Mahalo iā ʻoe no kou kipa ʻana iā Nature.com. ʻO ka polokalamu kele pūnaewele āu e hoʻohana nei he kākoʻo liʻiliʻi no CSS. No ka ʻike maikaʻi loa, paipai mākou iā ʻoe e hoʻohana i kahi polokalamu kele hou (a i ʻole e hoʻopau i ke ʻano hoʻohālikelike ma Internet Explorer).
Ke hoʻololi nei ka hana hoʻohui i ke ʻano o ka poʻe noiʻi a me ka poʻe ʻoihana ʻenehana e hoʻolālā a hana i nā mea kemika e hoʻokō i kā lākou mau pono kikoʻī. hoʻonui i ka hiki o ia mau mea hana. Ua hoʻohui maikaʻi ʻia a hoʻopaʻa ʻia e kahi hui Cu-mediated Huisgen 1,3-dipolar cycloaddition me ka hoʻohana ʻana i ka UAM chemistry set-up. no ka nānā ʻana a me ka hoʻonui ʻana.
Ma muli o kāna mau pono nui ma luna o kāna hui nui, ʻo ke kemika kahe he kahua koʻikoʻi a ulu nui i ka hoʻonaʻauao a me nā ʻoihana ʻoihana ma muli o kona hiki ke hoʻonui i ka koho a me ka pono o ka synthesis kemika. ʻOi aku ma mua o 50% o nā hopena i loko o nā ʻoihana kemika maikaʻi a me nā lāʻau lapaʻau hiki ke pōmaikaʻi mai ka hoʻohana ʻana i ka hoʻoheheʻe kahe mau ʻana7.
I kēia mau makahiki i hala iho nei, ua ulu nui nā pūʻulu e ʻimi ana e pani i nā mea aniani kahiko a i ʻole nā ​​​​mea hana kemika kahe me nā mea hana hoʻohui hoʻohui (AM) chemistry "nā moku pane" 8. ʻO ka hoʻolālā iterative, hana wikiwiki, a me nā mana 3-dimensional (3D) o kēia mau ʻenehana he pōmaikaʻi no ka poʻe makemake e hoʻopili i kā lākou mau mea hana i kahi hoʻonohonoho kikoʻī o ka hopena, nā mea hana, a i ʻole nā ​​kūlana kūikawā. ʻO nā ʻenehana paʻi 3D e like me stereolithography (SL)9,10,11, fused deposition modeling (FDM)8,12,13,14 a me ka paʻi inkjet 7, 15, 16. ʻO ka nele o ka paʻa a me ka hiki ʻana o ia mau mea hana ke hana i kahi ākea o nā hopena kemika / analyses17, 18, 19, ʻoi aku ka palena nui o kēia helu AM. kahua17, 18, 19, 20 .
Ma muli o ka hoʻohana nui ʻana o ka kemika kahe a me nā waiwai maikaʻi e pili ana me AM, pono e ʻimi i nā ʻenehana ʻoi aku ka maikaʻi e hiki ai i nā mea hoʻohana ke hana i nā moku hoʻoheheʻe kahe i hoʻonui ʻia me nā mana kemika a me nā analytical i hoʻonui ʻia.
Hoʻokahi kaʻina hana hoʻohui i hiki ke hoʻomohala i nā reactors kemika maʻamau, ʻo ia ka Ultrasonic Additive Manufacturing (UAM) . kaʻina hana, i loko o-situ manawa lolouila helu mana (CNC) milling a laser machining wehewehe i ka upena shape o ka papa o ka mea i hoʻopaʻa 'ia 24, 25. 'O ia hoʻi, 'aʻole i kaupalena 'ia ka mea hoʻohana i nā pilikia e pili ana i ka wehe 'ana i ke koena maka build material mai liʻiliʻi wai auwai, ka mea pinepine ka hihia me ka pauka a me ka wai AM systems26,27,28. ʻO ka koho ʻana o nā mea hui ma mua o ke kaʻina heheʻe, ʻo ia ka mea e hiki ke hoʻokō maikaʻi ʻia nā koi mechanical a me nā kemika o nā noi kikoʻī. hiki ke hoʻomaʻamaʻa i ka hāʻawi ʻana i ka ʻike manawa maoli mai ka mea hoʻohana i ka mea hoʻohana ma o ka loiloi hoʻohui.
Ua hōʻike ka hana mua32 a nā mea kākau i ka hiki o ke kaʻina hana UAM e hana i nā ʻano metala 3D microfluidic structures me nā mana hoʻohui i hoʻohui ʻia. He mea nānā wale nō kēia. ʻO kahi mea hana ikaika ʻaʻole nānā wale akā hoʻoulu i ka synthesis kemika ma o nā mea catalyst i hoʻohui ʻia. ka hana ʻana i nā mea he nui e hoʻohui i ka conductivity thermal kiʻekiʻe a me nā mea catalytic; a me ka hoʻokomo pono ʻana i nā mea ʻike wela ma waena o nā kahawai reagent no ka nānā pono ʻana i ka wela o ka hopena a me ka control.To demonstrate the functionality of the reactor, a library of pharmaceutically important 1,4-disubstituted 1,2,3-triazole compounds was synthesized by copper-catalyzed Huisgen 1,3-dipolar work cycloaddition design how can open computer cycloaddition. i nā manawa hou a me nā mea e hiki ai ke kemika ma o ka noiʻi multidisciplinary.
Ua kūʻai ʻia nā solvents a me nā reagents a pau mai Sigma-Aldrich, Alfa Aesar, TCI a i ʻole Fischer Scientific a ua hoʻohana ʻia me ka hoʻomaʻemaʻe ʻole ʻana. (CD3)2SO ma ke ʻano he mea hoʻoheheʻe. Ua hana ʻia nā hopena a pau me ka hoʻohana ʻana i ka Uniqsis FlowSyn flow chemistry platform.
Ua hoʻohana ʻia ʻo UAM e hana i nā mea hana a pau i loko o kēia haʻawina. Ua hana ʻia ka ʻenehana i ka makahiki 1999, a me kāna mau kikoʻī ʻenehana, nā ʻāpana hana a me nā hoʻomohala ʻana mai ka mea hiki ke aʻo ʻia ma o nā mea i hoʻopuka ʻia ma lalo nei 34,35,36,37. Ua hoʻokō ʻia ka mea hana (Figure 1) me ka hoʻohana ʻana i kahi mana ultra-kiʻekiʻe, 9kW SonicLayer 4000® UAM, ʻōnaehana no ka ʻōnaehana OHFabrisonic, ka ʻōnaehana OHFabrisonic. ʻO Cu-110 a me Al 6061. ʻO Cu-110 kahi mea keleawe kiʻekiʻe (ʻo 99.9% keleawe ka liʻiliʻi), e lilo ia i moho maikaʻi no nā reactions copper-catalyzed, a no laila ua hoʻohana ʻia ʻo ia he "papa hana i loko o kahi microreactor. Hoʻohana ʻia ʻo Al 6061 O ma ke ʻano he "bulk" mea me ka Alloy embedding layer i hoʻohana ʻia no ka nānā ʻana. ʻO ka papa Cu-110 Al 6061 O kahi mea i hōʻike ʻia e kūpono loa me nā kaʻina UAM38, 39, 40, 41 a ua hoʻāʻo ʻia a ʻike ʻia ʻO ka paʻa kemika me nā reagents i hoʻohana ʻia i kēia hana ʻO ka hui pū ʻana o Al 6061 O me Cu-110 ua manaʻo ʻia he mea hoʻohui ʻia no kēia papa 3 1 lalo.
Nā ʻanuʻu hana reactor (1) Al 6061 substrate (2) Ka hana ʻana o ke kahawai lalo i hoʻonohonoho ʻia i ka foil keleawe (3) Hoʻokomo ʻana i nā thermocouples ma waena o nā papa (4) Ke kahawai kiʻekiʻe (5) Inlet a me waho (6) Monolithic reactor.
ʻO ka manaʻo hoʻolālā o ke ala wai ka hoʻohana ʻana i kahi ala convoluted e hoʻonui i ka mamao o ka hele ʻana o ka wai i loko o ka chip, ʻoiai e mālama ana i ka chip i ka nui hiki ke mālama. ka hui 'ana i hiki ke ho'okō 'ia, 'o ka ho'olālā reactor 'elua mau inlets reagent i hui 'ia ma ka Y-junction ma mua o ke komo 'ana i ka serpentine hui 'āpana. 'O ke kolu o ka inlet, e intersects i ke kahawai i ka hapalua o kona noho, ua komo i loko o ka manao o ka hiki mai multistep reaction syntheses.
Loaʻa i nā kahawai a pau kahi ʻaoʻao huinahā (ʻaʻohe kihi kikoʻī), ka hopena o ka mīkini CNC i hoʻohana ʻia no ka hana ʻana i ka geometry channel. Ua koho ʻia nā ana o ke kahawai e hōʻoia i kahi puka kiʻekiʻe (no ka microreactor), ʻoiai he liʻiliʻi ia e hoʻomaʻamaʻa i ka pilina o ka ʻili (catalysts) no ka hapa nui o nā wai i loko. ʻO 750 µm a ʻo ka nui o ka reactor volume he 1 ml. ʻO kahi mea hoʻohui i hoʻohui ʻia (1/4″—28 UNF thread) i hoʻokomo ʻia i loko o ka hoʻolālā e ʻae i ka hoʻopili maʻalahi o ka hāmeʻa me nā lako kemika kahe kalepa. Hoʻopili ʻia ka nui o ke kahawai e ka mānoanoa o ka mea foil, kona mau waiwai mechanical, a me nā ʻāpana hoʻopaʻa i hoʻohana ʻia me nā ultrasonics. Ma kahi ākea kikoʻī no kahi mea i hāʻawi ʻia, e "kau" ka mea i loko o ke kahawai i hana ʻia. I kēia manawa ʻaʻohe kumu hoʻohālike kikoʻī no kēia helu ʻana, no laila ua hoʻoholo ʻia ka laulā o ke kahawai kiʻekiʻe loa no kahi mea i hāʻawi ʻia a hoʻolālā ʻia ma ka hoʻokolohua; i kēia hihia, ʻaʻole e hāʻule ka laula o 750 μm.
Hoʻoholo ʻia ke ʻano (square) o ke kahawai ma o ka hoʻohana ʻana i kahi ʻoki huinaha. Hiki ke hoʻololi ʻia ke ʻano a me ka nui o nā kahawai e nā mīkini CNC me ka hoʻohana ʻana i nā mea ʻoki ʻoki like ʻole e loaʻa ai nā kahe kahe like ʻole a me nā ʻano. hoʻopau.Ma kēia hana, i mea e mālama ai i ka symmetry o ke kahawai, ua hoʻohana ʻia kahi outline square.
I loko o kahi hoʻomaha i hoʻonohonoho mua ʻia i ka hana ʻana, ua hoʻokomo pololei ʻia nā ʻimi wela thermocouple (Type K) i loko o ka hāmeʻa ma waena o nā pūʻulu o luna a me lalo (Figure 1 - Stage 3).
Hana ʻia ke kaʻina hana hoʻoheheʻe metala e ka pu UAM e hoʻohana ana i ka 25.4 mm ākea, 150 micron mānoanoa metala foil. Hoʻopaʻa ʻia kēia mau ʻāpana pepa i loko o nā ʻāpana pili e uhi i ka wahi kūkulu holoʻokoʻa; ʻOi aku ka nui o ka mea i waiho ʻia ma mua o ka huahana hope loa e like me ke kaʻina subtractive e hoʻopuka i ke ʻano o ka ʻupena hope. ʻO ka ʻāpana i hoʻopau ʻia e hālāwai me nā pae pololei o ka wili palaoa CNC. He liʻiliʻi ka laula o ke kahawai i hoʻohana ʻia no kēia hāmeʻa e hōʻoia ʻaʻole e "kau" ka mea foil i loko o ke kahawai wai, no laila e mālama ke kahawai i kahi ʻāpana kūhā like.
Ua hōʻike ʻia nā haʻawina e loaʻa ana ka diffusion elemental liʻiliʻi ma ka UAM bonding interface 46, 47 me ka ʻole o ka mālama ʻana i ka wela, no laila no nā mea hana i kēia hana, ʻokoʻa ka papa Cu-110 mai ka papa Al 6061 a hoʻololi koke.
E hoʻouka i ka 250 psi (1724 kPa) back pressure regulator (BPR) i hoʻopaʻa mua ʻia i ka puka o ka reactor a paʻi i ka wai ma o ka reactor ma ka wikiwiki o 0.1 a 1 mL min-1. Ua nānā ʻia ke kaomi reactor me ka hoʻohana ʻana i ka ʻōnaehana ʻōnaehana i kūkulu ʻia ʻo FlowSyn e hōʻoia i hiki i ka ʻōnaehana ke hoʻomau i ka hoʻomau mau ʻana o ke kahe kahe mau ʻana. ʻokoʻa ma waena o nā thermocouples i hoʻokomo ʻia i loko o ka reactor a me nā mea i hoʻokomo ʻia i loko o ka FlowSyn chip heating plate. Loaʻa ʻia kēia ma ka hoʻololi ʻana i ka wela wela papahana ma waena o 100 a me 150 °C ma 25 °C increments a me ka ʻike ʻana i nā ʻokoʻa ma waena o nā mahana i hoʻopaʻa ʻia a hoʻopaʻa ʻia. lako polokalamu.
ʻO nā kūlana hopena o ka cycloaddition o ka phenylacetylene a me ka iodoethane ua hoʻonui ʻia (Scheme 1- Cyclloaddition of phenylacetylene a me iodoethane Scheme 1- Cyclloaddition o phenylacetylene a me iodoethane). ma ka hora 1:2.
Ua hoʻomākaukau ʻia nā mea hoʻokaʻawale kaʻawale o ka sodium azide (0.25 M, 4:1 DMF: H2O), iodoethane (0.25 M, DMF), a me phenylacetylene (0.125 M, DMF). Ua hui pū ʻia kahi 1.5 mL aliquot o kēlā me kēia hopena ma o ka reactor ma ka wahi i makemake ʻia e kahe ana a me ka mahana. phenylacetylene mea hoʻomaka a hoʻoholo ʻia e ka high performance liquid chromatography (HPLC).
Ua kālailai 'ia nā laʻana a pau me ka Chromaster HPLC nenoaiu (VWR, PA, USA) i loko o ka quaternary pauma, kolamu umu, loli hawewe UV detector a me autosampler.The kolamu mea he Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 mm i ka nui, 5 µm particle nui, mālama 'ia ma 40: wai me ka mea hoʻonāwaliwali °C. ma kahi kahe o 1.5 mL.min-1. ʻO ka nui o ka injection he 5 µL a ʻo ka lōʻihi o ka nalu detector he 254 nm. ʻO ka % peak area no ka laʻana DOE i helu ʻia mai nā wahi kiʻekiʻe o ke koena alkyne a me nā huahana triazole wale nō.
ʻO ka hoʻohui ʻana i ka hoʻopuka ʻana i ka reactor analysis i ka polokalamu MODDE DOE (Umetrics, Malmö, Suedena) i ʻae ʻia i ka nānā pono ʻana i nā ʻano hopena a me ka hoʻoholo ʻana i nā kūlana hoʻonā maikaʻi loa no kēia cycloaddition. ʻO ka holo ʻana i ka optimizer i kūkulu ʻia a koho i nā huaʻōlelo kumu hoʻohālike koʻikoʻi e hāʻawi i kahi hoʻonohonoho o nā kūlana hopena i hoʻolālā ʻia e hoʻonui i ka wahi kiʻekiʻe o ka huahana me ka hōʻemi ʻana i ka wahi kiʻekiʻe o ka acetylene.
Ua hoʻokō ʻia ka oxidation o ke keleawe ʻili i loko o ke keʻena hopena catalytic me ka hoʻohana ʻana i ka hopena o ka hydrogen peroxide (36%) e kahe ana ma ke keʻena pane (ka kahe kahe = 0.4 mL min-1, ka manawa noho = 2.5 min) ma mua o ka synthesis o kēlā me kēia waihona waihona triazole.
I ka manawa i ʻike ʻia ai kahi kūlana maikaʻi loa, ua hoʻohana ʻia lākou i kahi ʻano o ka acetylene a me ka haloalkane derivatives e ʻae i ka hui ʻana o kahi synthesis hale waihona puke liʻiliʻi, a laila e hoʻokumu ai i ka hiki ke hoʻopili i kēia mau kūlana i kahi ākea o nā reagents hiki ke loaʻa (Figure 1).2).
E hoʻomākaukau i nā mea hoʻonā kaʻawale o ka sodium azide (0.25 M, 4: 1 DMF: H2O), nā haloalkanes (0.25 M, DMF) a me nā alkynes (0.125 M, DMF). Ua hui pū ʻia nā ʻāpana 3 mL o kēlā me kēia haʻina a paʻi ʻia ma o ka reactor ma 75 µL.min-1 a me 150 °C. o ka ethyl acetate. Ua holoiʻia ka hāpana hāpana me ka 3 × 10 mL o ka wai. Ua hui pūʻia nā papa wai a laweʻia me 10 mL o ka ethyl acetate; ua huiia na papa organik, holoiia me 3 x 10 mL o ka brine, maloo ma luna o MgSO4 a kānana, a laila, ua wehe 'ia ka solvent i vacuo. Ua hoomaemaeia na laana e ka kolamu chromatography ma ka silica gel me ka ethyl acetate ma mua o ka ho'ā'o 'ana e ka hui 'ana o HPLC, 1H NMR, 13C NMR a me ka high resolution mass spectrometry.
Ua loaʻa nā spectra a pau me ka Thermofischer precision Orbitrap resolution mass spectrometer me ESI ma ke kumu ionization.
Hana ʻia ka loiloi TLC ma nā papa silica i kākoʻo ʻia i ka alumini.
Ua kālailai ʻia nā laʻana a pau me ka hoʻohana ʻana i ka VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) i lako me kahi autosampler, kolamu umu binary pump a me ka hawewe lōʻihi hoʻokahi. ʻO ke kolamu i hoʻohana ʻia he ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland).
Injections (5 µL) ua hana pololei ia mai diluted crude reaction mixture (1:10 dilution) a kālailai ʻia me ka wai: methanol (50:50 or 70:30), koe wale no kekahi mau laʻana e hoʻohana ana i ka 70:30 solvent system (denoted as a star number) ma ke kahe kahe o 1.5 mL/min. The kolamu 40°Cptth is malama.
Ua helu ʻia ka % wahi kiʻekiʻe o ka laʻana mai ka wahi kiʻekiʻe o ke koena alkyne, ʻo ka huahana triazole wale nō, a ʻo ka hoʻokomo ʻana i ka mea hoʻomaka e ʻae i ka ʻike ʻana i nā piko kūpono.
Hoʻopili ʻia nā hōʻailona a pau me ka Thermo iCAP 6000 ICP-OES. Ua hoʻomākaukau ʻia nā kūlana calibration a pau me ka hoʻohana ʻana i ka 1000 ppm Cu maʻamau solution ma 2% nitric acid (SPEX Certi Prep).
UAM utilizes ultrasonic metala kuʻihao e like me ka hoʻopaʻa 'enehana no ka metala foil mea i hoʻohana 'ia e kūkulu i ka hope hui.Ultrasonic metala kuʻihao utilizes ka vibrating metala mea paahana (i kapaia he horn a kani ultrasonic horn) e pili puʻe i ka foil papa / mua consolidated papa e hoʻopaʻa 'oiai vibrating ka mea. a hoʻohana ʻia ka haʻalulu, hiki i nā oxides ma ka ʻili o ka mea ke pohā. ʻO ka hoʻomau ʻana a me ka haʻalulu hiki ke hoʻohaʻahaʻa i nā asperities o ka mea 36 . ʻO ka pilina pili me ka wela a me ke kaomi kūloko a laila alakaʻi i ka hoʻopaʻa paʻa ʻana i nā mea pili; Hiki iā ia ke kōkua i ka hoʻopili ʻana ma o ka hoʻololi ʻana i ka ikehu ili 48. ʻO ke ʻano o ka mīkini hoʻopaʻa e lanakila ai i nā pilikia he nui e pili ana i ka wela hoʻoheheʻe ʻana a me ka wela kiʻekiʻe ma hope o nā hopena i ʻōlelo ʻia i loko o nā ʻenehana hana hoʻohui ʻē aʻe.
ʻO ka lua o ka mea maikaʻi no ka UAM, ʻo ia ke kahe kiʻekiʻe o ka plastik i ʻike ʻia i nā mea metala, ʻoiai ma nā haʻahaʻa haʻahaʻa, ʻo ia hoʻi ma lalo o ka helu heheʻe o nā mea metala. foil, papa ma ka papa. Ua hookomo pono ia na mea e like me na fiber optical 49, reinforcements 46, electronics 50, and thermocouples (kēia hana) i loko o na hale UAM no ka hana ana i na hui hui hooikaika a me ka passive.
Ma kēia hana, ua hoʻohana ʻia nā mea like ʻole o ka hoʻopaʻa ʻana a me ka intercalation o UAM no ka hana ʻana i ka microreactor nānā ʻana i ka wela catalytic.
Ke hoʻohālikelike ʻia me ka palladium (Pd) a me nā mea hoʻoheheʻe metala ʻē aʻe i hoʻohana mau ʻia, he nui nā pōmaikaʻi o Cu catalysis. Hana maikaʻi nā hopena Cu-catalyzed me ka loaʻa ʻole o nā ligands ʻē aʻe, He mea maʻalahi kēia mau ligands inā makemake ʻia, akā ʻo nā mea i hoʻohana ʻia ma Pd chemistry he paʻakikī, pipiʻi, a me ka ea-ʻeleʻele (iv) Cu, ʻike nui ʻia no kona hiki ke hoʻopaʻa i nā alkynes i ka synthesis. (v) Hiki iā Cu ke hoʻoikaika i ka arilation o kekahi mau nucleophiles ma nā ʻano ʻano Ullmann.
ʻO nā hiʻohiʻona o ka heterogenization o kēia mau hopena a pau i hōʻike ʻia ma ke alo o Cu (0). ʻO kēia ka mea nui ma muli o ka ʻoihana lāʻau lapaʻau a me ka ulu ʻana o ka nānā ʻana i ka hoʻihoʻi ʻana i ka catalyst metala a me ka hoʻohana hou ʻana55,56.
Paionia e Huisgen i ka 1960s57, ka 1,3-dipolar cycloaddition reaction ma waena o ka acetylene a me ka azide i ka 1,2,3-triazole i manaʻo ʻia he synergistic demonstration reaction. ʻO ka hopena 1,2,3 triazole moieties he mea hoihoi loa ia e like me ka pharmacophore i ka hoʻohana ʻana i nā lāʻau lapaʻau.
Ua hoʻomaka hou kēia hopena i ka wā i hoʻokomo ai ʻo Sharpless a me nā mea ʻē aʻe i ka manaʻo o ka "click chemistry"59. Ua hoʻohana ʻia ka huaʻōlelo "click chemistry" e wehewehe i kahi hoʻonohonoho paʻa, hilinaʻi a koho hoʻi no ka synthesis wikiwiki o nā pūhui hou a me nā hale waihona puke ma o heteroatom linkage (CXC) maʻalahi61.
ʻAʻole pili ka huila Huisgen 1,3-dipole cycloaddition i ka waeʻano o "click chemistry". Akā naʻe, ua hōʻike ʻo Medal a me Sharpless i kēia hanana hui ʻana azide-alkyne i 107 a 108 ma ke alo o Cu (I) i hoʻohālikelike ʻia me ka uncatalyzed 1,3-dipolar cycload3 i hoʻomaikaʻi maikaʻi ʻia. ʻaʻole koi i nā pūʻulu pale a i ʻole nā ​​kūlana hopena koʻikoʻi a me nā hua kokoke i ka hoʻololi piha ʻana a me ke koho ʻana i ka 1,4-disubstituted 1,2,3-triazoles (anti-1,2,3-triazole) ma kahi manawa (Figure 3).
Nā hualoaʻa Isometric o Huisgen cycloadditions maʻamau a me ke keleawe. stereoisomers o nā azole.
ʻO ka hapa nui o nā protocols e pili ana i ka hōʻemi ʻana i nā kumu Cu (II) paʻa, e like me ka hoʻemi ʻana o CuSO4 a i ʻole Cu(II)/Cu(0) i hui pū ʻia me nā paʻakai sodium.
Nā haʻawina kinetic a me isotopic labeling e Worrell et al. 65 hōʻike i, ma ka hihia o terminal alkynes, elua equivalent o ke keleawe i komo i ka ho'ā 'ana i ka reactivity o kela a me keia mole i azide.The noiʻi mechanical proceeds ma o eono lala keleawe apo metala i hanaia e ka coordination o azide i σ-hoʻopaʻa keleawe acetylide me π-hoʻopaʻa keleawe like me ka stable derivazoor apo apo apo derivative. ka emi ʻana, a ukali ʻia e ka proton decomposition e hāʻawi i nā huahana triazole a pani i ka pōʻai catalytic.
ʻOiai ua kākau maikaʻi ʻia nā pōmaikaʻi o nā hāmeʻa kemika kahe, aia ka makemake e hoʻohui i nā mea hana analytical i loko o kēia mau ʻōnaehana no ka nānā ʻana i ka laina, in-situ, kaʻina hana66,67.UAM ua hōʻike ʻia he ala kūpono no ka hoʻolālā ʻana a me ka hana ʻana i nā reactors kahe 3D paʻakikī i hana ʻia me nā mea catalytically active, thermally conductive me nā mea hoʻokomo pono ʻia 4 (Figure sensing elements).
Aluminum-keleawe kahe reactor fabricated e kani ultrasonic additive manufacturing (UAM) me ka paʻakikī i loko o ke ala kanal, embedded thermocouples a catalytic reaction chamber.To visualize kūloko wai ala, a transparent prototype fabricated me ka stereolithography.
No ka hōʻoia ʻana i ka hana ʻana o nā reactors no nā hopena kūlohelohe e hiki mai ana, pono e hoʻomehana ʻia nā mea hoʻoheheʻe ma luna o kahi e hoʻolapalapa ai; ua ho'āʻoʻia ke kaomi a me ka mahana. Ua hōʻike ka ho'āʻo kaomi e mālama ka pūnaewele i ka paʻa a me ka paʻa mau me ka piʻiʻana o ka pūnaewele (1.7 MPa).
ʻO ka hoʻohui ʻana i ka thermocouple i hoʻokomo ʻia (Figure 1) i ka mea hoʻopaʻa ʻikepili wela ua hōʻike ʻia he 6 °C (± 1 °C) ka thermocouple ma mua o ka mahana i hoʻonohonoho ʻia ma ka ʻōnaehana FlowSyn. ʻO ka maʻamau, ʻo ka piʻi ʻana o ka wela he 10 °C ka hopena o ka pālua ʻana o ka pane ʻana, no laila hiki i ka ʻokoʻa wela o nā degere liʻiliʻi ke hoʻololi nui i ka ʻokoʻa o ke kino i ke kiʻekiʻe o ka wela. diffusivity o nā mea i hoʻohana ʻia i ke kaʻina hana. He kūlike kēia thermal drift a no laila hiki ke helu ʻia i ka hoʻonohonoho lako e hōʻoia i ka loaʻa ʻana o nā mahana kūpono a ana ʻia i ka wā o ka hopena.
ʻO ka reactor i hōʻike ʻia ma kēia hana ʻo ia ka laʻana mua o ka hoʻohana ʻana i ka ʻenehana UAM i ka hana ʻana i nā reactors kemika a kamaʻilio i kekahi mau palena nui e pili ana i kēia manawa me ka paʻi AM/3D o kēia mau mea, e like me: (i) ka lanakila ʻana i nā pilikia i hōʻike ʻia e pili ana i ka hana keleawe a i ʻole ka alumini alumini (ii) hoʻomaikaʻi ʻia ka hoʻonā ʻana o ke kahawai kūloko i hoʻohālikelike ʻia me nā ʻenehana melting powder bed fusion (PBF) melting (69 rough material) melting (69 rough laser) melting (69 rough material) ili kino26 (iii) Hoemi ana ka wela wela, ka mea e maʻalahi ka pili pono o na ike, ka mea hiki ole i loko o ka pauda moe enehana, (v) lanakila ilihune mechanical waiwai a me ka sensitivity o ka polymer-e pili ana i nā mea i nāʻano likeʻole organic solvents17,19.
Ua hōʻike ʻia ka hana o ka reactor e ke ʻano o ka copper-catalyzed alkyne azide cycloaddition reactions ma lalo o nā kūlana kahe mau (Fig. 2) . ʻO nā hui alkyl halides i ke alo o ka sodium chloride (Figure 3). ʻO ka hoʻohana ʻana i kahi ala kahe mau e hoʻēmi i nā pilikia palekana e hiki ke ala mai i nā kaʻina hana, no ka mea, ua hoʻopuka kēia hopena i nā intermediates azide reactive a weliweli loa [317], [318]. phenylacetylene a me iodoethane) (e nānā i ke Kiʻi 5).
(Ma luna hema) Hoʻolālā o ka hoʻonohonoho hoʻonohonoho i hoʻohana ʻia e hoʻokomo i ka reactor 3DP i loko o ka ʻōnaehana kahe (luna ʻākau) i loaʻa i ka optimized (lalo) scheme o ka Huisgen cycloaddition 57 scheme ma waena o ka phenylacetylene a me ka iodoethane no ka hoʻonui ʻana a me ka hōʻike ʻana i ka helu hoʻololi hoʻololi ʻana.
Ma ka mālama ʻana i ka manawa noho o nā reagents i loko o ka ʻāpana catalytic o ka reactor a me ka nānā pono ʻana i ka wela o ka hopena me ka thermocouple probe i hoʻohui pono ʻia, hiki ke hoʻopaʻa ʻia nā kūlana hopena me ka liʻiliʻi o ka manawa a me ka hoʻohana ʻana i ka waiwai. Manaʻo ʻia ka manawa noho a me ka mahana pane ʻana i nā huaʻōlelo koʻikoʻi. ʻO ka holo ʻana i ka optimizer i kūkulu ʻia me ka hoʻohana ʻana i kēia mau huaʻōlelo i koho ʻia e hana i kahi hoʻonohonoho o nā kūlana hopena i hoʻolālā ʻia e hoʻonui i nā wahi kiʻekiʻe o ka huahana me ka hōʻemi ʻana i nā wahi kiʻekiʻe o ka mea hoʻomaka.
Ma muli o nā palapala e hōʻike ana e hiki ke hana i ka copper(I) oxide (Cu2O) ma ke ʻano he catalytic species ma luna o ka zero-valent copper surfaces i kēia mau hopena, ua noiʻi ʻia ka hiki ke pre-oxidize i ka ʻili reactor ma mua o ka hoʻokō ʻana i ka hopena i ke kahe 70,71. ka piʻi nui o ka hoʻololi ʻana o ka mea hoʻomaka, i helu ʻia he> 99%. Akā naʻe, ua hōʻike ʻia ka nānā ʻana e ka HPLC ua hōʻemi nui kēia hoʻololi ʻana i ka manawa hoʻonā lōʻihi loa a hiki i 90 mau minuke, a laila ʻike ʻia ka hana i ka pae a hiki i kahi "kūlana kūpaʻa". ʻano CuO a me Cu2O ʻaʻole nā ​​papa pale ponoʻī. Hoʻopau kēia i ka pono e hoʻohui i kahi kumu keleawe (II) kōkua no ka hui pū ʻana71.