobo.
Enye inkqubo yokuvelisa i-additive enekhono lokuphuhlisa i-reactors yekhemikhali yesiko i-Ultrasonic Additive Manufacturing (UAM) .Le ndlela eqinile ye-lamination sheet isebenzisa i-oscillations ye-ultrasonic kwii-foil zetsimbi ezinqabileyo ukwenzela ukuba zidibanise kunye noluhlu kunye nobushushu obuncinci kunye neqondo eliphezulu lokuhamba kweplastiki 21, 22, 23 njengenkqubo yokuvelisa i-hybrid, apho i-in-situ periodic computer numberal control (CNC) milling okanye i-laser machining ichaza ubume bomnatha bomaleko wezinto ezidityanisiweyo 24, 25.Oku kuthetha ukuba umsebenzisi akakhawulelwanga ziingxaki ezinxulumene nokususa izinto ezishiyekileyo zokwakha ezikrwada kumajelo amancinci, okuhlala kunjalo ngomgubo kunye nolwelo olunokwandiswa kwezixhobo ze-AM26,27. I-bond thermally efanayo kunye ne-dissimilar material combinations in a single process process.Ukukhethwa kwezinto ezidityanisiweyo ngaphaya kwenkqubo yokunyibilika kuthetha ukuba iimfuno zoomatshini kunye neekhemikhali zezicelo ezithile zinokuhlangatyezwa ngcono.Ukongezelela kwi-solid state bonding, enye into eyenzeka ngexesha lokubambisana kwe-ultrasonic ukuhamba okuphezulu kwezinto zeplastiki kumaqondo okushisa aphantsi kakhulu29,30,31,31,32,33. iileyile ngaphandle komonakalo.Iinzwa ezifakwe kwi-UAM zinokuququzelela ukuhanjiswa kolwazi lwexesha langempela ukusuka kwisixhobo ukuya kumsebenzisi ngokusebenzisa uhlalutyo oludibeneyo.
Umsebenzi odlulileyo wababhali32 ubonise amandla enkqubo ye-UAM ukwenza i-metallic 3D izakhiwo ze-microfluidic kunye nobuchule obudibeneyo bokuva.Le yisixhobo kuphela sokubeka iliso.Eli phepha libonisa umzekelo wokuqala we-microfluidic chemical reactor eyenziwe yi-UAM; isixhobo esisebenzayo esingagcini nje ngokubeka iliso kodwa siphinde sibangele ukuhlanganiswa kweekhemikhali ngokusebenzisa izinto ezidityanisiweyo ze-catalyst.Isixhobo sidibanisa iingenelo ezininzi ezinxulumene neteknoloji ye-UAM kwi-3D yokuvelisa izixhobo zekhemikhali, ezifana: ukukwazi ukuguqula ii-3D ezipheleleyo zoyilo ngokuthe ngqo kwiimodeli ze-computer-aid (CAD) kwimveliso; ukuveliswa kwezinto ezininzi ukudibanisa i-conductivity ephezulu ye-thermal kunye nezixhobo ze-catalytic; Ukubonisa ukusebenza kwe-reactor, ilayibrari ye-pharmaceutically ibalulekile 1,4-disubstituted 1,2,3-triazole ikhompawundi yadityaniswa ngobhedu-catalyzed Huisgen 1,3-dipolar i-dipolar i-computer. uyilo unokuvula amathuba amatsha kunye namathuba ekhemistri ngophando lwezifundo ezininzi.
Zonke izinyibilikisi kunye ne-reagents zathengwa kwi-Sigma-Aldrich, Alfa Aesar, TCI okanye i-Fischer Scientific kwaye zisetyenziswe ngaphandle kokuhlanjululwa kwangaphambili.1H kunye ne-13C NMR i-spectra erekhodwe kwi-400 MHz kunye ne-100 MHz, ngokulandelanayo, yafunyanwa ngokusebenzisa i-JEOL ECS-400 kerrovance 400 MHz 400 MHz 400 MHz i-spectrometer kunye ne-CDCl3 okanye (CD3) 2SO njenge-solvent.Zonke iimpendulo zenziwe kusetyenziswa i-Uniqsis FlowSyn chemistry platform.
I-UAM yayisetyenziselwa ukwenza zonke izixhobo kule sifundo.Iteknoloji yasungulwa kwi-1999, kunye neenkcukacha zayo zobugcisa, iiparameters zokusebenza kunye nophuhliso ukususela ekubeni ukuveliswa kwayo kunokufundwa ngokusebenzisa izinto ezilandelayo ezipapashiweyo34,35,36,37.Isixhobo (Umfanekiso 1) siphunyezwe ngokusebenzisa amandla aphezulu aphezulu, i-9kW SonicLayer® UAM 4000, izixhobo ze-U. Ukwenziwa kwesixhobo sokuhamba kwaba yi-Cu-110 kunye ne-Al 6061.Cu-110 inomxholo ophezulu wobhedu (ubuncinci be-99.9% yobhedu), iyenza ibe ngumviwa olungileyo kwiimpendulo ze-copper-catalyzed, kwaye ngoko isetyenziswe "njengomaleko osebenzayo ngaphakathi kwe-microreactor. imeko ye-annealed idibene ne-Cu-110 layer i-Al 6061 O yinto ebonakaliswe ukuba ihambelana kakhulu neenkqubo ze-UAM38, 39, 40, 41 kwaye ihlolwe kwaye ifunyenwe i-Chemical stable kunye ne-reagents esetyenziswe kulo msebenzi. 38,42 Ezi zixhobo zidweliswe kwiThebhile 1 ngezantsi.
Amanqanaba okwenziwa kwesixhobo sombane (1) I-Al 6061 substrate (2) Ukwenziwa komjelo ongezantsi oseti kwifoyile yobhedu (3) Ukufakela i-thermocouples phakathi komaleko (4) Umjelo ophezulu (5) Umjelo kunye nokuphuma (6) i-Monolithic reactor.
Ifilosofi yoyilo lwendlela yolwelo kukusebenzisa indlela edibeneyo ukunyusa umgama ohambahambayo ulwelo ngaphakathi kwetshiphu, ngelixa ugcina itshiphu kwisayizi elawulekayo.Olu lwando lomgama lunqweneleka ukunyusa ixesha lokusebenzisana kwe-catalyst / reagent kunye nokubonelela ngemveliso ebalaseleyo.Iitshiphusi zisebenzisa i-90 ° bend ekupheleni kwendlela ethe tye ukuphembelela ngaphakathi kwesixhobo sokudibanisa umxube we-4 kunye nokwandisa umphezulu wesixhobo sokudibanisa kunye nokwandisa umxube we-4 nokwandisa umxube wesixhobo sokudibanisa. (i-catalyst) .Ukuqhubela phambili ukunyusa ukuxuba okunokuthi kuphunyezwe, i-reactor design ine-inlets ezimbini ze-reagent ezidibeneyo kwi-Y-junction ngaphambi kokungena kwicandelo lokuxuba inyoka.I-inlet yesithathu, enqumla umlambo wesiqingatha ngokuhlala kwayo, ifakwe kwi-design ye-multistep reaction syntheses yexesha elizayo.
Zonke iziteshi zineprofayili yesikweri (akukho-engile eziyidrafti), isiphumo se-periodic CNC milling esetyenziselwa ukudala i-channel geometry.Imilinganiselo yetshaneli ikhethwa ukuze kuqinisekiswe ukukhutshwa kwevolumu ephezulu (ye-microreactor), ngelixa incinci ngokwaneleyo ukuququzelela ukusebenzisana komphezulu (i-catalysts) kuninzi lwamanzi aqulethwe. µm x 750 µm kunye nevolumu yereactor iyonke yayiyi-1 ml. Isidibanisi esihlanganisiweyo (1/4″—28 intambo ye-UNF) ibandakanyiwe kuyilo ukuvumela ukudibanisa okulula kwesixhobo kunye nezixhobo zekhemistri eziqukuqelayo zorhwebo. Ubungakanani beshaneli bukhawulelwe ngobunzima bezinto ze-foil, iipropathi zayo zomatshini, kunye neeparitha zokudibanisa ezisetyenziswa kunye ne-ultrasonics. Ngobubanzi obuthile bezinto ezinikeziweyo, izinto eziphathekayo "ziya kugxumeka" kumjelo owenziweyo. Okwangoku akukho modeli ithile yolu balo, ngoko ke obona bubanzi bejelo lobuninzi besixhobo esinikiweyo kunye noyilo bumiselwa ngokomfuniselo; kule meko, ububanzi be-750 μm abuyi kubangela i-sag.
Ubume (isikwere) somjelo sichongwa ngokusebenzisa i-square cutter.Imilo kunye nobukhulu bemijelo inokutshintshwa ngoomatshini be-CNC besebenzisa izixhobo ezahlukeneyo zokusika ukuze bafumane amanqanaba okuqukuqela ahlukeneyo kunye neempawu.Umzekelo wokudala umjelo wemilo egobileyo usebenzisa isixhobo se-125 μm unokufumaneka kumsebenzi we-Monaghan45.Xa umaleko we-foil ufakwe kwi-foil ye-foil ifakwe kwi-flatial channel ye-foil, i-foil ifakwe kwi-flatial channel ye-foil. (isikwere) ukugqiba.Kulo msebenzi, ukwenzela ukugcina i-symmetry yeshaneli, i-square outline isetyenziswe.
Ngethuba lokumisa okucwangcisiweyo kwangaphambili ekuvelisweni, iiprobes zeqondo lokushisa le-thermocouple (Uhlobo K) lufakwe ngokuthe ngqo ngaphakathi kwesixhobo phakathi kwamaqela angaphezulu kunye nasezantsi (Umfanekiso 1 - Inqanaba lesi-3) .Ezi thermocouples zinokubeka iliso utshintsho lweqondo lokushisa ukusuka -200 ukuya kwi-1350 ° C.
Inkqubo yokubeka isinyithi yenziwa ngophondo lwe-UAM kusetyenziswa i-25.4 mm ububanzi, i-150 micron ye-foil yensimbi engqingqwa. Ezi zingqimba ze-foil ziboshwe zibe yimichilo edibeneyo yokugubungela yonke indawo yokwakha; ubungakanani bezinto ezigciniweyo zikhulu kunemveliso yokugqibela njengoko inkqubo yokukhupha ivelisa umnatha wokugqibela. I-CNC machining isetyenziselwa umatshini i-contours yangaphandle kunye yangaphakathi yesixhobo, okubangelwa ukugqitywa komphezulu wezixhobo kunye nemijelo elinganayo nesixhobo esikhethiweyo kunye neeparitha zenkqubo ye-CNC (malunga ne-1.6 μm Ra kulo mzekelo) . qinisekisa ukuchaneka kwe-dimensional kugcinwa kwaye inxalenye egqityiweyo iya kudibana ne-CNC yokugqiba amanqanaba okuchaneka kokuchaneka.Ububanzi betshaneli esetyenziselwa esi sixhobo buncinci ngokwaneleyo ukuze kuqinisekiswe ukuba izinto ze-foil azi "sag" kumjelo we-fluid, ngoko ke umjelo ugcina i-square cross-section.Izikhewu ezinokwenzeka kwizinto ze-foil kunye neeparamitha zenkqubo ye-UAM zamiselwa ngovavanyo ngumlingane wokuvelisa, i-USA.
Uphononongo lubonise ukuba ukusabalalisa okuncinci kwe-elemental kwenzeka kwi-interface ye-UAM yokudibanisa i-46, i-47 ngaphandle kwonyango olongezelelweyo lwe-thermal, ngoko ke izixhobo ezikulo msebenzi, i-Cu-110 layer ihlala ihluke kwi-Al 6061 layer kunye nokutshintsha ngokukhawuleza.
Faka i-pre-calibrated 250 psi (1724 kPa) i-back pressure regulator (BPR) kwi-outlet ye-reactor kunye nokumpompa amanzi ngokusebenzisa i-reactor kwizinga le-0.1 ukuya kwi-1 mL min-1. Uxinzelelo lwe-reactor lwalubekwe iliso ngokusebenzisa i-FlowSyn eyakhelwe-ngaphakathi yenkqubo yoxinzelelo lwenzwa yokuqinisekisa ukuba inkqubo inokugcina i-testential flowing gradie i-testential yokuchonga uxinzelelo oluqhubekayo lwe-reactor. Umahluko phakathi kwe-thermocouples efakwe ngaphakathi kwe-reactor kunye nezo zifakwe ngaphakathi kwe-FlowSyn chip yokufudumeza ipleyiti.Oku kuphunyezwa ngokutshintsha iqondo lobushushu le-hotplate elicwangcisiweyo phakathi kwe-100 kunye ne-150 °C nge-25 °C yokunyuka kunye nokuqaphela nawuphi na umahluko phakathi kweqondo lokushisa elicwangcisiweyo kunye nerekhodiweyo.Oku kwaphunyezwa ngokusebenzisa i-UK datach, i-Pico8 yedathach, i-Cambridge ehamba nesoftware yePicoLog.
Iimeko zokusabela kwe-cycloaddition ye-phenylacetylene kunye ne-iodoethane ziye zaphuculwa (iSkimu 1- Cycloaddition ye-phenylacetylene kunye ne-iodoethane Scheme 1- Cycloaddition ye-phenylacetylene kunye ne-iodoethane) .Olu lungelelaniso lwenziwe ngoyilo olupheleleyo lwe-factorial yeemvavanyo (i-DOE) kunye ne-residence ye-experiments, usebenzisa i-parameter ye-fixing (i-DOE) alkyne:azide ratio ku 1:2.
Izisombululo ezahlukileyo 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 kwaye yapontshwa nge-reactor kwisantya esifunwayo sokuhamba kunye neqondo lokushisa njengoko imodeli yendawo yempendulo ye-pezole ithathwe kwimveliso ye-pezole. phenylacetylene ukuqala imathiriyeli kwaye igqitywe yi-high performance liquid chromatography (HPLC) .Ukwenzela ukuhambelana kohlalutyo, zonke iimpendulo zaye zathathwa nje emva kokuba umxube wokusabela ushiye i-reactor.Uluhlu lweparameter ekhethiweyo ukwenzela ukulungelelanisa luboniswe kwiThebhile 2.
Zonke iisampulu zahlalutywa kusetyenziswa inkqubo ye-Chromaster HPLC (VWR, PA, USA) equka impompo ye-quaternary, i-oven yekholomu, i-variable wave wave detector ye-UV kunye ne-autosampler.Ikholamu yayiyi-Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 mm ubukhulu, i-5 µm igcinwe ngobukhulu, i-5 µm ubukhulu. isocratic 50:50 methanol:amanzi kumyinge wokuqukuqela we-1.5 mL.min-1.Umthamo wenaliti wawuyi-5 µL kunye ne-wavelength ye-detector yayiyi-254 nm.Indawo eyincopho ye-% yesampulu ye-DOE ibalwe ukusuka kwiindawo eziphakamileyo ze-alkyne ezishiyekileyo kunye ne-triazole ye-injection yezinto ezifanelekileyo zokuqalisa i-injedent kuphela.
Ukudibanisa imveliso yohlalutyo lwe-reactor kwi-software ye-MODDE DOE (i-Umetrics, i-Malmö, e-Sweden) ivumele uhlalutyo olucokisekileyo lweendlela zeziphumo kunye nokuzimisela kweemeko zokusabela ezifanelekileyo kule cycloaddition.Ukuqhuba i-optimizer eyakhelwe-ngaphakathi kunye nokukhetha yonke imimiselo yomzekelo obalulekileyo kuvelisa isethi yeemeko zokusabela ezenzelwe ukwandisa indawo yencopho yemveliso ngelixa kuncitshiswa indawo yencopho yokuqalisa.
I-oxidation yobhedu yomhlaba ngaphakathi kwegumbi lokuphendula i-catalytic yaphunyezwa kusetyenziswa isisombululo se-hydrogen peroxide (36%) egeleza kwigumbi lokusabela (isantya sokuhamba = 0.4 mL min-1, ixesha lokuhlala = 2.5 min) phambi kokuhlanganiswa kwelayibrari nganye ye-triazole.
Emva kokuba isethi efanelekileyo yeemeko zichongiwe, zisetyenziswe kuluhlu lwe-acetylene kunye ne-haloalkane derivatives ukuvumela ukuhlanganiswa kwelayibrari encinci ye-synthesis, ngaloo ndlela kusekwa ukukwazi ukusebenzisa le miqathango kuluhlu olubanzi lwee-reagents ezinokubakho (Umfanekiso 1) .2).
Lungiselela izisombululo ezahlukeneyo ze-sodium azide (0.25 M, 4: 1 DMF: H2O), i-haloalkanes (0.25 M, i-DMF) kunye ne-alkynes (0.125 M, i-DMF) i-aliquots ye-3 mL yesisombululo ngasinye yaxutywa kwaye yaphonswa nge-reactor kwi-75 µL.min-1 kunye ne-150 ° C kunye ne-150 ° C. I-ethyl acetate.Isisombululo sesampuli sihlanjwe nge-3 × 10 mL yamanzi. Iingqimba ezinamanzi zidibene kwaye zikhutshwe nge-10 mL ye-ethyl acetate; iileyile zezinto eziphilayo zaye zadibaniswa, zihlanjwe nge-3 x 10 mL ye-brine, yomiswa phezu kwe-MgSO4 kwaye yahluzwa, emva koko i-solvent yasuswa kwi-vacuo.Iisampulu zahlanjululwa ngekholomu ye-chromatography kwi-silica gel usebenzisa i-ethyl acetate ngaphambi kokuhlalutya ngokudibanisa i-HPLC, i-1H ​​NMR, i-13C i-HR-spection ye-HR (i-NMR) kunye ne-high resolution ye-HR.
Zonke ii-spectra zifunyenwe kusetyenziswa i-Thermofischer echanekileyo ye-Orbitrap isisombululo se-mass spectrometer kunye ne-ESI njengomthombo we-ionization.Zonke iisampuli zalungiswa kusetyenziswa i-acetonitrile njenge-solvent.
Uhlalutyo lwe-TLC lwenziwa kwi-aluminium-backed silica plates.Iiplates zabonwa ngokukhanya kwe-UV (254 nm) okanye i-vanillin staining kunye nokufudumala.
Zonke iisampulu zahlalutywa kusetyenziswa i-VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) inkqubo exhotyiswe nge-autosampler, i-oven oven pump binary pump kunye ne-single wavelength detector.Ikholamu esetyenzisiweyo yayiyi-ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Ltd.,Skotland Technologies).
Izitofu (5 µL) zenziwe ngokuthe ngqo kumxube oxutyiweyo okrwada wokusabela (1:10 dilution) kwaye zahlalutywa ngamanzi: methanol (50:50 okanye 70:30), ngaphandle kweesampulu ezithile zisebenzisa inkqubo yokunyibilikisa eyi-70:30 (echazwe njengenani lenkwenkwezi) kumyinge wokuqukuqela we-1.5 mL igcinwe kwikholamu ye-1.5 mL / i-wangvele ye-4 ° . 254 nm.
I-% indawo encopho yesampulu yabalwa ukusuka kwindawo encopho ye-alkyne eseleyo, imveliso ye-triazole kuphela, kunye nokutofa kwezinto zokuqala kuvunyelwe ukuchongwa kweencopho ezifanelekileyo.
Zonke iisampulu zahlalutywa kusetyenziswa i-Thermo iCAP 6000 ICP-OES.Yonke imigangatho yokulinganisa yalungiswa ngokusebenzisa isisombululo esiqhelekileyo se-1000 ppm Cu kwi-2% ye-nitric acid (SPEX Certi Prep) .Yonke imigangatho yalungiswa kwi-5% ye-DMF kunye ne-2% isisombululo se-HNO3, kwaye zonke iisampuli zahlanjululwa kwisisombululo se-DMF se-20-HNO3.
I-UAM isebenzisa i-ultrasonic metal welding njengendlela yokudibanisa kwi-foil yensimbi esetyenziselwa ukwakha i-asembly yokugqibela.I-ultrasonic metal welding isebenzisa isixhobo setsimbi esingcangcazelayo (esibizwa ngokuba luphondo okanye uphondo lwe-ultrasonic) ukufaka uxinzelelo kwi-foil layer / ngaphambili edibeneyo edibeneyo ukuze idibaniswe ngelixa i-vibrating impahla. ukudibanisa yonke indawo.Xa uxinzelelo kunye nokunyakaza kusetyenziswe, i-oxides ebusweni bezinto eziphathekayo zinokuqhekeka.Uxinzelelo oluqhubekayo kunye nokunyakaza kunokubangela ukuba i-asperities yezinto zidibanise i-36 .Uqhagamshelwano olusondeleyo kunye nokushisa okubangelwa kwendawo kunye noxinzelelo emva koko kukhokelela kwi-solid-state bonding kwi-interfaces eziphathekayo; inokunceda kwakhona ukubambelela ngokutshintsha kwi-surface energy48.Ubume bendlela yokudibanisa iyahlula ezininzi iingxaki ezinxulumene neqondo lokushisa lokunyibilika okuguquguqukayo kunye nobushushu obuphezulu emva kwemiphumo ekhankanywe kwezinye iindlela zokuvelisa ezongezelelweyo.Oku kuvumela ukudibanisa ngokuthe ngqo (okt, ngaphandle kokuguqulwa komphezulu, iifayili okanye ukunamathela) kwiingqimba ezininzi zezinto ezahlukeneyo kwisakhiwo esisodwa esidibeneyo.
Into yesibini ethandekayo ye-UAM yinqanaba eliphezulu lokuhamba kweplastiki ebonwe kwizinto zensimbi, nakwiqondo lokushisa eliphantsi, oko kukuthi ngaphantsi kwendawo yokunyibilika yezinto zetsimbi.Ukudibanisa kwe-ultrasonic oscillation kunye noxinzelelo kubangela amanqanaba aphezulu okufuduka komda wengqolowa yendawo kunye nokuhlaziywa kwakhona ngaphandle kokunyuka okukhulu kweqondo lokushisa ngokwesiko elihambelana nezinto ezininzi.Ngexesha lokwakhiwa kwendibano yokugqibela, le ngqungquthela esebenzayo kunye ne-explosive layers inokuthi ibe ne-explosion esebenzayo kunye ne-explosive layers. i-metal foil, i-layer by layer.Elements ezifana ne-optical fibers 49, i-reinforcements 46, i-electronics 50, kunye ne-thermocouples (lo msebenzi) zonke zifakwe ngempumelelo kwizakhiwo ze-UAM ukudala iindibano ezidibeneyo ezisebenzayo kunye ne-passive.
Kulo msebenzi, zombini izinto ezahlukeneyo zokudityaniswa kwezinto ezinokwenzeka kunye nokunxibelelana okunokwenzeka kwe-UAM zisetyenzisiwe ukwenza eyona nto iphambili yokubeka iliso kubushushu bemicroreactor.
Xa kuthelekiswa ne-palladium (Pd) kunye nezinye izixhobo zentsimbi ezisetyenziswa ngokuqhelekileyo, iCu catalysis ineenzuzo ezininzi: (i) Ngokwezoqoqosho, iCu inexabiso eliphantsi kunezinye iintsimbi ezininzi ezisetyenziselwa i-catalysis kwaye ngoko ke iyindlela ekhangayo kwishishini lokulungisa imichiza (ii) Uluhlu lwe-Cu-catalyzed reactions cross-coupling reactions luyanda kwaye lubonakala luyi-Pd51o esekelwe kwi-Pd51o (3) reactions Cu-catalyzed ukusebenza kakuhle xa ukungabikho ezinye ligands, Ezi ligands zidla ngolwakhiwo elula kwaye ezingabizi ukuba zifunwa, kanti ezo zisetyenziswa kwi-Pd chemistry zisoloko ezintsonkothileyo, zibiza, kwaye emoyeni-sensitive (iv) Cu, eyaziwa kakhulu ngokukwazi ukubopha alkynes kwi-synthesis, Umzekelo, bimetallic-catalyzedcling-catalyzedcling-cocatalyzedupling ikhemistri) (v)Cu iyakwazi nokukhuthaza i-arylation yeenucleophiles ezininzi kwi-Ullmann-type reactions.
Imizekelo ye-heterogenization yazo zonke ezi mpendulo isandul 'ukubonakaliswa phambi kweCu (0) .Oku kubangelwa kakhulu kwishishini lamachiza kunye nokugxila okukhulayo kwi-metal catalyst recovery and reuse55,56.
Ivulwe ngu-Huisgen ngeminyaka yee-1960s57, i-1,3-dipolar cycloaddition reaction phakathi kwe-acetylene kunye ne-azide ukuya kwi-1,2,3-triazole ithathwa njenge-synergistic demonstration reaction.Iziphumo ze-1,2,3 ze-triazole moieties zinomdla ngokukodwa njenge-pharmacophore yokusetyenziswa kweziyobisi kwi-pharmacophore eyahlukahlukeneyo kwi-biological applications ii-arhente zonyango 58.
Le mpendulo yaphinda yagxila kwakhona xa i-Sharpless kunye nabanye bazisa ingcamango "cofa i-chemistry" 59. Igama elithi "cofa i-chemistry" lisetyenziselwa ukuchaza isethi eqinile, ethembekileyo kunye nekhethiweyo yeempendulo zokwenziwa ngokukhawuleza kweekhompawundi ezintsha kunye namathala eencwadi adibeneyo nge-heteroatom linkage (CXC) 60 I-synthetic ye-synthetic yezi mpendulo zivela kwi-reactivity yamanzi, i-oksijini ehambelanayo kunye nokuchasana kwamanzi kunye nemveliso ye-oksijini ehambelanayo, imveliso ye-oksijini ehambelanayo kunye nokuchasana kwemveliso kunye ne-oksijini. ukwahlukana kulula61.
I-classical Huisgen 1,3-dipole cycloaddition ayiyona inxalenye ye "cofa chemistry".Nangona kunjalo, iMedali kunye neSharpless ibonise ukuba lo mcimbi wokudibanisa i-azide-alkyne uhamba nge-107 ukuya kwi-108 phambi kwe-Cu (I) xa kuthelekiswa ne-uncatalyzed 1,3-dipolar rate 6acceledi 626 yempendulo ebalulekileyo. ayifuni amaqela akhuselayo okanye iimeko zokusabela ezinzima kunye nezivuno ezikufutshane nokuguqulwa okupheleleyo kunye nokukhetha kwi-1,4-disubstituted 1,2,3-triazoles (anti-1,2,3-triazole) kwinqanaba lexesha (Umfanekiso 3).
Iziphumo ze-Isometric ze-Huisgen cycloadditions eqhelekileyo kunye ne-copper-catalyzed.Cu (I) -catalyzed Huisgen cycloadditions ivelisa kuphela i-1,4-disubstituted 1,2,3-triazoles, kanti i-thermal-induced Huisgen cycloadditions ivame ukuvelisa i-1,51-triazoles kunye ne-1,51-triazoles. ii-stereoisomers ze-azoles.
Uninzi lweeprotocol lubandakanya ukunciphisa imithombo ye-Cu (II) ezinzileyo, njengokunciphisa i-CuSO4 okanye i-Cu (II) / Cu (0) yeentlobo ezidibeneyo kunye neetyuwa ze-sodium.Xa kuthelekiswa nezinye iimpendulo ze-metal-catalyzed, ukusetyenziswa kwe-Cu (I) kuneenzuzo ezinkulu zokungabizi kwaye kulula ukuyiphatha.
Izifundo zeKinetic kunye ne-isotopic zokulebula nguWorrell et al. I-65 ibonise ukuba, kwimeko ye-alkynes ye-terminal, ezimbini ezilinganayo zobhedu zibandakanyeka ekuvuleni ukuphinda kusebenze kwe-molecule nganye ukuya kwi-azide.Indlela ecetywayo iqhubela phambili ngekhonkco yentsimbi yobhedu enamalungu amathandathu eyenziwe ngolungelelwaniso lwe-azide ukuya kwi-acetylide yobhedu edityanisiweyo kunye ne-π-bonded copper eyenziwe ngumnikelo we-copper ozinzileyo. Ukucutheka kweringi, kulandelwa kukubola kweproton ukubonelela ngeemveliso zetriazole kunye nokuvala umjikelo we-catalytic.
Ngelixa iinzuzo zezixhobo zekhemistri ezijikelezayo zibhalwe kakuhle, kuye kwakho umnqweno wokudibanisa izixhobo zokuhlalutya kwezi nkqubo ze-in-line, in-situ, inkqubo yokubeka iliso66,67.UAM ibonakalise ukuba yindlela efanelekileyo yokuyila kunye nokuvelisa i-3D flow reactors enzima kakhulu eyenziwe nge-catalytically active, i-thermal conductive materials kunye nezinto ezifakwe ngokuthe ngqo kwi-fibre sensing.
I-Aluminium-copper flow reactor eyenziwe yi-ultrasonic additive production (UAM) kunye nesakhiwo seshaneli esiyinkimbinkimbi yangaphakathi, i-thermocouples edibeneyo kunye ne-catalytic reaction chamber.Ukujonga iindlela zangaphakathi zamanzi, i-prototype ecacileyo eyenziwe ngokusebenzisa i-stereolithography nayo ibonisiwe.
Ukuqinisekisa ukuba ii-reactors zenzelwe ukwenzeka kwezinto eziphilayo kwixesha elizayo, izinyibilikisi kufuneka zifudunyezwe ngokukhuselekileyo ngaphezu kwendawo yokubilisa; zixinzelelo kunye nobushushu obuvavanyiweyo.Uvavanyo loxinzelelo lubonise ukuba inkqubo igcina uxinzelelo oluzinzileyo kunye noluqhubekayo nangona ukunyuka kwenkqubo yoxinzelelo (1.7 MPa) .Uvavanyo lwe-hydrostatic lwenziwa kwiqondo lokushisa lokushisa usebenzisa i-H2O njenge-fluid.
Ukudibanisa i-embedded (Figure 1) thermocouple kwi-data data logger ibonise ukuba i-thermocouple yi-6 °C (± 1 °C) epholileyo kunokushisa okucwangcisiweyo kwi-FlowSyn system. Ngokuqhelekileyo, ukunyuka kwe-10 °C kwiziphumo zokushisa ekuphindwe kabini kwereyithi yokusabela, ngoko ke umahluko weqondo lokushisa kwi-degrees nje ezimbalwa ngenxa yokulahlekelwa kweqondo lokushisa kunokutshintsha ngokuphawulekayo kwiqondo lokushisa. high diffusivity thermal izinto ezisetyenziselwa inkqubo yokuvelisa.Le thermal drift iyahambelana kwaye ke ngoko inokubalelwa kwi-setup yesixhobo sokuqinisekisa ubushushu obuchanekileyo bufikelelwa kwaye bulinganiswe ngexesha le-reaction.Therefore, esi sixhobo sokubeka iliso kwi-intanethi siququzelela ulawulo oluqinileyo lobushushu bokusabela kwaye luququzelele ukulungelelaniswa kwenkqubo echanekileyo kunye nophuhliso lweenkqubo ezifanelekileyo.
I-reactor echazwe kulo msebenzi ngumzekelo wokuqala wokusetyenziswa kweteknoloji ye-UAM ekwenzeni i-reactors yamakhemikhali kunye needilesi ezininzi ezilinganiselweyo ngoku ezihambelana ne-AM / 3D yokuprintwa kwezi zixhobo, ezifana: (i) ukoyisa iingxaki ezixeliweyo ezinxulumene nobhedu okanye i-aluminium alloy processing (ii) ukuphuculwa kwesisombululo sesiteshi sangaphakathi xa kuthelekiswa ne-powder bed fusion (PBF) izixhobo ezifana ne-powder bed fusion (PBF) izixhobo ezifana ne-SLM ye-laser5 kunye nokukhetha izixhobo ze-laser2, i-SLM, i-laser okanye i-pomel ye-SLM. rough surface texture26 (iii) Ubushushu bokusebenza obucuthiweyo, obuququzelela ukudityaniswa okuthe ngqo kwezivamvo, okungenakwenzeka kubuchwepheshe bebhedi engumgubo, (v) yoyisa iipropati ezilambathayo zoomatshini kunye novakalelo lwamacandelo asekelwe kwipolima kwiintlobo ngeentlobo zezinyibilikisi eziqhelekileyo eziphilayo17,19.
Ukusebenza kwe-reactor kuboniswe ngoluhlu lwee-alkyne azide cycloaddition reactions zobhedu-catalyzed phantsi kweemeko zokuhamba okuqhubekayo (Umfanekiso 2) .I-reactor ye-copper eprintiweyo ye-ultrasonic echazwe kwi-Figure 4 idityaniswe nenkqubo yokuhamba kwezorhwebo kwaye isetyenziselwa ukudibanisa i-azides yelayibrari eyahlukeneyo ye-1,4-disubstituted i-athol-azoled-1,4-disubstituted 1,4-disubstituted the-control-azoled-azoled-control, i-1,4-disubstituted i-actoral-azoled-azoled-1, i-1, i-azoled reaction reaction. kunye namaqela e-alkyl i-halides phambi kwe-sodium chloride (Umfanekiso 3) .Ukusetyenziswa kwendlela yokuhamba ngokuqhubekayo kunciphisa iinkxalabo zokhuseleko ezinokuvela kwiinkqubo ze-batch, njengoko le mpendulo ivelisa i-aside intermediates esebenzayo kunye neyingozi kakhulu [317], [318] . I-Cycloaddition ye-phenylacetylene kunye ne-iodoethane) (jonga umfanekiso 5).
(Phezulu ekhohlo) Isicwangciso sokuseta esetyenziselwe ukubandakanya i-reactor ye-3DP kwinkqubo yokuhamba (phezulu ekunene) efunyenwe kwisikimu esiphuculweyo (ezantsi) seskimu se-Huisgen cycloaddition 57 phakathi kwe-phenylacetylene kunye ne-iodoethane yokuphucula kunye nokubonisa iiparameters eziphuculweyo zokuphendula izinga lokuguqulwa.
Ngokulawula ixesha lokuhlala le-reagents kwindawo ye-catalytic ye-reactor kunye nokubeka iliso ngokusondeleyo ubushushu bokusabela kunye neprobe edibeneyo ye-thermocouple, iimeko zokusabela zinokuphuculwa ngokukhawuleza nangokuchanekileyo kunye nexesha elincinane kunye nokusetyenziswa kwezinto eziphathekayo. zombini ixesha lokuhlala kunye nobushushu impendulo zithathwa imizekelo ebalulekileyo imodeli.Ukuqhuba i-optimizer eyakhelwe-ngaphakathi usebenzisa le migaqo ikhethiweyo ivelisa isethi yeemeko zokusabela ezenzelwe ukwandisa iindawo zencopho yemveliso ngelixa kuncitshiswa ukuqala kweendawo eziphakamileyo zezinto eziphathekayo.Olu lungelelaniso luvelise i-53% yokuguqulwa kwemveliso ye-triazole, ehambelana ngokusondeleyo noqikelelo lwemodeli ye-54%.
Ngokusekwe kuncwadi olubonisa ukuba icopper(I) oxide (Cu2O) inokusebenza njengohlobo olusebenzayo lwe-catalytic kwimiphezulu ye-zero-valent yobhedu kwezi mpendulo, ukukwazi ukwenza i-oxidize umphezulu wereactor phambi kokwenza ukusabela kokuqukuqela kwaphandwa70,71.Ukusabela phakathi kwephenylacetylene kunye ne-iodoethane kuye kwenziwa kwakhona phantsi kweemeko ezichanekileyo zokonyuka kwaphinda kwajongwa phantsi kwesiphumo esibalulekileyo. ekuguqulweni kwezinto zokuqala, ezibalwe ukuba> 99% .Nangona kunjalo, ukubeka iliso yi-HPLC kubonise ukuba olu kuguqulwa lunciphise kakhulu ixesha lokuphendula ixesha elide kakhulu de kube malunga nemizuzu ye-90, apho umsebenzi ubonakala ufikeleleka kwaye ufikelele "kwimeko ezinzileyo". lobushushu ukwenza CuO kunye Cu2O ezingezizo layers zokuzikhusela.Oku kuphelisa imfuneko yokongeza ithusi (II) umthombo co-composition71.