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O loʻo suia le auala e suʻesuʻe ai le au suʻesuʻe ma le aufaipisinisi ma gaosia masini vailaʻau e faʻafetaui ai o latou manaʻoga faapitoa. I lenei galuega, matou te lipotia le faʻataʻitaʻiga muamua o se reactor tafe na fausia e le faʻaogaina o le uʻamea faʻapipiʻi malosi Ultrasonic Additive Manufacturing (UAM) faʻatasi ai ma vaega catalytic tuʻufaʻatasia ma elemene faʻalogo. faateleina le gafatia o ia masini.O se faasologa o biologically taua 1,4-disubstituted 1,2,3-triazole compounds sa faamanuiaina synthesized ma optimized e se Cu-mediated Huisgen 1,3-dipolar cycloaddition reaction e faaaoga ai se UAM chemistry set-up.By leveraging le tulaga tulaga ese o le UAM ma faʻagasolo faʻagaioiga faʻagaioiga masini faʻaauau pea gaioiga faʻagaioiga, faʻafofoga faʻaauau pea gaioiga faʻagaioiga, ma faʻafofoga faʻaauau gaioiga faʻagaioiga. mo le mata'ituina o tali ma le fa'alelei.
Ona o lona tulaga lelei tele i luga o lona vaega tele, tafe kemisi o se fanua taua ma tuputupu aʻe i tulaga uma tau aʻoaʻoga ma alamanuia ona o lona gafatia e faateleina ai le filifilia ma le lelei o le synthesis kemikolo.E oo atu lenei mai le faigofie organic molecule formation1 i pharmaceutical compounds2,3 ma oloa faalenatura4,5,6. E sili atu nai lo le 50% o gaioiga i totonu o vailaʻau ma vailaʻau lelei e mafai ona faʻamanuiaina mai le faʻaogaina o le faʻaogaina o le tafe faifaipea7.
I tausaga talu ai nei, o loʻo i ai le faʻatupulaia o vaega o loʻo vaʻavaʻai e sui mea tioata masani poʻo mea faʻamisi kemisi faʻatasi ma mea faʻapipiʻi faʻapipiʻi faʻapipiʻi (AM) kemisi "vaa tali" 8. O le mamanu faʻasolosolo, gaosiga vave, ma le 3-dimensional (3D) gafatia o nei metotia e aoga mo i latou e manaʻo e faʻavasega a latou masini i se seti faʻapitoa o tali, masini, poʻo tulaga faʻapitoa e faʻatatau i le faʻaogaina o galuega, aso, poʻo tulaga faʻapitoa. 3D lomitusi auala e pei o stereolithography (SL)9,10,11, fused deposition modeling (FDM) 8,12,13,14 ma inkjet lomitusi 7, 15, 16. Le leai o le malosi ma le gafatia o ia masini e faatino ai le tele o chemical reactions / analyses17, 18, 19 faʻatapulaʻa o lenei faʻatinoga lautele, faʻatapulaʻa AM. fanua17, 18, 19, 20 .
Ona o le faʻateleina o le faʻaogaina o le kemisi tafe ma mea lelei e fesoʻotaʻi ma AM, e manaʻomia le suʻesuʻeina o auala sili atu e mafai ai e tagata faʻaoga ona faʻapipiʻi vaʻa faʻafefe faʻatasi ma le faʻaleleia o vailaʻau ma analytical gafatia.
O se tasi o gaosiga faʻaopoopo faʻapipiʻi e iai le gafatia e atiaʻe ai vailaʻau faʻaleaganuʻu masani o le Ultrasonic Additive Manufacturing (UAM). faagasologa, lea i totonu o-situ komipiuta numera pulea (CNC) milling po o le laser machining e faamatalaina ai le foliga upega o se vaega o mea fusifusia 24, 25. O lona uiga e le faatapulaaina le tagata e faaaogāina e faafitauli e fesootai ma le aveesea o totoe raw fausia mea mai ala vai laiti, lea e masani lava o le tulaga i le paʻu ma vai AM systems26,27,28.E mafai foi ona faalautele atu lenei mea le filifiliga saoloto mamanu UAM i le filifiliga saoloto mea. tu'ufa'atasiga o mea eseese i totonu o se la'asaga e tasi. O le filifiliga o fa'atasiga meafaitino i tua atu o le fa'afefeteina o lona uiga e mafai ona sili atu ona fetaui le mana'oga fa'ainisinia ma vaila'au o talosaga fa'apitoa. I le fa'aopoopoina i le fa'amauina o le tulaga mautu, o le isi mea fa'apitoa e fa'afeiloa'i i le taimi o le fa'apipi'iina o le ultrasonic o le maualuga o le tafe o mea palasitika i le maualalo o le vevela29,30,31,32,33. O lenei tulaga tulaga ese o le UAM fa'apipi'i elemene e mafai ona fa'aogaina e aunoa ma le fa'apipi'iina o elemene eletise. e mafai ona faafaigofieina le tuʻuina atu o faʻamatalaga taimi moni mai le masini i le tagata faʻaoga e ala i auʻiliʻiliga tuʻufaʻatasia.
O galuega a le au tusitala ua mavae32 na faʻaalia ai le gafatia o le faiga o le UAM e fausia ai fausaga uʻamea 3D microfluidic faʻatasi ai ma le mafai ona tuʻufaʻatasia. E naʻo se masini mataʻituina lenei pepa. o se masini malosi e le gata ina mataʻituina ae faʻaosoina foi le faʻaogaina o vailaʻau e ala i mea faʻapipiʻi faʻapipiʻi faʻapipiʻiina.O le masini e tuʻufaʻatasia le tele o mea lelei e fesoʻotaʻi ma tekinolosi UAM i le gaosiga o masini vailaʻau 3D, e pei o le: le mafai ona faʻaliliu saʻo mamanu 3D atoa mai faʻataʻitaʻiga fesoasoani komepiuta (CAD) i oloa; fa'asologa o mea e tele e tu'ufa'atasia ai le fa'auluina o le vevela ma mea fa'amamafa; ma embedding thermal sensors tuusao i le va reagent vaitafe mo tali saʻo le mataituina o le vevela ma le control.To faaalia le functionality o le reactor, o se faletusi o pharmaceutically taua 1,4-disubstituted 1,2,3-triazole compounds sa synthesized e apamemea-catalyzed Huisgen 1,3-dipolar galuega cycloaddition e mafai ona tatala le mea cycloaddition komipiuta matala lenei. maua avanoa fou ma avanoa mo le kemisi e ala i su'esu'ega fa'apitoa.
O solvents ma reagents uma na faʻatau mai Sigma-Aldrich, Alfa Aesar, TCI poʻo Fischer Scientific ma sa faʻaaogaina e aunoa ma le faʻamamaina muamua. (CD3) 2SO e pei o le solvent.O tali uma na faia i le faʻaaogaina o le Uniqsis FlowSyn flow chemistry platform.
UAM na faʻaaogaina e faʻapipiʻi ai masini uma i lenei suʻesuʻega. O le tekonolosi na fausia i le 1999, ma o ana faʻamatalaga faʻapitoa, faʻasologa o galuega ma atinaʻe talu mai lona mea fou e mafai ona suʻesuʻeina e ala i mea faʻasalalau faʻasalalau nei34,35,36,37. O le masini (Ata 1) na faʻaaogaina e faʻaaoga ai se malosiaga ultra-maualuga, 9kW SonicLayer 4000® UAM, mea faʻapipiʻi (OHFabrisonic), faʻaogaina o le ISA. masini tafe sa Cu-110 ma Al 6061.Cu-110 ei ai se mea maualuga apamemea (maualalo 99.9% apamemea), avea ai o se sui tauva lelei mo tali apamemea-catalyzed, ma o lea ua faaaogaina e avea o se "vaega malosi i totonu o se microreactor. Al 6061 O o loo faaaogaina e avea o se "tele" mea, e faʻapipiʻi vaega faʻapipiʻi faʻaogaina ma auiliiliga faʻaogaina; Cu-110 layer. Al 6061 O o se mea ua faʻaalia e matua fetaui lelei ma faiga UAM38, 39, 40, 41 ma ua faʻataʻitaʻiina ma maua E mautu le vailaʻau faʻaaogaina i lenei galuega O le tuʻufaʻatasia o le Al 6061 O ma le Cu-110 o loʻo faʻatatauina o se mea faʻaoga talafeagai mo le 3 1 lalo.
Laasaga o le gaosiga o le reactor (1) Al 6061 substrate (2) Fausia o le alavai pito i lalo ua seti i pepa apamemea (3) Fa'apipi'i o le thermocouples i le va o apa (4) Alalaupapa pito i luga (5) Ulufale ma fafo (6) Reactor Monolithic.
O le filosofia mamanu o le auala vai o le faʻaaogaina lea o se auala faʻafefeteina e faʻateleina ai le mamao e alu ai le sua i totonu o le vaʻa, aʻo tausia le vaʻa i se mea e mafai ona faʻaogaina.O lenei faʻaopoopoga o le mamao e manaʻomia e faʻateleina ai le taimi o fesoʻotaʻiga catalyst / regent ma tuʻuina atu oloa sili ona lelei. O meataalo e faʻaaogaina 90 ° piʻo i pito o le ala saʻo e faʻaosofia ai le faʻalavelave faʻafefe i totonu o le masini faʻafesoʻotaʻi44 ma faʻateleina le faʻafefiloi o le vai (catalyst time44). fefiloi e mafai ona ausia, o le mamanu reactor foliga lua inlets reagent tuufaatasia i le Y-soʻo i luma o le ulu atu i le gata fefiloi section.The lona tolu inlet, lea intersects le vaitafe afa e ala i lona nofomau, ua aofia i le mamanu o le lumanai multistep tali syntheses.
O alalaupapa uma ei ai se faʻailoga sikuea (leai ni faʻataʻitaʻiga), o le taunuuga o le faʻaogaina o le CNC i taimi uma e faʻaaogaina ai le geometry o le auala. E filifilia le tele o auala e faʻamautinoa ai le maualuga (mo se microreactor) voluma, aʻo laʻititi lava e faʻafaigofie ai fegalegaleaiga i luga o le eleele (catalysts) mo le tele o vai o loʻo i ai. 750 µm ma le voluma reactor atoa o le 1 ml.O se fesoʻotaʻiga tuʻufaʻatasia (1/4″-28 UNF filo) o loʻo aofia i totonu o le mamanu e faʻatagaina ai le faʻafesoʻotaʻi faigofie o le masini ma meafaigaluega kemisi faʻatau pisinisi. O le tele o le alalaupapa e faʻatapulaʻaina i le mafiafia o mea pepa pepa, o ona mea faʻainisinia, ma faʻamaufaʻailoga faʻaogaina faʻaaogaina i ultrasonics. I se lautele faʻapitoa mo se mea ua tuʻuina atu, o mea o le a "saʻo" i totonu o le auala na faia. I le taimi nei e leai se fa'ata'ita'iga fa'apitoa mo lenei fa'atusatusaga, o lea o le maualuga o le lautele o le alalaupapa mo se mea tu'uina atu ma le mamanu e fuafuaina fa'ata'ita'i; i lenei tulaga, o le lautele o le 750 μm o le a le mafua ai le sag.
O le foliga (sikuea) o le auala e fuafuaina e ala i le faaaogaina o se tipi sikuea.O le foliga ma le tele o auala e mafai ona suia e masini CNC e faaaoga meafaigaluega tipi eseese e maua ai fua faatatau tafe eseese ma uiga.O se faataitaiga o le fatuina o se auala curved foliga e faaaoga ai le meafaigaluega 125 μm e mafai ona maua i le galuega a Monaghan45.When le pepa foil ua teuina i luga o se mea laupapa o le a maua i luga o se mafolafola o le pepa foilqua. maeʻa.I lenei galuega, ina ia faʻatumauina le faʻatusa o le alalaupapa, sa faʻaaogaina se faʻasologa sikuea.
I le taimi o se taofi na muaʻi faʻapipiʻiina i le gaosiga, o loʻo faʻapipiʻi saʻo i totonu o le masini i le va o vaega pito i luga ma lalo o le alalaupapa (Ata 1 - Stage 3).
O le faʻagasologa o le faʻapipiʻiina o uʻamea e faia e se pu UAM e faʻaaoga ai le 25.4 mm lautele, 150 micron mafiafia uʻamea uʻamea. O nei laupepa pepa o loʻo faʻapipiʻiina i se faasologa o fasi pepa lata ane e ufiufi ai le fale atoa; o le tele o le mea na teuina e sili atu nai lo le oloa mulimuli e pei o le subtractive faagasologa e maua ai le foliga upega mulimuli.CNC machining o loʻo faʻaaogaina e faʻaogaina ai le faʻaogaina o fafo ma totonu o le meafaigaluega, e mafua ai le maeʻa o le masini ma alalaupapa tutusa ma le meafaigaluega filifilia ma CNC process parameters (e tusa ma le 1.6 μm Ra i lenei faʻataʻitaʻiga) . o le vaega maeʻa o le a fetaui ma le CNC maeʻa vili saʻo tulaga. O le lautele o le alalaupapa e faʻaaogaina mo lenei masini e laʻititi lava e faʻamautinoa ai e le o "sag" le pepa pepa i totonu o le alavai vai, o lea e tausia ai e le alalaupapa se sikuea sikuea sikuea. Avanoa e ono i totonu o mea pepa ma faʻasologa o le UAM na fuafuaina faʻataʻitaʻiga e se paaga gaosi oloa (Fabrisonic LLC, ISA).
O suʻesuʻega ua faʻaalia ai e itiiti le faʻasalalauina o elemene e tupu i le UAM bonding interface 46, 47 e aunoa ma se togafitiga faʻamalo faaopoopo, o lea mo masini i lenei galuega, o le Cu-110 layer e tumau pea le tulaga ese mai le Al 6061 layer ma suia faʻafuaseʻi.
Fa'apipi'i le 250 psi (1724 kPa) fa'atonuina muamua (1724 kPa) fa'atonuina o le mamafa (BPR) i le pusa o le fa'amalo ma pamu vai e ala i le reactor i se fua faatatau o le 0.1 i le 1 mL min-1. Na mata'ituina le mamafa o le reactor i le fa'aogaina o le FlowSyn fausia-i totonu o le masini masini e fa'amaonia ai e mafai e le faiga ona fa'amaumau so'o se fa'amaualuga tumau o le vevela fa'amanino. eseesega i le va o le thermocouples faʻapipiʻiina i totonu o le reactor ma i latou o loʻo faʻapipiʻiina i totonu o le FlowSyn chip faʻavevela plate.E ausia lenei mea e ala i le fesuiaʻiina o le vevela vevela programmable i le va o le 100 ma le 150 ° C i le 25 ° C faʻaopoopoga ma matauina soʻo se eseesega i le va o le vevela ua faʻapipiʻiina ma faʻamaumau. Na ausia lenei mea i le faʻaaogaina o le tc-08 faʻamaumauga a Cambridge, Cambridge ma le Picologger. polokalame.
O tulaga o le tali atu o le cycloaddition o le phenylacetylene ma le iodoethane na sili ona lelei (Scheme 1- Cyclloaddition of phenylacetylene and iodoethane Scheme 1- Cyclloaddition of phenylacetylene ma iodoethane). i le 1:2.
O vaifofo eseese o le sodium azide (0.25 M, 4:1 DMF: H2O), iodoethane (0.25 M, DMF), ma le phenylacetylene (0.125 M, DMF) na saunia. O le 1.5 mL aliquot o vaifofo taitasi na faʻafefiloi ma pamu e ala i le reactor i le vaega o loʻo manaʻomia le tafe o le fua faatatau o le triazole ma le vevela. phenylacetylene mea amata ma fuafuaina e le maualuga faatinoga sua chromatography (HPLC). Mo le faifai pea o le auʻiliʻiliga, o tali uma sa faʻataʻitaʻiina ina ua maeʻa ona tuʻu ese le faʻafefiloi o tali mai le reactor. O laina parakalafa ua filifilia mo le sili ona lelei o loʻo faʻaalia i le Laulau 2.
Sa suʻesuʻeina faʻataʻitaʻiga uma e faʻaaoga ai le Chromaster HPLC system (VWR, PA, ISA) e aofia ai se pamu quaternary, ogaumu koluma, vaʻavaʻai umi o le galu o le UV ma le autosampler.O le koluma o se Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 mm i le tele, 5 µm particle size, tausia i le 40: Water 5 µm , faʻamauina i le 40: 5 µm sol tha water: i le fua o le tafe o le 1.5 mL.min-1.O le voluma tui o le 5 µL ma le umi o le galu o le detector o 254 nm. O le % pito i luga mo le faʻataʻitaʻiga DOE na fuafuaina mai vaega pito i luga o le alkyne totoe ma triazole oloa naʻo. O le tui o mea amata e mafai ai ona faʻamaonia o tumutumu talafeagai.
Faʻapipiʻiina le faʻauluina o le gaosiga o le reactor i le polokalama MODDE DOE (Umetrics, Malmö, Suetena) faʻatagaina se suʻesuʻega maeʻaeʻa o faʻasologa o taunuʻuga ma le faʻamautuina o tulaga lelei tali atu mo lenei cycloaddition.Running le fausia-i totonu optimizer ma le filifilia o faaupuga faʻataʻitaʻiga taua uma e maua ai se seti o tulaga tali fuafuaina e faʻateleina le vaega pito i luga o oloa aʻo faʻaitiitia le vaega amata o le acetylene.
O le faʻamaʻiina o le kopa i luga o le eleele i totonu o le potu faʻafefe catalytic na ausia e ala i le faʻaogaina o se vaifofo o le hydrogen peroxyide (36%) o loʻo tafe atu i totonu o le potu faʻafefe (vave = 0.4 mL min-1, taimi nofo = 2.5 min) aʻo leʻi faʻapipiʻiina o faletusi taʻitasi triazole.
O le taimi lava na iloa ai se seti sili ona lelei o tulaga, na faʻaaogaina i le tele o acetylene ma haloalkane derivatives e faʻatagaina ai le tuʻufaʻatasia o se faʻasologa o faletusi laiti, ma faʻamautuina ai le mafai ona faʻaogaina nei tulaga i se lautele lautele o mea e mafai ona faʻaogaina (Ata 1).2).
Saunia vaifofo eseese o le sodium azide (0.25 M, 4: 1 DMF: H2O), haloalkanes (0.25 M, DMF) ma alkynes (0.125 M, DMF).3 mL aliquots o vaifofo taitasi na faʻafefiloi ma pamu i le reactor i le 75 µL.min-1 ma le 150 °C le aofaʻi na aoina i le 150 °C. o le ethyl acetate. O le faʻataʻitaʻiga faʻataʻitaʻiga na fufuluina i le 3 × 10 mL o le vai. Na tuʻufaʻatasia le faʻafefeteina o le vai ma aveese mai i le 10 mL o le ethyl acetate; ona tuʻufaʻatasia lea o laulau faʻalaʻau, fufuluina i le 3 x 10 mL o le brine, faʻagogo i luga o le MgSO4 ma faʻamamaina, ona aveese lea o le solvent i le vacuo.The samples na faʻamamaina e ala ile koluma chromatography i luga ole silica gel e faʻaaoga ai le ethyl acetate aʻo leʻi suʻesuʻeina e se tuufaatasiga o le HPLC, 1H NMR, 13C NMR ma le maualuga resolution mass spectrometry.
Na maua uma alaleo e faʻaaoga ai le Thermofischer precision Orbitrap resolution mass spectrometer ma le ESI e avea ma puna faʻamea.
O suʻesuʻega a le TLC na faia i luga o ipu silica faʻapipiʻi alumini. O papatusi na faʻaalia i le malamalama o le UV (254 nm) poʻo le vanillin staining ma le vevela.
O faʻataʻitaʻiga uma na suʻesuʻeina e faʻaaoga ai le VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) faʻapipiʻiina i le autosampler, koluma ogaumu binary pamu ma le umi o le galu e tasi.
Injections (5 µL) na faia tuusao mai diluted crude reaction mixture (1:10 dilution) ma suʻesuʻeina i le vai: methanol (50:50 poʻo le 70:30), sei vagana ai nisi faʻataʻitaʻiga e faʻaaoga ai le 70:30 solvent system (faʻailogaina o se numera fetu) i le tafe o le 1.5 mL / min. O le galu 40 °Cpt.
O le % pito maualuga o le faʻataʻitaʻiga na fuafuaina mai le pito i luga ole alkyne totoe, naʻo le triazole oloa, ma o le tui ole mea amata na faʻatagaina ai le faʻamaoniaina o tumutumu talafeagai.
O faʻataʻitaʻiga uma na suʻesuʻeina e faʻaaoga ai le Thermo iCAP 6000 ICP-OES. O tulaga faʻavasega uma na saunia e faʻaaoga ai le 1000 ppm Cu solution standard i le 2% nitric acid (SPEX Certi Prep) .Na saunia tulaga uma i le 5% DMF ma le 2% HNO3 solution, ma faʻataʻitaʻiga uma na faʻafefeteina 20-HNO3 fofo DMF faʻataʻitaʻiga.
UAM faʻaaogaina le uʻamea uʻamea ultrasonic e avea o se metotia faʻapipiʻi mo mea faʻapipiʻi uʻamea na faʻaaogaina e fausia ai le faʻapotopotoga mulimuli.Ultrasonic metal welding e faʻaogaina ai se meafaigaluega uʻamea vibrating (taʻua o se pu poʻo se pu ultrasonic) e faʻaoga ai le mamafa i luga o le pepa faʻapipiʻi / muamua faʻapipiʻi faʻapipiʻi e faʻapipiʻiina aʻo vibrating le meafaitino. ma le vibration o loʻo faʻaaogaina, o le oxides i luga o le mea e mafai ona taʻe. Faʻaauau le mamafa ma le vibration e mafai ona mafua ai asperities o le meafaitino e paʻu 36 . Fesoʻotaʻiga vavalalata ma le vevela faʻapitonuʻu ma le mamafa ona taʻitaʻia ai lea i le soʻotaga mautu i mea faʻaoga; e mafai foi ona fesoasoani i le adhesion e ala i suiga i luga o le malosi48.O le natura o le faiga faʻapipiʻi e manumalo i le tele o faʻafitauli e fesoʻotaʻi ma le fesuiaiga o le vevela vevela ma le maualuga o le vevela i le maeʻa ai o aʻafiaga o loʻo taʻua i isi auala faʻapipiʻi gaosiga.
O se tulaga lelei lona lua mo le UAM o le maualuga maualuga o le tafe palasitika ua matauina i mea uamea, e oo lava i le maualalo o le vevela, o lona uiga i lalo ifo o le liusuavai o mea uʻamea. O le tuufaatasiga o le ultrasonic oscillation ma le mamafa e mafua ai le maualuga o le femalagaiga o tuaoi o saito i le lotoifale ma le recrystallization e aunoa ma le faateleina o le vevela tele masani e fesootaʻi ma mea tetele. pepa iila, fa'alava ma fa'a.Elemene e pei o alava opitika 49, fa'amalosi 46, mea fa'aeletonika 50, ma thermocouples (lenei galuega) ua fa'apipi'iina lelei uma i totonu o fausaga UAM e fatu ai fa'atasiga tu'ufa'atasiga ma fa'agaoioi.
I lenei galuega, na fa'aogaina uma le feso'ota'iga meafaitino eseese ma avanoa fa'afeso'ota'i a le UAM e fa'atupu ai le mata'ituina o le vevela pito sili ona lelei.
Pe a faatusatusa i le palladium (Pd) ma isi u'amea e masani ona fa'aogaina, o le Cu catalysis e tele ona lelei: (i) I le tamaoaiga, Cu e taugofie nai lo le tele o isi metala o lo'o fa'aaogaina i le catalysis ma o le mea lea o se filifiliga manaia mo le gaosiga o vaila'au (ii) O lo'o fa'atupula'ia le tele o tali fa'a'oso'o fa'asaga i le Cu-catalyzed ma e foliga mai e fai si fa'atasi i le P532. O tali Cu-catalyzed e galue lelei i le leai o isi ligands, O nei ligands e masani ona faʻapipiʻiina faigofie ma taugofie pe a manaʻomia, ae o na mea e faʻaaogaina i le kemisi Pd e masani ona lavelave, taugata, ma le ea (iv) Cu, aemaise lava le lauiloa mo lona mafaia ona fusifusia alkynes i le faʻasologa, Mo se faʻataʻitaʻiga, bimetallic-catalyzed Sonogashiradesiclickupling and chemistry. (v) E mafai foi e Cu ona faʻalauteleina le faʻauluina o le tele o nucleophiles i gaioiga Ullmann-ituaiga.
O faʻataʻitaʻiga o le heterogenization o nei gaioiga uma na faʻaalia talu ai nei i le i ai o le Cu (0) .E tele lava ona mafua mai i le falemaʻi falemaʻi ma le faʻatupulaia o le taulai atu i le toe faʻaleleia o le uʻamea ma toe faʻaaogaina55,56.
Paionia e Huisgen i le 1960s57, o le 1,3-dipolar cycloaddition reaction i le va o le acetylene ma le azide i le 1,2,3-triazole ua manatu o se synergistic demonstration reaction. O le taunuuga o le 1,2,3 triazole moieties e sili ona fiafia e pei o le pharmacophore i le faʻaaogaina o vailaʻau faʻamaʻi.
O lenei tali na toe taulai atu ina ua faailoa mai e Sharpless ma isi le manatu o le "kiliki kemisi" 59. O le faaupuga "kiliki kemisi" e faʻaaogaina e faʻamatala ai se seti malosi, faʻatuatuaina ma filifilia o tali mo le faʻapipiʻiina vave o mea fou ma faletusi tuʻufaʻatasia e ala i le heteroatom linkage (CXC) 60 O le apili faʻapipiʻi o nei tali e mafua mai i a latou vai ma le maualuga o le faʻaogaina o mea e maua ai, o le gaosiga o le okesene e faigofie. faigofie61.
O le masani o Huisgen 1,3-dipole cycloaddition e le auai i le vaega o le "kiliki kemisi" .Ae ui i lea, Medal ma Sharpless faʻaalia o lenei mea faʻapipiʻi azide-alkyne e aʻafia ai le 107 i le 108 i le i ai o Cu (I) pe a faʻatusatusa i le uncatalyzed 1,3-dipolar cycload3 cycload3 faʻaleleia atili le faʻaogaina o le 62,63 reaction. e le manaʻomia le puipuia o kulupu poʻo tulaga faʻalavelave faʻafefe ma maua mai latalata i le liua atoatoa ma le filifilia i le 1,4-disubstituted 1,2,3-triazoles (anti-1,2,3-triazole) i luga o se fua taimi (Ata 3).
Isometric i'uga o mea masani ma kopa-catalyzed Huisgen cycloadditions.Cu(I)-catalyzed Huisgen cycloadditions e maua ai na o le 1,4-suia 1,2,3-triazoles, ae o le vevela o le Huisgen cycloadditions e masani ona maua mai 1,54-triazole 1,54-triazoles. stereoisomers o azoles.
O le tele o faʻasalalauga e aofia ai le faʻaitiitiga o punaʻoa o le Cu (II), e pei o le faʻaitiitia o le CuSO4 poʻo le Cu (II) / Cu (0) ituaiga faʻatasi ma masima sodium. Faʻatusatusa i isi faʻamaʻi uamea, o le faʻaogaina o le Cu (I) o loʻo i ai le sili ona lelei o le taugofie ma faigofie ona taulimaina.
Su'esu'ega fa'ailoga kinetic ma isotopic e Worrell et al. 65 faaalia e faapea, i le tulaga o alkynes terminal, e lua tutusa o le apamemea o loo aafia i le faagaoioia o le reactivity o mole taitasi agai i azide. O le faiga fuafuaina e alu atu e ala i se mama apamemea apamemea e ono sui na faia e le faamaopoopoina o azide i le σ-fusia apamemea acetylide ma π-fusifusi apamemea e pei o se stable donary rings. fa'aitiitiga, soso'o ai ma le fa'aleagaina o le proton e tu'uina atu ai oloa triazole ma tapuni ai le taamilosaga catalytic.
E ui o aoga o masini kemisi tafe o loʻo faʻamaonia lelei, o loʻo i ai se manaʻoga e tuʻufaʻatasia meafaigaluega auʻiliʻili i totonu o nei faiga mo le in-line, in-situ, process monitoring66,67.UAM faʻamaonia e avea o se auala talafeagai mo le mamanuina ma le gaosia o mea faʻafefe 3D sili ona faigata e faia i catalytically active, thermally conductive material with direct embedded sensing elements (Figure sensing elements).
Aluminum-kopa tafe reactor fabricated e ultrasonic additive manufacturing (UAM) faʻatasi ai ma faʻalavelave faʻapipiʻi auala i totonu, faʻapipiʻiina thermocouples ma catalytic reaction chamber.To vaai faalemafaufau ala vai totonu, o se prototype manino fabricated faʻaaogaina stereolithography o loʻo faʻaalia foi.
Ina ia fa'amautinoaina o lo'o fa'apipi'iina mea fa'a'ave'a mo gaioiga fa'aola i le lumana'i, e mana'omia le fa'avevela lelei o so'o i luga a'e o le mea fa'apuna; o loʻo faʻataʻitaʻiina le mamafa ma le vevela. O le suʻega o le mamafa na faʻaalia ai o loʻo faʻatumauina e le faiga se faʻamautu ma faʻaauau pea le mamafa e oʻo lava i le faʻateleina o le mamafa o le faiga (1.7 MPa). O le suʻega hydrostatic na faia i le vevela o le potu e faʻaaoga ai le H2O e pei o le vai.
Faʻafesoʻotaʻi le thermocouple faʻapipiʻiina (Ata 1) i le logger data vevela na faʻaalia ai o le thermocouple e 6 °C (± 1 °C) e sili atu le malulu nai lo le vevela na faʻapipiʻiina i luga o le FlowSyn system. E masani lava, o le 10 °C o le faateleina o le vevela e mafua ai le faaluaina o le fua o le tali, o lea o le eseesega o le vevela o na o ni nai tikeri e mafai ona matua suia ai le maualuga o le vevela e mafua ona o le maualuga o le vevela. diffusivity o mea o loʻo faʻaaogaina i le gaosiga o le gaosiga. O lenei vevela vevela e tumau ma e mafai ona faʻamauina i le seti meafaigaluega e faʻamautinoa ai le saʻo o le vevela e ausia ma fuaina i le taimi o le tali.
O le reactor o loʻo tuʻuina atu i lenei galuega o le faʻataʻitaʻiga muamua lea o le faʻaaogaina o tekinolosi UAM i le fausiaina o vailaʻau kemisi ma faʻatalanoaina le tele o tapulaʻa tetele o loʻo fesoʻotaʻi nei ma le AM ​​/ 3D lomitusi o nei masini, e pei o le: (i) faʻatoʻilaloina o faʻafitauli Lipoti e fesoʻotaʻi ma le kopa poʻo le alumini alumini gaosi (ii) faʻaleleia le faʻaogaina o le ala i totonu e faʻatusatusa i le paʻu o le moega fusion (PBF) metotia e pei o le faʻaogaina o le paʻu (PBF) faʻataʻitaʻiga 5, poʻo leisa 6, poʻo leisa 6. texture i luga26 (iii) Faʻaitiitia le vevela o le gaosiga, lea e faʻafaigofie ai le tuʻufaʻatasia tuusaʻo o masini, lea e le mafai ona faʻaogaina i le tekonolosi moega, (v) faʻatoʻilaloina mea faʻainisinia leaga ma le maʻaleʻale o vaega faʻavae polymer i le tele o solvents masani masani17,19.
O le faʻatinoga o le reactor na faʻaalia e se faʻasologa o alkyne azide cycloaddition reactions i lalo o le faʻaauau pea o le tafe (Fig. 2) . vaega alkyl halides i le i ai o le sodium chloride (Ata 3) .O le faʻaogaina o le faʻaauau pea o le tafe e faʻaitiitia ai popolega saogalemu e mafai ona tulaʻi mai i faiga faʻaputuga, ona o lenei gaioiga e maua ai ni mea e sili ona faʻafefe ma matautia azide intermediates [317], [318]. I le taimi muamua, o le tali na sili ona lelei mo le cycloaddition o le cycloaddition of phenylacetanethylene ma le phenylacetanetylene. phenylacetylene ma iodoethane) (silasila i le Ata 5).
(I luga agavale) Fuafuaga o le seti na faʻaaogaina e faʻaogaina ai le 3DP reactor i totonu o le tafe (taumatau pito i luga) na maua i le optimized (lalo) polokalame o le Huisgen cycloaddition 57 fuafuaga i le va o le phenylacetylene ma le iodoethane mo le faʻamalosia ma le faʻaalia o le optimized parameters reaction rate conversion rate.
E ala i le puleaina o le taimi e nofo ai le reagents i le vaega catalytic o le reactor ma mataʻituina lelei le vevela o le tali ma se suʻega thermocouple tuʻufaʻatasia tuusaʻo, e mafai ona vave faʻaleleia tulaga faʻaalia ma le saʻo ma le itiiti o le taimi ma le faʻaaogaina o meafaitino. Na vave ona iloa o le suiga sili ona maualuga na maua pe a oʻo i le taimi e nofo ai i le 15 minute ma le vevela o le tali o le 150 °C e mafai ona faʻaaogaina le polokalama faakomepiuta. taimi nofomau ma le vevela o tali e manatu o faaupuga faʻataʻitaʻiga taua.O le faʻaogaina o le faʻaogaina o le faʻaogaina o nei faaupuga filifilia e faʻatupuina ai se seti o tulaga tali fuafuaina e faʻateleina ai vaega pito i luga o oloa aʻo faʻaititia le amataga o meafaitino vaega pito i luga.
Faʻavae i luga o tusitusiga o loʻo faʻaalia ai o le kopa (I) oxide (Cu2O) e mafai ona galue e avea o se ituaiga catalytic aoga i luga o luga o le apamemea zero-valent i nei gaioiga, o le gafatia e muai faʻamaʻiina le faʻamaʻi luga aʻo leʻi faia le gaioiga i le tafe na suʻesuʻeina 70,71. taua faateleina i le liua o mea amata, lea na fuafuaina e avea ma> 99%. Ae ui i lea, o le mataituina e le HPLC na faaalia ai o lenei liua na matua faaitiitia ai le tele o le umi o le tali atu taimi seia oo i le 90 minute, lea na foliga mai ai le gaoioiga e tulaga ese ma oo atu i se "tulaga tumau" . fa'apena CuO ma Cu2O e le'o ni mea e puipuia ai le tagata lava ia.O lenei mea e fa'ate'aina ai le mana'oga e fa'aopoopo se puna apamemea (II) fesoasoani mo le tu'ufa'atasiga71.