Ndiyabulela ngokundwendwela i-Nature.com.Uguqulelo lwesikhangeli oyisebenzisayo lunenkxaso elinganiselweyo ye-CSS.Ukufumana amava angcono kakhulu, sincoma ukuba usebenzise i-browser ehlaziyiweyo (okanye ucime imodi yokuhambelana kwi-Internet Explorer). Okwangoku, ukuqinisekisa inkxaso eqhubekayo, siya kubonisa isayithi ngaphandle kwezitayela kunye neJavaScript.
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 nolu luhlu lwezixhobo ze-biological eziye zayanyaniswa ngokubonakalayo. Iikhompawundi ezibalulekileyo ze-1,4-disubstituted 1,2,3-triazole 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 nge-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, okanye ukusetyenziswa kwe-poly-based kuphela kwi-poly-based based 3D. iindlela zoshicilelo ezifana ne-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 / uhlalutyo17, 18, 18, 2019, ukuphunyezwa okukhulu kwe-2019 kwintsimi ebanzi, i-201919 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 yi-Ultrasonic Additive Manufacturing (UAM) .Le ndlela ye-solid-state sheet lamination technique isebenzisa i-oscillations ye-ultrasonic kwi-foil yensimbi encinci ukwenzela ukuba idibanise kunye kunye noluhlu kunye nobushushu obuncinci kunye neqondo eliphezulu lokuhamba kweplastiki 21, 22, 23 inkqubo, apho in-situ periodic computer numberal control (CNC) milling okanye laser machining ichaza imilo yomnatha yomaleko wezinto ezidityanisiweyo 24, 25.Oku kuthetha ukuba umsebenzisi akakhawulelwanga ziingxaki ezinxulumene nokususa izinto ezishiyekileyo zokwakha ezikrwada kumajelo amancinci olwelo, nto leyo edla ngokuba ngumgubo kunye nolwelo lwe-AM system26,27,28. Ukuhlanganiswa kwezinto eziphathekayo kwisinyathelo esisodwa senkqubo.Ukukhethwa kwezinto ezixutywayo ngaphaya kwenkqubo yokunyibilika kuthetha ukuba iimfuno zomatshini kunye neekhemikhali zezicelo ezithile zinokufezekiswa ngcono.Ukongezelela kwi-solid state bonding, enye into eyenzekayo ngexesha lokubambisana kwe-ultrasonic ukuhamba okuphezulu kwezinto zeplastiki kumaqondo okushisa aphantsi29,30,31,32,33.Olu phawu olukhethekileyo lwe-UAM lunokwenza i-UAM ifake i-metal embedding. ukuhanjiswa kolwazi lwexesha langempela ukusuka kwisixhobo ukuya kumsebenzisi ngokusebenzisa uhlalutyo oluhlanganisiweyo.
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;kunye nokufakela abenzi boluvo abashushu ngokuthe ngqo phakathi kwemijelo yereagent yokujonga ubushushu obuchanekileyo kunye nolawulo.Ukubonisa ukusebenza kwe-reactor, ithala leencwadi elibalulekileyo ngokwamayeza 1,4-disubstituted 1,2,3-triazole ikhompawundi yadityaniswa ngobhedu-catalyzed Huisgen 1,3-dipolar 1,3-dipolar 1,3-dipolar 1. amathuba kunye namathuba ekhemistri ngophando lwezifundo ezininzi.
Zonke i-solvents 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 kusetyenziswa i-JEOL ECS-400 kerrovance 400 MHz spectra imitha ye-400 MHz okanye i-CD 400 MHz I-l3 okanye (CD3) 2SO njenge-solvent.Zonke iimpendulo zenziwa 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 ye-SonicLayer, i-U. isixhobo yayiyi-Cu-110 kunye ne-Al 6061.Cu-110 inomxholo ophezulu wobhedu (ubuncinci be-99.9% yobhedu), okwenza kube ngumviwa olungileyo kwiimpendulo ezenziwe nge-copper-catalyzed, kwaye ke isetyenziswe njenge "maleko asebenzayo ngaphakathi kwe-microreactor.I-Al 6061 O isetyenziswa njenge "bulk" imathiriyeli, kunye ne-Embedding layer esetyenziselwa uhlalutyo;I-alloy encedisayo yokufakelwa kwecandelo kunye nemeko ye-annealed idibene ne-Cu-110 layer.I-Al 6061 O yinto ebonakaliswe ukuba ihambelana kakhulu neenkqubo ze-UAM38, 39, 40, 41 kwaye ivavanywe kwaye ifunyenwe I-Chemically stable kunye ne-reagents esetyenziswe kulo msebenzi.Indibaniselwano ye-Al 6061 O kunye ne-Cu-110 nayo ithathwa njengendibaniselwano yezinto eziphathekayo kwi-UAM kwaye ngoko yinto efanelekileyo yolu phononongo.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 lomzila we-fluid kukusebenzisa indlela edibeneyo yokwandisa umgama ohambayo we-fluid ngaphakathi kwe-chip, ngelixa ugcina i-chip kwi-size. ukuxutywa okunokuthi kuphunyezwe, i-reactor design ifaka i-reagent inlets ezimbini ezidityanisiweyo kwi-Y-junction ngaphambi kokungena kwicandelo lokuxuba inyoka.I-inlet yesithathu, enqumla umlambo kwisiqingatha sokuhlala kwayo, ifakwe kwi-design ye-multistep reaction syntheses yexesha elizayo.
Onke amajelo aneprofayile yesikweri (akukho ma-engile ayidrafti), isiphumo sokusila se-CNC sexesha esisetyenzisiweyo ukwenza ijeyometri yetshaneli.Imilinganiselo yetshaneli ikhethwa ukuze kuqinisekiswe ukukhutshwa kwevolumu ephezulu (ye-microreactor), ngelixa incinci ngokwaneleyo ukulungiselela ukusebenzelana komphezulu (i-catalysts) kuninzi lwe-fluid equlethwe. I-750 µm kunye nevolumu yereactor iyonke yayiyi-1 ml. Isidibanisi esihlanganisiweyo (1/4″—28 intambo ye-UNF) ibandakanyiwe kuyilo ukuvumela ukudityaniswa okulula kwesixhobo kunye nesixhobo sokurhweba sekhemistri.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 okuhamba kunye neempawu ezahlukeneyo.Umzekelo wokudala umjelo wemilo egobileyo usebenzisa isixhobo se-125 μm sinokufumaneka kumsebenzi we-Monaghan45.Xa umaleko we-foil ufakwe kwi-flat le-foil ye-foil, ifakwe kwi-flatial channel. umsebenzi, 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 kwendawo yezixhobo kunye nemijelo elingana nesixhobo esikhethiweyo kunye neeparitha zenkqubo ye-CNC (malunga ne-1.6 μm Ra kulo mzekelo) . ukuchaneka kugcinwa kwaye inxalenye egqityiweyo iya kudibana ne-CNC yokugqiba amanqanaba okuchaneka kokugaya.Ububanzi bejelo elisetyenziselwa esi sixhobo lincinci ngokwaneleyo ukuze kuqinisekiswe ukuba izinto ze-foil aziyi "sag" kwi-channel ye-fluid, ngoko ke umjelo ugcina i-square cross-section.Izithuba ezinokwenzeka kwizinto ze-foil kunye neeparamitha zenkqubo ye-UAM zaye zamiselwa ngokulinga ngumlingane wokuvelisa (Fabrisonic LLC, 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 umahluko phakathi kwe-testential flowing gradie phakathi kwe-testential steady reactor. I-rmocouples efakwe ngaphakathi kwe-reactor kunye nezo zifakwe ngaphakathi kwe-FlowSyn chip heat plate.Oku kuphunyezwa ngokutshintsha iqondo lobushushu le-hotplate elicwangcisiweyo phakathi kwe-100 kunye ne-150 °C kwi-25 °C yokunyuka kunye nokuqaphela nawuphi na umahluko phakathi kobushushu obucwangcisiweyo kunye norekhodiweyo.Oku kwaphunyezwa ngokusebenzisa i-tc-08 yedatha ye-Pigcong, i-Cambridge data logger
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 ratio ye-experiments kwi-experimentation ye-experience ye-experimentation, i-DOE yokulinganisa ubushushu kunye ne-reside imitha yovavanyo, i-DOE yokulinganisa ubushushu kunye ne-reside. 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 kwaye yaphonswa nge-reactor kwisantya esifunwayo sokuhamba kunye neqondo lokushisa njengoko imodeli ye-pelace iqale imveliso kunye nobushushu bendawo yokuphendula imodeli ye-pelace kunye nobushushu. ngolwelo oluphezulu lwekhromatografi (HPLC)
Zonke iisampulu zahlalutywa kusetyenziswa inkqubo yeChromaster HPLC (VWR, PA, USA) equka impompo ye-quaternary, i-oven yekholomu, i-variable wavelength UV detector kunye ne-autosampler.Ikholamu yayiyi-Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 × 100 mm ubukhulu, i-particle 500 ye-isocracy, i-500 mm ye-isocra I-50 methanol:amanzi kumyinge wokuhamba we-1.5 mL.min-1.Umthamo wenaliti wawuyi-5 µL kunye ne-wavelength ye-detector yi-254 nm.I-% indawo encopho yesampulu ye-DOE ibalwe ukusuka kwiindawo eziphakamileyo zentsalela ye-alkyne kunye ne-triazole yeemveliso 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 ezahlukileyo ze-sodium azide (0.25 M, 4: 1 DMF: H2O), i-haloalkanes (0.25 M, DMF) kunye ne-alkynes (0.125 M, i-DMF) .I-aliquots ye-3 mL yesisombululo ngasinye yaxutywa kwaye yampontshwa nge-reactor kwi-75 µL.min-1 kunye ne-150 °C eqokelelweyo kunye ne-150 °C edityanisiweyo kunye ne-dicetyl ye-ml ye-alum kunye ne-150 ° C. .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 ye-C2 okanye i-4 i-wave ye-4 igcinwe kwi-4 °. .
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 yokubambisana kwi-metal foil material esetyenziselwa ukwakha indibano yokugqibela.I-Ultrasonic metal welding isebenzisa isixhobo setsimbi esingcangcazelayo (esibizwa ngokuba luphondo okanye uphondo lwe-ultrasonic) ukufaka uxinzelelo kuluhlu lwe-foil / ngaphambili oludityanisiweyo oludityanisiweyo oluza kudityaniswa ngelixa lungcangcazela. Xa uxinzelelo kunye ne-vibration zisetyenziselwa, i-oxides ebusweni bezinto eziphathekayo zinokuqhekeka.Uxinzelelo oluqhubekayo kunye nokunyakaza kunokubangela ukuba i-asperities yezinto eziphathekayo 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 weenkozo zendawo kunye ne-recrystallization ngaphandle kokunyuka okukhulu kweqondo lokushisa ngokwesiko kuhambelana nezinto ezininzi.Ngexesha lokwakhiwa kwendibano yokugqibela, le ngqungquthela esebenzayo kunye ne-fombe i-fombe esebenzayo, i-fombe esebenzayo ye-metal layer inokuqhuma, kunye ne-fombe esebenzayo. ngomaleko.Iizinto ezifana neentambo ze-optical 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) Ngokoqoqosho, iCu inexabiso eliphantsi kunezinye isinyithi ezininzi ezisetyenziswa kwi-catalysis kwaye ngoko ke iyindlela ekhangayo kwishishini lokulungisa imichiza (ii) Uluhlu lwe-Cu-catalyzed reactions cross-coupling reactions luyanda kwaye lubonakala ngathi luyi-Pd51-based complementary,3,3,3,3, 3, 3. zed reactions zisebenza kakuhle xa kungekho ezinye ligands, Ezi ligands zidla ngolwakhiwo elula kwaye ezingabizi ukuba zifunwa, kanti ezo zisetyenziswa kwi-Pd chemistry zisoloko ezintsonkothileyo, zibiza, kwaye umoya-sensitive (iv) Cu, ingakumbi eyaziwa ngokuba ukukwazi ukubopha alkynes in synthesis, Umzekelo, bimetallic-catalyzed chemistry kunye chemistry azicycload ekwaziyo ukukhuthaza Sonogashirade coupp coupling Ukutshatyalaliswa kweenucleophiles ezininzi kwii-reactions zohlobo lwe-Ullmann.
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.
Yaqalwa ngu-Huisgen ngeminyaka yoo-1960s57, i-1,3-dipolar cycloaddition reaction phakathi kwe-acetylene kunye ne-azide ukuya kwi-1,2,3-triazole ithathwa njenge-synergistic demonstration reaction. .
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 kwaye ekhethiweyo yeempendulo zokwenziwa ngokukhawuleza kweekhompawundi ezintsha kunye namathala eencwadi adibeneyo nge-heteroatom linkage (CXC) 60 I-synthetic ye-synthetic yezi meko zokusabela zivela kwi-reactions ye-oxygen elula, i-oksijini edibeneyo yokusabela kunye ne-oksijini yesibheno esilula, kunye ne-oksijini edibeneyo yokusabela, i-reactivity ye-oksijini edibeneyo kunye ne-oksijini ephezulu, i-reactivity yamanzi avela kwi-reactivity elula kunye ne-oksijeni. 1.
I-classical Huisgen 1,3-dipole cycloaddition ayiyonxalenye ye "cofa chemistry".Nangona kunjalo, iMedali kunye neSharpless babonise ukuba lo mcimbi wokudibanisa i-azide-alkyne udlula i-107 ukuya kwi-108 phambi kweCu (I) xa kuthelekiswa ne-1,3-dipolar engatshintshiyo le nqanaba lokuphucula i-cycload 3 i-action aydipolar ayifuni 6cceledi ye-62. amaqela 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).
Isometric results of conventional and copper-catalyzed Huisgen cycloadditions.Cu(I)-catalyzed Huisgen cycloadditions yield only 1,4-disubstituted 1,2,3-triazoles, whereas thermally induced Huisgen cycloadditions typically yield 1,4- and 1,5-triazoles 1:1 mixture of stereoisomers of 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, i-alkynes ezimbini ezilinganayo zobhedu zibandakanyeka ekusebenzeni kwakhona kwe-molecule nganye ukuya kwi-azide.Indlela ecetywayo iqhubela phambili ngekhonkco yentsimbi yobhedu enamalungu amathandathu eyenziwe ngolungelelwaniso lwe-azide ukuya kwi-acetylide yobhedu ene-π-bonded copper njenge-copper edityanisiweyo yi-copper estable yi-copper e-stable yi-copper e-stable yi-copper e-TrinkTrinkT yobhedu. , kulandelwa ukubola kweproton ukubonelela ngeemveliso ze-triazole kunye nokuvala umjikelezo 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.
Ukuqhagamshela 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 zobushushu ekuphindaphindeni kwereyithi yokusabela, ngoko ke umahluko weqondo lobushushu kwiqondo eliphezulu lokusabela kwiqondo lobushushu elinokutshintsha ngokuphawulekayo kwiqondo eliphezulu leqondo lobushushu. ffusivity izinto ezisetyenziswa kwinkqubo yokuvelisa inkqubo.Le thermal drift iyahambelana kwaye ke ngoko inokubalelwa kwi-setup yezixhobo ukuqinisekisa ukuba ubushushu obuchanekileyo bufikelelwa kwaye bulinganiswe ngexesha le-reaction.Therefore, esi sixhobo sokubeka iliso kwi-intanethi siququzelela ulawulo oluqinileyo lobushushu bokusabela kwaye luququzelele ukuphuculwa kwenkqubo echanekileyo kunye nophuhliso lwezona zivamvo ezifanelekileyo.
I-reactor eboniswe kulo msebenzi ngumzekelo wokuqala wokusetyenziswa kweteknoloji ye-UAM ekwenzeni i-reactors yeekhemikhali kunye nokujongana nemida emininzi ekhoyo ngoku ehambelana ne-AM / 3D yoshicilelo lwezi zixhobo, ezifana: (i) ukoyisa iingxaki ezixeliweyo ezinxulumene ne-copper 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-laser ye-powder2 kunye nokukhetha izixhobo ze-laser2, i-SLM, i-textile ye-laser2, kunye nokukhetha izixhobo ze-laser2. (iii) Ukushisa okucuthayo okucutshungulwayo, okuququzelela ukudibanisa ngokuthe ngqo kwee-sensor, ezingenakwenzeka kwi-teknoloji ye-powder bed, (v) yoyisa iimpawu ezimbi zemishini kunye novakalelo lwamacandelo amacandelo asekelwe kwi-polymer kwiintlobo ezahlukeneyo ze-solvents eziqhelekileyo eziphilayo17,19.
Ukusebenza kwe-reactor kuboniswe ngoluhlu lwee-alkyne azide cycloaddition reactions zobhedu-catalyzed phantsi kweemeko ezihamba ngokuqhubekayo (Umfanekiso 2) .I-ultrasonic-printed copper reactor echazwe kwi-Figure 4 idityaniswe nenkqubo yokuhamba kwezorhwebo kwaye isetyenziselwa ukudibanisa ama-azides elayibrari ehlukeneyo ye-1,4-disubstituted i-athomu ye-1,4-disubstituted i-athom ye-athom ye-athom, i-athom, i-athom, i-athom, i-athom, i-athom, i-athom, i-1,4-disubstituted, i-athom, i-athom, i-athom, i-athom, kunye ne-1,4-disubstituted, i-athom, i-athom, i-athom, i-athom, i-athom, i-athom, i-1,4-disubstituted. i-halides phambi kobukho be-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]. 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 kwi-catalytic part ye-reactor kunye nokubeka esweni ngokusondeleyo ubushushu bokusabela kunye neprobe edibeneyo ye-thermocouple edibeneyo, iimeko zokuphendula zinokuphuculwa ngokukhawuleza nangokuchanekileyo kunye nexesha elincinane kunye nokusetyenziswa kwezinto eziphathekayo. kunye neqondo lobushushu reaction zijongwa imodeli ebalulekileyo terms.Ukuqhuba i-optimizer eyakhelwe-ngaphakathi usebenzisa le migaqo ikhethiweyo ivelisa isethi yeemeko zokusabela ezenzelwe ukwandisa iindawo eziphezulu zemveliso ngelixa kuncitshiswa ukuqala kwezinto eziphathekayo.
Ngokusekwe kuncwadi olubonisa ukuba icopper(I) oxide (Cu2O) inokusebenza njengohlobo olusebenzayo lwe-catalytic kwimiphezulu yobhedu eyi-zero-valent 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 zokonyuka kwemveliso kwaye kwabonwa kwakhona phantsi kwesiphumo esibalulekileyo solungiselelo. yezinto zokuqala, ezibalwe ukuba> 99%.Nangona kunjalo, ukubeka iliso yi-HPLC kubonise ukuba olu kuguqulwa lunciphise kakhulu ixesha lokuphendula ixesha elide de kube malunga nemizuzu ye-90, apho umsebenzi wabonakala uhambela phezulu kwaye ufikelele "kwimeko ezinzileyo". ayizizo iileya ezizikhuselayo.Oku kuphelisa isidingo sokongeza ithusi (II) umthombo wokuncedisa ngokubambisana71.