Mahalo iā ʻoe no ka 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 e hoʻohana ʻoe i kahi polokalamu kele hou (a i ʻole e hoʻopau i ke ʻano hoʻohālikelike i Internet Explorer).
Ke hoʻololi nei ka hana hoʻohui i ke ʻano o ka hoʻolālā ʻana a me ka hana ʻana o nā mea noiʻi a me nā mea hana kemika e hoʻokō i kā lākou mau pono kikoʻī. ʻO nā pūhui 1,4-disubstituted 1,2,3-triazole koʻikoʻi koʻikoʻi i hoʻohui ʻia a hoʻopaʻa ʻia e ka hui Cu-mediated Huisgen 1,3-dipolar cycloaddition me ka hoʻohana ʻana i kahi kemika UAM hoʻonohonoho.
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 ia no ka poʻe e makemake e hoʻopilikino i kā lākou mau mea hana i kahi hoʻonohonoho kikoʻī o ka hopena, nā mea paʻi, a i ʻole nā ​​kūlana kūikawā. ʻenehana 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 e hana i kahi ākea o nā hopena kemika / analyses17, 18, 18, 19, 20 nui no ka hoʻokō 19, 20 nui no kēia kahua 19 AM. 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.
ʻO kahi kaʻina hana hoʻohui hoʻohui e hiki ai i keʻano o nā mea hana uila e pili ana iā Ultras i ka papa hana liʻiliʻi ʻO ka hana hana id id, i loko o kahi o ka mana o ka mana o ka mana o ka mahana e pili ana i nā mea kūʻai aku ma kahi o nā mea kūʻai aku a me nā hui hui likeʻole i ka hana hana hoʻokahi ʻO nā mea ma waena o nā'āpana metala me kaʻole o ka hōʻino'ia.uam i hoʻopiliʻia e ka laweʻana i ka mea hoʻohana i ka mea hoʻohana i ka mea hoʻohana i nā mea hoʻohana i hoʻopiliʻia.
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 ʻana i ka wela o ka hopena a me ka mana. nā ʻoihana no 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 mua ʻole. nt. 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 paʻi 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 o ka mea hoʻohana i koho ʻia ʻo UAM. 110 a me Al 6061.Cu-110 he keleawe kiʻekiʻe (99.9% keleawe ka liʻiliʻi), e lilo ia i moho maikaʻi no nā hopena copper-catalyzed, a no laila ua hoʻohana ʻia ma ke ʻano he "papa hana i loko o kahi microreactor.Hoʻohana ʻia ʻo Al 6061 O ma ke ʻano he mea "nui", a me ka Embedding layer i hoʻohana ʻia no ka nānā ʻana;Alloy auxiliary embedding a me annealed condition i hui pū ʻia me Cu-110 layer.ʻO Al 6061 O kahi mea i hōʻike ʻia he kūpono loa me nā kaʻina UAM38, 39, 40, 41 a ua hoʻāʻo ʻia a loaʻa ʻo Chemically stable me nā reagents i hoʻohana ʻia i kēia hana.ʻO ka hui pū ʻana o Al 6061 O me Cu-110 ka mea i manaʻo ʻia he hui kūpono no ka UAM a no laila he mea kūpono ia no kēia haʻawina.38,42 Ua helu ʻia kēia mau mea hana ma ka Papa 1 ma lalo nei.
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 ʻo ia 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. d, o ka reactor design features two reagent inlets i hui 'ia ma ka Y-junction ma mua o ke komo 'ana i ka serpentine mixing section. The third inlet, which intersects the stream halfway through its residency, is in the design of future multistep reaction syntheses.
Loaʻa i nā kahawai a pau kahi ʻaoʻao huinahā (ʻaʻohe kikoʻī kikoʻī), ʻo ka hopena o ka CNC milling manawa i hoʻohana ʻia no ka hana ʻana i ke kahawai geometry. Ua koho ʻia nā ana o ke kahawai e hōʻoia i kahi kiʻekiʻe (no ka microreactor) puka puka, ʻoiai he liʻiliʻi ia e hoʻomaʻamaʻa i ka launa ʻana o ka honua (catalysts) no ka hapa nui o nā wai i loko. 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.Ua kaupalena 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 ultrasonic.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 laulā o 750 μm.
Hoʻoholo ʻia ke ʻano (square) o ke kahawai ma ka hoʻohana ʻana i kahi ʻokiʻoki 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 no ka loaʻa ʻana o nā kahe kahe like ʻole a me nā ʻano. , no ka mālama ʻana 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 ka ʻupena hope loa. ʻO nā pae pololei o ka wili palaoa CNC. ʻAʻole liʻiliʻi ka laulā 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 kūhāhā.
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 250 psi (1724 kPa) hoʻoponopono hoʻihoʻi (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 i ka 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 ʻokoʻa ma waena o ka ʻokoʻa ʻokoʻa. ʻO nā kāne i hoʻokomoʻia i loko o ka reactor a me nā mea i hoʻokomoʻia i loko o ka FlowSyn chip heating plate. Loaʻa kēia ma ka hoʻololiʻana i ka mahana wela wela ma waena o 100 a me 150 °C i nā hoʻonui 25 °C a me kaʻikeʻana i nā mea likeʻole ma waena o nā mahana i hoʻopaʻaʻia a hoʻopaʻaʻia.
ʻO nā kūlana hopena o ka cycloaddition o ka phenylacetylene a me ka iodoethane ua hoʻokō ʻia (Scheme 1- Cycloaddition o phenylacetylene a me iodoethane Scheme 1- Cyclloaddition o phenylacetylene a me iodoethane). .
Hoʻokaʻawale ʻia nā mea hoʻonā o ka sodium azide (0.25 M, 4:1 DMF: H2O), iodoethane (0.25 M, DMF), a me phenylacetylene (0.125 M, DMF) i hoʻomākaukau ʻia. Ua hui pū ʻia kahi 1.5 mL aliquot o kēlā me kēia hopena ma o ka reactor i ka makemake o ke kahe kahe a me ka mahana. d by high performance liquid chromatography (HPLC). No ke kūlike o ka nānā 'ana, ua hō'ike 'ia nā hopena a pau ma hope koke iho o ka ha'alele 'ana o ka hui 'ana i ka reactor. Ua hō'ike 'ia ma ka Papa 2 nā pae ho'ohālikelike i koho 'ia no ka ho'onui 'ana.
Ua kālailai 'ia nā la'ana a pau me ka Chromaster HPLC nenoai (VWR, PA, USA) i loko o ka quaternary pump, kolamu umu, variable wavelength UV detector and autosampler.The kolamu he Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 mm ka nui, 5 µm particle size, mālama 'ia ma 40 me ka nui o ka wai i 50 °C. 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. Ua helu ʻia ka % peak area no ka laʻana DOE 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 ʻokoʻa 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 ʻia nā ʻāpana 3 mL o kēlā me kēia haʻina a hoʻomoʻi ʻia ma o ka reactor ma 75 µL.min-1 a me 150 °C i hōʻiliʻili ʻia me ka 150 °C. cetate. 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 standard solution i 2% nitric acid (SPEX Certi Prep).
UAM utilizes ultrasonic metala kuʻihao e like me ka hoʻopaʻa 'ana no ka mea metala foil mea i hoʻohana 'ia e kūkulu i ka hope hui.Ultrasonic metala kuʻihao utilizes ka vibrating metala mea paahana (i kapaia he pu kani a kani ultrasonic horn) e pili puʻe i ka foil papa / mua consolidated papa e hoʻopaʻa 'ia oiai vibrating ka mea. i hoʻohana ʻia, hiki i nā oxides ma ka ʻili o ka mea ke crack.Continued pressure and vibration can cause asperities of the material to collapse 36 . Intimate contact with locally induced heat and pressure then lead to solid-state bonding at material interfaces;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 kiʻekiʻe o ke kahe 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. .Ua hoʻokomo pono ʻia nā mea e like me nā fiber optical 49, reinforcements 46, electronics 50, a me nā thermocouple (kēia hana) i loko o nā hale UAM e hana i nā hui hui hoʻoikaika a 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.
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. s hana maikaʻi i ka nele o nā ligands ʻē aʻe, He mea maʻalahi kēia mau ligands a maʻalahi hoʻi inā makemake ʻia, akā ʻo nā mea i hoʻohana ʻia i ka Pd chemistry he paʻakikī, pipiʻi, a me ka lewa (iv) Cu, ʻike nui ʻia no kona hiki ke hoʻopaʻa i nā alkynes i ka synthesis, No ka laʻana, bimetallic-catalyzed Sonogashira hoʻohui ʻia me ka azideshira hoʻohui ʻia me ka azideshira hoʻohui ʻia me ka azideshira hoʻohui ʻia me ka azideshira. nucleophiles i 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 pane 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 hui ma o heteroatom linkage (CXC)60 ʻO ka hoʻopiʻi synthetic o kēia mau hopena ke kumu mai ko lākou mau ʻano wai kiʻekiʻe a maʻalahi.
ʻAʻole pili ka Huisgen 1,3-dipole cycloaddition maʻamau i ka ʻāpana o ka "click chemistry". Akā naʻe, ua hōʻike ʻo Medal a me Sharpless i kēia hui hui azide-alkyne i 107 a 108 ma ke alo o Cu (I) i hoʻohālikelike ʻia me ka uncatalyzed 1,3-dipolar cycload3 ʻaʻole pono e hoʻomaikaʻi i nā hui. aiʻole nā ​​kūlana hoʻopiʻi koʻikoʻi a me nā hua kokoke i ka hoʻololi pihaʻana a me ka kohoʻana i ka 1,4-disubstituted 1,2,3-triazoles (anti-1,2,3-triazole) ma kahi manawa (Figure 3).
ʻO nā hopena o nā isometric o ka maʻamau a me nā copper-catalyzed recloaddicitions reigding 1,4-tyrialyzed 1,2-tyrialy
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 equivalents o ke keleawe i komo i ka ho'ā 'ana i ka reactivity o kela a me keia mole i ka azide.The noiʻi hana e hele mai 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 derivage rings. , 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 i 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 o ka pane ʻana, no laila hiki i ka ʻokoʻa wela o kekahi mau degere ke hoʻololi nui i ka ʻokoʻa o ke kino ma muli o ke kiʻekiʻe o ka wela. ʻO 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 alumini alumini (ii) hoʻomaikaʻi ʻia ka hoʻonā ʻana o ke kahawai kūloko i hoʻohālikelike ʻia me nā ʻano hana melting powder bed fusion (PBF). iii) Ho'emi 'ia ka wela o ka ho'oponopono 'ana, ka mea e ma'alahi i ka ho'opa'a 'ana o nā mea 'ike, 'a'ole hiki ke ho'ohana 'ia i ka 'enekinia moena pauda, ​​(v) lanakila 'ino i nā waiwai mechanical a me ka na'au o nā 'āpana polymer-based i nā 'ano mea ho'ohenehene ma'amau17,19.
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) . ides i mua 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 azide intermediates kiʻekiʻe loa [317], [318]. ʻO ka hoʻomaka ʻana, ua hoʻomaikaʻi ʻia ka hopena no ka cycloaddition o phenylacetylene -Schemodocetylene a me iʻa. ) (e nānā i ke Kiʻi 5).
(Ma luna hema) Hoʻolālā o ka hoʻonohonoho hoʻonohonoho i hoʻohana ʻia no ka hoʻokomo ʻana i ka reactor 3DP i loko o ka ʻōnaehana kahe (luna ʻākau) i loaʻa i ka hoʻolālā i hoʻopaʻa ʻia (lalo) o ka hui huisgen cycloaddition 57 ma waena o ka phenylacetylene a me ka iodoethane no ka hoʻonui ʻana a me ka hōʻike ʻana i ka helu hoʻololi hoʻololi ʻana i nā palena.
Ma ka mālama ʻana i ka manawa noho o nā reagents ma ka ʻāpana catalytic o ka reactor a me ka nānā pono ʻana i ka wela o ka hopena me kahi ʻimi thermocouple i hoʻohui pono ʻia, hiki ke hoʻopaʻa ʻia nā kūlana hopena me ka liʻiliʻi o ka manawa a me ka hoʻohana ʻana i nā mea. ʻO 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 i ka wā e hōʻemi ana i ka hoʻomaka ʻana i nā wahi kiʻekiʻe.
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. ʻO ka mea hoʻomaka, i helu ʻia he> 99%. Akā naʻe, ua hōʻike ʻia ka nānā ʻana e HPLC ua hoʻemi nui kēia hoʻololi ʻana i ka manawa hoʻolōʻihi ʻia a hiki i ka 90 mau minuke, a laila ʻike ʻia ka hana i ka pae a hiki i kahi "kūlana kūpaʻa". nā papa pale pono'ī. Hoʻopau kēia i ka pono e hoʻohui i kahi kumu keleawe (II) kōkua no ka hui pū ʻana71.