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Kei te whakarerekē te hanga tāpiri i te huarahi e hoahoa ai, e hanga ai hoki e ngā kairangahau me ngā kaipakihi ngā taputapu matū hei whakatutuki i ā rātou hiahia motuhake. I roto i tēnei mahi, ka pūrongohia e mātou te tauira tuatahi o tētahi tauhohenga rere i hangaia e te tikanga whakakī rau whakarewa totoka Ultrasonic Additive Manufacturing (UAM) me ngā wāhanga whakaterenga me ngā huānga pūoko kua whakauruhia tika. Ehara i te mea ka hinga noa te hangarau UAM i ngā herenga maha e pā ana ki te hanga tāpiringa o ngā tauhohenga matū, engari ka whakanuia hoki te kaha o aua taputapu. I hangaia me te arotauhia he raupapa o ngā matū koiora nui 1,4-disubstituted 1,2,3-triazole e te tauhohenga cycloaddition Huisgen 1,3-dipolar Cu mā te whakamahi i tētahi tatūnga matū UAM. Mā te whakamahi i ngā āhuatanga ahurei o te UAM me te tukatuka rere tonu, ka taea e te taputapu te whakatere i ngā tauhohenga tonu me te whakarato urupare wā-tūturu mō te aroturuki me te arotau tauhohenga.
Nā ōna painga nui ki tōna hoa papatipu, he mara nui te matū rere, ā, he mara tipu haere tonu i roto i ngā taiao mātauranga me ngā taiao ahumahi nā tōna kaha ki te whakanui ake i te whiriwhiringa me te whai huatanga o te hanganga matū. Ka toro atu tēnei mai i te hanganga ngota waro māmā1 ki ngā pūhui rongoā2,3 me ngā hua taiao4,5,6. Neke atu i te 50% o ngā tauhohenga i roto i ngā ahumahi matū pai me te rongoā ka whai hua mai i te whakamahinga o te tukatuka rere tonu7.
I ngā tau tata nei, kua piki haere te ia o ngā rōpū e hiahia ana ki te whakakapi i ngā taputapu karāhe tuku iho, i ngā taputapu matū rere rānei, ki ngā "ipu tauhohenga" matū hanga tāpiri (AM) ka taea te whakarite.8. Ko te hoahoa auau, te hanga tere, me ngā āheinga 3-ahu (3D) o ēnei tikanga he mea whai hua mō te hunga e hiahia ana ki te whakarite i ā rātou taputapu ki tētahi huinga tauhohenga, taputapu, āhuatanga rānei.Tae noa ki tēnei wā, kua aro nui tēnei mahi ki te whakamahinga o ngā tikanga tā 3D e hangai ana ki te polymer pērā i te stereolithography (SL)9,10,11, te whakatauira tāpui whakakotahi (FDM)8,12,13,14 me te tā waituhi waituhi 7, 15, 16. Ko te kore o te pakari me te kaha o aua taputapu ki te mahi i te whānuitanga o ngā tauhohenga/tātari matū17, 18, 19, 20 he mea nui hei whakawhāiti i te whakatinanatanga whānui o te AM i roto i tēnei mara17, 18, 19, 20.
Nā te pikinga ake o te whakamahinga o te matū rere me ngā āhuatanga pai e pā ana ki te AM, me tūhura ngā tikanga matatau ake e āhei ai ngā kaiwhakamahi ki te hanga i ngā oko tauhohenga rere me ngā āheinga matū me te tātari kua whakarei ake. Me āhei ēnei tikanga i ngā kaiwhakamahi ki te whiriwhiri mai i te whānuitanga o ngā rauemi tino pakari, mahi rānei e kaha ana ki te whakahaere i te whānuitanga o ngā āhuatanga tauhohenga, me te whakahaere hoki i ngā momo putanga tātari mai i te taputapu kia taea ai te aroturuki me te whakahaere i te tauhohenga.
Ko tētahi tukanga hanga tāpiritanga e whai pūmanawa ana ki te whakawhanake i ngā tauhohenga matū ritenga ko te Ultrasonic Additive Manufacturing (UAM). Ka whakamahia e tēnei tikanga whakapiri rau totoka ngā oscillations ultrasonic ki ngā pepa whakarewa angiangi kia honoa ai rātou paparanga i te paparanga me te iti o te wera nui me te nui o te rere kirihou 21, 22, 23. Kāore i rite ki te nuinga o ngā hangarau AM kē atu, ka taea te whakauru tika i te UAM ki te hanga tango, e mōhiotia ana ko te tukanga hanga ranu, e tautuhia ana e te mira mana rorohiko ā-wā (CNC) ā-roto, te miihini laser rānei te āhua kupenga o te paparanga o te rauemi here 24, 25. Ko te tikanga o tēnei kāore te kaiwhakamahi e herea e ngā raruraru e pā ana ki te tango i ngā rauemi hanga mata toenga mai i ngā awa wai iti, he mea e tupu pinepine ana me ngā pūnaha AM paura me te wai26,27,28. Ka horapa atu hoki tēnei herekoretanga hoahoa ki ngā kōwhiringa rauemi e wātea ana - ka taea e te UAM te hono i ngā huinga rauemi rite me ngā rerekē i roto i te taahiraa tukanga kotahi. Ko te kōwhiringa o ngā huinga rauemi i tua atu i te tukanga rewa ko te tikanga ka taea te whakatutuki pai ake i ngā tono miihini me te matū o ngā tono motuhake. Haunga te hononga totoka, tētahi atu āhuatanga Ko te mea e tūpono ana i te wā e honoa ana te ultrasonic ko te rere nui o ngā rauemi kirihou i ngā pāmahana iti rawa29,30,31,32,33. Mā tēnei āhuatanga ahurei o te UAM ka taea te whakauru i ngā huānga miihini/wera i waenga i ngā paparanga whakarewa me te kore e pakaru. Ka taea e ngā pūoko UAM te whakauru i ngā mōhiohio wā-tūturu mai i te taputapu ki te kaiwhakamahi mā roto i ngā tātaritanga whakauru.
I whakaatuhia e ngā mahi o mua a ngā kaituhi32 te kaha o te tukanga UAM ki te waihanga i ngā hanganga moroiti 3D whakarewa me ngā āheinga pūoko whakauru. He taputapu aroturuki anake tēnei. E whakaatu ana tēnei pepa i te tauira tuatahi o tētahi tauhohenga matū moroiti i hangaia e te UAM; he taputapu hohe e kore e aroturuki anake engari e whakaoho ana hoki i te hanganga matū mā roto i ngā rauemi whakakorikori kua whakauruhia ki te hanganga. Ka whakakotahi te taputapu i ētahi painga e pā ana ki te hangarau UAM i roto i te hanga taputapu matū 3D, pēnei i: te kaha ki te huri i ngā hoahoa 3D katoa mai i ngā tauira hoahoa āwhina-rorohiko (CAD) ki ngā hua; te hanga rauemi maha hei whakakotahi i te kawe wera teitei me ngā rauemi whakakorikori; me te whakauru i ngā pūoko wera i waenga i ngā awa reagent mō te aroturuki me te whakahaere pāmahana tauhohenga tika. Hei whakaatu i te mahi a te tauhohenga, i hangaia he whare pukapuka o ngā matū 1,4-disubstituted 1,2,3-triazole nui-rongoā mā te cycloaddition Huisgen 1,3-dipolar i whakakorikorihia ki te parahi. E whakaatu ana tēnei mahi me pēhea te whakamahinga o te pūtaiao rauemi me te hoahoa āwhina-rorohiko ka taea te whakatuwhera i ngā whai wāhitanga hou me ngā mea ka taea mō te matū mā roto i te rangahau maha-mātauranga.
I hokona ngā whakarewa me ngā matū katoa mai i Sigma-Aldrich, Alfa Aesar, TCI, Fischer Scientific rānei, ā, i whakamahia me te kore e purea i mua. Ko ngā hihi 1H me te 13C NMR i tuhia i te 400 MHz me te 100 MHz, ia, i whiwhihia mā te whakamahi i te hihi JEOL ECS-400 400 MHz, i te hihi Bruker Avance II 400 MHz rānei me te CDCl3, (CD3)2SO rānei hei whakarewa. I mahia ngā tauhohenga katoa mā te whakamahi i te tūāpapa matū rere Uniqsis FlowSyn.
I whakamahia te UAM hei hanga i ngā taputapu katoa i roto i tēnei rangahau. I hangaia te hangarau i te tau 1999, ā, ko ōna taipitopito hangarau, ngā tawhā whakahaere me ngā whanaketanga mai i tōna hanganga ka taea te ako mā roto i ngā rauemi kua whakaputaina e whai ake nei34,35,36,37. I whakatinanahia te taputapu (Pikitia 1) mā te whakamahi i tētahi pūnaha UAM 9kW SonicLayer 4000® mana tino teitei (Fabrisonic, OH, USA). Ko ngā rauemi i whiriwhiria mō te hanganga o te taputapu rere ko Cu-110 me Al 6061. He nui te ihirangi parahi o te Cu-110 (iti rawa 99.9% parahi), he pai mō ngā tauhohenga parahi-whakakorikori, nō reira ka whakamahia hei "paparanga hohe i roto i tētahi microreactor." Ka whakamahia te Al 6061 O hei rauemi "paparanga", me te paparanga whakauru e whakamahia ana mō te tātari; te whakauru wāhanga āwhina koranu me te āhua whakamahana i honoa ki te paparanga Cu-110. Ko te Al 6061 O he rauemi kua whakaatuhia he tino hototahi ki ngā tukanga UAM38, 39, 40, 41, ā, kua whakamatautauria, ā, kua kitea he pumau te matū me ngā matū i whakamahia i roto i tēnei mahi. Ko te whakakotahitanga o te Al 6061 O me te Cu-110 e kiia ana hoki he huinga rauemi hototahi mō te UAM, nō reira he rauemi tika mō tēnei rangahau. 38,42 Kua whakarārangihia ēnei taputapu ki te Ripanga 1 i raro nei.
Ngā wāhanga hanga o te tauhohenga (1) Papa Al 6061 (2) Te hanga o te hongere raro kua whakatakotoria ki te pepa parahi (3) Te whakauru i ngā takirua wera i waenga i ngā paparanga (4) Hongere o runga (5) Te tomokanga me te putanga (6) Te tauhohenga monolithic.
Ko te rapunga whakaaro hoahoa o te ara wai he whakamahi i tētahi ara piko hei whakanui ake i te tawhiti e haere ai te wai i roto i te maramara, me te pupuri tonu i te rahi o te maramara kia taea te whakahaere. He mea hiahia tēnei whakanui i te tawhiti hei whakanui ake i te wā taunekeneke o te whakakorikori/kaiwhakaora me te whakarato i ngā hua hua tino pai. Ka whakamahia e ngā maramara ngā piko 90° i ngā pito o te ara tika hei whakaoho i te whakaranu pōrearea i roto i te taputapu44 me te whakanui ake i te wā pa o te wai ki te mata (kaiwhakaora). Hei whakanui ake i te whakaranu ka taea te whakatutuki, kei roto i te hoahoa tauhohenga e rua ngā tomokanga o te kaiwhakaora kua honoa ki te hononga-Y i mua i te urunga ki te wāhanga whakaranu serpentine. Ko te tomokanga tuatoru, e whakawhiti ana i te awa i waenganui o tōna nohoanga, kei roto i te hoahoa o ngā hanganga tauhohenga maha-taahiraa a meake nei.
He tapawhā te āhua o ngā hongere katoa (kāore he koki tauira), ko te hua o te mira CNC ā-wā i whakamahia hei hanga i te āhua o te hongere. Ka whiriwhiria ngā āhua o te hongere kia nui ai te putanga rōrahi (mō te microreactor), engari he iti hoki hei whakahaere i ngā taunekeneke mata (ngā kaiwhakaoho) mō te nuinga o ngā wai kei roto. Ko te rahi e tika ana i ahu mai i ngā wheako o mua o ngā kaituhi me ngā taputapu whakarewa-wai mō te tauhohenga. Ko ngā āhua o roto o te hongere whakamutunga he 750 µm x 750 µm, ā, ko te rōrahi katoa o te tauhohenga he 1 ml. Kei roto i te hoahoa he hononga whakauru (1/4″—28 miro UNF) hei tuku i te hononga ngāwari o te taputapu ki ngā taputapu matū rere arumoni. Ka herea te rahi o te hongere e te matotoru o te rauemi pepa konutea, ōna āhuatanga miihini, me ngā tawhā here e whakamahia ana me ngā ultrasonics. I te whānui motuhake mō tētahi rauemi kua hoatu, ka "totoka" te rauemi ki roto i te hongere kua hangaia. Kāore he tauira motuhake mō tēnei tatau i tēnei wā, nō reira ka whakatauhia te whānui mōrahi o te hongere mō tētahi rauemi me te hoahoa kua hoatu mā te whakamātautau; i tēnei wā, e kore te whānui o te 750 μm e whakaheke.
Ka whakatauhia te āhua (tapawhā) o te awa mā te whakamahi i tētahi taputapu tapahi tapawhā. Ka taea te whakarerekē i te āhua me te rahi o ngā awa mā ngā mīhini CNC mā te whakamahi i ngā taputapu tapahi rerekē hei whiwhi i ngā tere rere me ngā āhuatanga rerekē. Ka kitea tētahi tauira o te hanga i tētahi awa āhua piko mā te whakamahi i te taputapu 125 μm i roto i te mahi a Monaghan45. Ina whakatakotoria te paparanga pepa konutea ki te āhua papatahi, ka whai āhua papatahi te paninga o te rauemi pepa konutea ki runga i ngā awa. I roto i tēnei mahi, hei pupuri i te ōritetanga o te awa, i whakamahia he āhua tapawhā.
I te wā o te whakamutua o te hanga i mua i te hōtaka, ka whakauruhia ngā whakamātautau pāmahana takirua wera (Momo K) ki roto i te taputapu i waenganui i ngā rōpū hongere o runga me raro (Pikitia 1 – Wāhanga 3). Ka taea e ēnei takirua wera te aroturuki i ngā huringa pāmahana mai i te −200 ki te 1350 °C.
Ka mahia te tukanga whakatakoto whakarewa mā te haona UAM mā te whakamahi i te pepa whakarewa 25.4 mm te whānui, 150 micron te matotoru. Ka herea ēnei paparanga pepa whakarewa ki roto i tētahi raupapa o ngā rīpene tata hei kapi i te rohe hanga katoa; he nui ake te rahi o te rauemi kua whakatakotoria i te hua whakamutunga i te mea ka puta te āhua kupenga whakamutunga mā te tukanga tango. Ka whakamahia te mīhini CNC hei mīhini i ngā āhua o waho me roto o te taputapu, ka hua ake he mutunga mata o te taputapu me ngā awaawa e ōrite ana ki te taputapu kua tohua me ngā tawhā tukanga CNC (tata ki te 1.6 μm Ra i tēnei tauira). Ka whakamahia ngā huringa whakatakoto rauemi me te mīhini ultrasonic tonu, puta noa i te tukanga hanga taputapu hei whakarite kia mau tonu te tika o te rahinga, ā, ka tutuki te wāhanga kua oti i ngā taumata tika o te mira whakaoti CNC. He iti te whānui o te awaawa e whakamahia ana mō tēnei taputapu kia kore ai te rauemi pepa whakarewa e "totoka" ki roto i te awaawa wai, kia mau tonu ai te awaawa i tētahi wāhanga tapawhā. I whakatauhia ngā āputa pea i roto i te rauemi pepa whakarewa me ngā tawhā tukanga UAM mā te whakamātautau e tētahi hoa hanga (Fabrisonic LLC, USA).
Kua whakaatuhia e ngā rangahau he iti noa te horapa o ngā huānga i te atanga hononga UAM 46, 47 me te kore he maimoatanga wera tāpiri, nō reira mō ngā taputapu o tēnei mahi, ka noho motuhake tonu te paparanga Cu-110 mai i te paparanga Al 6061, ā, ka huri ohorere.
Tāutahia he kaiwhakahaere pēhanga whakamuri 250 psi (1724 kPa) (BPR) kua whakatikatikaina i mua i te putanga o te tauhohenga, ā, ka papuhia te wai mā roto i te tauhohenga i te tere o te 0.1 ki te 1 mL min-1. I aroturukitia te pēhanga o te tauhohenga mā te whakamahi i te pūoko pēhanga pūnaha FlowSyn kua hangaia hei manatoko ka taea e te pūnaha te pupuri i te pēhanga pumau tonu. I whakamatautauria ngā pikinga pāmahana pea puta noa i te tauhohenga rere mā te tautuhi i ngā rerekētanga i waenga i ngā thermocouples kua whakauruhia ki roto i te tauhohenga me ērā kua whakauruhia ki roto i te pereti whakamahana maramara FlowSyn. Ka tutuki tēnei mā te whakarerekē i te pāmahana pereti wera ka taea te whakarite i waenga i te 100 me te 150 °C i roto i ngā pikinga 25 °C me te tuhi i ngā rerekētanga i waenga i ngā pāmahana kua whakaritea me ngā pāmahana kua tuhia. I tutuki tēnei mā te whakamahi i te kaitatau raraunga tc-08 (PicoTech, Cambridge, UK) me te pūmanawa PicoLog e haere tahi ana.
I arotauhia ngā āhuatanga tauhohenga cycloaddition o te phenylacetylene me te iodoethane (Kaupapa 1- Cycloaddition o te phenylacetylene me te iodoethane Kaupapa 1- Cycloaddition o te phenylacetylene me te iodoethane). I mahia tēnei arotautanga mā te huarahi hoahoa whakamātautau tauwehe katoa (DOE), mā te whakamahi i te pāmahana me te wā noho hei tawhā taurangi, me te whakatika i te ōwehenga alkyne:azide i te 1:2.
I whakaritea ngā otinga motuhake o te konutai azide (0.25 M, 4:1 DMF:H2O), te iodoethane (0.25 M, DMF), me te phenylacetylene (0.125 M, DMF). I konatunatua he 1.5 mL o ia otinga, ā, i papua mā roto i te tauhohenga i te tere rere me te pāmahana e hiahiatia ana. I tangohia te urupare tauira hei ōwehenga horahanga tihi o te hua triazole ki te rauemi tīmatanga phenylacetylene, ā, i whakatauhia mā te chromatography wai mahi teitei (HPLC). Mō te ōrite o te tātari, i tauirahia ngā tauhohenga katoa i muri tata mai i te wehenga atu o te ranunga tauhohenga i te tauhohenga. Kei te Ripanga 2 ngā awhe tawhā i tīpakohia mō te arotautanga.
I tātarihia ngā tauira katoa mā te whakamahi i te pūnaha Chromaster HPLC (VWR, PA, USA) kei roto ko te papu quaternary, te oumu pou, te pūoko UV roangaru rerekē me te autosampler. Ko te pou he Equivalence 5 C18 (VWR, PA, USA), he 4.6 × 100 mm te rahi, he 5 µm te rahi o te matūriki, i puritia i te 40 °C. Ko te whakarewa he isocratic 50:50 methanol:wai i te tere rere o te 1.5 mL.min-1. Ko te rōrahi werohanga he 5 µL, ā, ko te roangaru pūoko he 254 nm. Ko te % horahanga tihi mō te tauira DOE i tatauhia mai i ngā horahanga tihi o ngā hua alkyne me triazole toenga anake. Mā te werohanga o te rauemi tīmatanga ka taea te tautuhi i ngā tihi e tika ana.
Mā te hono i te putanga tātari tauhohenga ki te pūmanawa MODDE DOE (Umetrics, Malmö, Sweden) i taea ai te tātari hohonu i ngā au o ngā hua me te whakatau i ngā āhuatanga tauhohenga tino pai mō tēnei tāpiringa haurua. Mā te whakahaere i te arotau kua hangaia, me te whiriwhiri i ngā kupu tauira nui katoa, ka puta he huinga o ngā āhuatanga tauhohenga kua hangaia hei whakanui ake i te horahanga tihi hua me te whakaiti i te horahanga tihi mō te rauemi tīmatanga acetylene.
I tutuki te waikura o te parahi mata i roto i te rūma tauhohenga whakakorikori mā te whakamahi i te otinga o te hauwai waikura (36%) e rere ana i roto i te rūma tauhohenga (tere rere = 0.4 mL min-1, wā noho = 2.5 min) i mua i te hanganga o ia whare pukapuka matū triazole.
I te wā i kitea ai he huinga āhuatanga tino pai, ka whakamahia ēnei ki te whānuitanga o ngā matū acetylene me ngā matū haloalkane hei tuku i te whakahiato o tētahi whare pukapuka iti, ā, ka whakatūria te kaha ki te whakamahi i ēnei āhuatanga ki te whānuitanga o ngā matū tauhohenga pea (Pikitia 1).2).
Whakaritea ngā otinga motuhake o te konutai azide (0.25 M, 4:1 DMF:H2O), ngā haloalkane (0.25 M, DMF) me ngā alkyne (0.125 M, DMF). I konatunatuahia ngā wāhanga 3 mL o ia otinga, ā, i pupuhihia mā roto i te tauhohenga i te 75 µL.min-1 me te 150 °C. I kohia te rōrahi katoa ki roto i tētahi ipu, ā, i whakaranua ki te 10 mL o te ethyl acetate. I horoia te otinga tauira ki te 3 × 10 mL o te wai. I whakakotahihia ngā paparanga wai, ā, i tangohia ki te 10 mL o te ethyl acetate; kātahi ka whakakotahihia ngā paparanga rauropi, i horoia ki te 3 x 10 mL o te tote, i whakamaroketia ki runga i te MgSO4, ā, i tātarihia, kātahi ka tangohia te whakarewa i roto i te korehau. I purea ngā tauira mā te chromatography pou i runga i te silica gel mā te whakamahi i te ethyl acetate i mua i te tātaritanga mā te whakakotahitanga o te HPLC, 1H NMR, 13C NMR me te spectrometry papatipu taumira teitei (HR-MS).
I kohia ngā ira katoa mā te whakamahi i tētahi inenga papatipu taumira Orbitrap Thermofischer me te ESI hei pūtake ionization. I whakaritea ngā tauira katoa mā te whakamahi i te acetonitrile hei whakarewa.
I whakahaerehia te tātaritanga TLC ki runga i ngā pereti silica kei roto i te konumohe. I tirohia ngā pereti mā te mārama UV (254 nm) mā te tae vanilla rānei, kātahi ka whakamahana.
I tātarihia ngā tauira katoa mā te whakamahi i tētahi pūnaha VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) kua rite ki tētahi autosampler, he papu rua oumu pou me tētahi pūoko ngaru kotahi. Ko te pou i whakamahia he ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland).
I hangaia ngā werohanga (5 µL) mai i te ranunga tauhohenga mata kua whakaranua (whakaranutanga 1:10) ā, i tātarihia ki te wai:methanol (50:50, 70:30 rānei), engari ko ētahi tauira e whakamahi ana i te pūnaha whakarewa 70:30 (e tohuhia ana he tau whetu) i te tere rere o te 1.5 mL/min. I puritia te pou i te 40 °C. Ko te roangaru o te pūoko he 254 nm.
I tatauhia te % o te horahanga tihi o te tauira mai i te horahanga tihi o te toenga alkyne, ko te hua triazole anake, ā, mā te werohanga o te rauemi tīmatanga i taea ai te tautuhi i ngā tihi e tika ana.
I tātarihia ngā tauira katoa mā te whakamahi i te Thermo iCAP 6000 ICP-OES. I whakaritea ngā paerewa whakatikatika katoa mā te whakamahi i te otinga paerewa Cu 1000 ppm i roto i te waikawa hauota 2% (SPEX Certi Prep). I whakaritea ngā paerewa katoa i roto i te otinga DMF 5% me te HNO3 2%, ā, i whakaranua ngā tauira katoa kia 20 ngā wā ki roto i te otinga DMF-HNO3 tauira.
Ka whakamahia e te UAM te whakarewa whakarewa ultrasonic hei tikanga here mō te rauemi pepa whakarewa i whakamahia hei hanga i te huihuinga whakamutunga. Ka whakamahia e te whakarewa whakarewa ultrasonic he taputapu whakarewa wiri (e kiia ana he haona, he haona ultrasonic rānei) hei pēhi i te paparanga pepa whakarewa/paparanga kua whakakotahihia i mua kia herea i te wā e wiri ana te rauemi. Mō te mahi tonu, he porotaka te sonotrode ka hurihuri i runga i te mata o te rauemi, ka herea te rohe katoa. Ina whakamahia te pēhanga me te wiri, ka pakaru pea ngā waikura i runga i te mata o te rauemi. Ka taea e te pēhanga me te wiri tonu te hinga o te rauemi 36. Ko te whakapā tata ki te wera me te pēhanga i puta i te rohe ka arahi ki te here totoka i ngā atanga rauemi; ka taea hoki e ia te āwhina i te piri mā roto i ngā huringa o te kaha o te mata 48. Ko te āhua o te tikanga here ka wikitoria i te maha o ngā raruraru e pā ana ki te pāmahana rewa rerekē me ngā pānga pāmahana teitei kua whakahuatia i roto i ētahi atu tikanga hanga tāpiri. Mā tēnei ka taea te here tika (arā, me te kore he whakarerekētanga mata, he whakakī, he piripiri rānei) o ngā paparanga maha o ngā rauemi rerekē ki roto i te hanganga kotahi kua whakakotahihia.
Ko tētahi atu āhuatanga pai mō te UAM ko te nui o te rere kirihou e kitea ana i roto i ngā rauemi whakarewa, ahakoa i ngā pāmahana iti, arā, i raro iho i te ira rewa o ngā rauemi whakarewa. Ko te whakakotahitanga o te oscillation ultrasonic me te pēhanga ka puta he taumata teitei o te hekenga rohe witi ā-rohe me te whakahounga me te kore e piki ake te pāmahana nui e pā ana ki ngā rauemi papatipu. I te wā o te hanganga o te huihuinga whakamutunga, ka taea te whakamahi i tēnei āhuatanga hei whakauru i ngā wāhanga hohe me ngā wāhanga kore mahi i waenga i ngā paparanga o te pepa whakarewa, paparanga i te paparanga. Ko ngā huānga pēnei i ngā muka whatu 49, ngā whakapakari 46, ngā hikohiko 50, me ngā thermocouples (tēnei mahi) kua angitu te whakauru ki roto i ngā hanganga UAM hei hanga i ngā huihuinga hiato hohe me te kore mahi.
I roto i tēnei mahi, kua whakamahia ngā momo hononga rauemi me ngā āheinga whakauru o te UAM hei waihanga i te pūwero aroturuki pāmahana catalytic tino pai.
Ki te whakatauritea ki te palladium (Pd) me ētahi atu whakakorikori konganuku e whakamahia whānuitia ana, he maha ngā painga o te whakakorikori Cu: (i) I te taha ōhanga, he iti ake te utu o te Cu i te maha atu o ngā konganuku e whakamahia ana i roto i te whakakorikori, nō reira he kōwhiringa ātaahua mō te umanga tukatuka matū (ii) Kei te piki haere te whānuitanga o ngā tauhohenga honohono whakawhiti-whakakorikori Cu, ā, te āhua nei he rite tonu ki ngā tikanga e hangai ana ki te Pd51,52,53 (iii) He pai te mahi a ngā tauhohenga whakakorikori Cu i te korenga o ētahi atu ligands, He maha ngā wā he ngāwari te hanganga o ēnei ligands, ā, he iti te utu mēnā e hiahiatia ana, engari ko ngā mea e whakamahia ana i roto i te matū Pd he maha ngā wā he uaua, he utu nui, ā, he tairongo ki te hau (iv) Cu, e mōhiotia whānuitia ana mō tōna kaha ki te here i ngā alkynes i roto i te hanganga, Hei tauira, ko te hononga Sonogashira whakakorikori-rua me te cycloaddition me ngā azides (matū pāwhiri) (v) Ka taea hoki e Cu te whakatairanga i te arylation o ētahi nucleophiles i roto i ngā tauhohenga momo-Ullmann.
Kua whakaaturia tata nei ngā tauira o te heterogenization o ēnei tauhohenga katoa i te aroaro o Cu(0). Ko te nuinga o tēnei nā te umanga rongoā me te arotahi nui ki te whakaora me te whakamahi anō i ngā whakakorikori whakarewa55,56.
I tīmatahia e Huisgen i ngā tau 196057, ko te tauhohenga cycloaddition 1,3-dipolar i waenga i te acetylene me te azide ki te 1,2,3-triazole e kiia ana he tauhohenga whakaaturanga synergistic. Ko ngā wāhanga 1,2,3 triazole hua he mea tino pārekareka hei pharmacophore i roto i te mara o te kimi rongoā nā ō rātou tono koiora me te whakamahinga i roto i ngā momo kaihoko rongoā 58.
I puta anō te aro ki tēnei tauhohenga i te wā i whakaurua ai e Sharpless mā te ariā o te "matū pāwhiri"59. Ko te kupu "matū pāwhiri" e whakamahia ana hei whakaahua i tētahi huinga tauhohenga pakari, pono, me te whiriwhiri mō te hanga tere o ngā matū hou me ngā whare pukapuka whakakotahi mā te hononga heteroatom (CXC)60 Ko te ataahua hanga o ēnei tauhohenga i ahu mai i ō rātou hua teitei e pā ana, he māmā ngā āhuatanga tauhohenga, he ātete ki te hāora me te wai, ā, he māmā te wehenga hua61.
Kāore te cycloaddition Huisgen 1,3-dipole matarohia i roto i te kāwai o te "matū pāwhiri". Heoi, i whakaatu a Medal me Sharpless ka pāngia tēnei huihuinga hononga azide-alkyne e te 107 ki te 108 i te aroaro o Cu(I) ki te whakataurite ki te tere whakaterenga nui o te cycloaddition 1,3-dipolar 62,63 kāore i whakakorikoria. Kāore tēnei tikanga tauhohenga kua whakapaitia e hiahia ki ngā rōpū tiaki, ki ngā āhuatanga tauhohenga kino rānei, ā, ka tata ki te katoa te huringa me te whiriwhiringa ki te 1,4-disubstituted 1,2,3-triazoles (anti-1,2,3-triazole) i runga i te tauine wā (Pikitia 3).
Ngā hua isometric o ngā cycloadditions Huisgen tikanga me ngā cycloadditions Huisgen kua whakakōkīhia ki te parahi. Ko ngā cycloadditions Huisgen kua whakakōkīhia ki te Cu(I) ka puta ko ngā 1,4-disubstituted 1,2,3-triazoles anake, engari ko ngā cycloadditions Huisgen i whakakōkīhia ki te wera ka puta ko ngā 1,4- me te 1,5-triazoles 1:1 ranunga o ngā stereoisomers o ngā azoles.
Ko te nuinga o ngā tikanga e pā ana ki te whakaiti i ngā pūtake Cu(II) pumau, pērā i te whakaiti i te CuSO4, i ngā momo Cu(II)/Cu(0) rānei mā te whakakotahitanga me ngā tote konutai. Ki te whakaritea ki ētahi atu tauhohenga whakarewa-whakakorikori, ko ngā painga nui o te whakamahinga o te Cu(I) he iti te utu, he ngāwari hoki te whakahaere.
I whakaatuhia e ngā rangahau tapanga kinetic me te isotopic a Worrell et al. 65, i roto i te take o ngā alkynes whakamutunga, e rua ngā rite o te parahi e uru ana ki te whakahohe i te tauhohenga o ia ngota ki te azide. Ka puta te tikanga kua whakaarohia mā roto i te mowhiti whakarewa parahi ono-mema i hangaia e te whakakotahitanga o te azide ki te acetylide parahi kua herea ki te σ me te parahi kua herea ki te π hei ligand kaituku pumau. Ka hangaia ngā matū parahi triazolyl mā te whakahekenga mowhiti, ā, ka whai ake ko te wetewete proton hei whakarato i ngā hua triazole me te kati i te huringa catalytic.
Ahakoa kua tuhia pai ngā painga o ngā taputapu matū rere, kua puta te hiahia ki te whakauru i ngā taputapu tātari ki roto i ēnei pūnaha mō te aroturuki tukanga ā-roto, ā-tūnga hoki66,67. I whakamātauhia te UAM hei tikanga pai mō te hoahoa me te whakaputa i ngā tauhohenga rere 3D tino uaua i hangaia mai i ngā rauemi kawe wera kaha, me ngā huānga pūoko kua whakauruhia tika (Pikitia 4).
He tauhohenga rere konumohe-parahi i hangaia mā te hanga tāpiri ultrasonic (UAM) me te hanganga hongere ā-roto matatini, ngā takirua wera kua whakauruhia, me te rūma tauhohenga catalytic. Hei tiro i ngā ara wai ā-roto, ka whakaaturia hoki he tauira mārama i hangaia mā te whakamahi i te stereolithography.
Hei whakarite kia hangaia ngā tauhohenga mō ngā tauhohenga rauropi a meake nei, me whakamahana haumaru ngā whakarewa ki runga ake i te pūwāhi kohua; ka whakamatautauria te pēhanga me te pāmahana. I whakaatuhia e te whakamātautau pēhanga he pumau, he pumau tonu te pēhanga o te pūnaha ahakoa te pikinga o te pēhanga o te pūnaha (1.7 MPa). I mahia te whakamātautau waipū i te pāmahana rūma mā te whakamahi i te H2O hei wai.
I te hononga o te thermocouple kua whakauruhia (Pikitia 1) ki te pūrakau raraunga pāmahana, i whakaatuhia ko te thermocouple he 6 °C (± 1 °C) te mātao ake i te pāmahana kua whakaritea i runga i te pūnaha FlowSyn. I te nuinga o te wā, ko te pikinga o te pāmahana 10 °C ka hua ake he rua te tere o te tauhohenga, nō reira ko te rerekētanga pāmahana o te torutoru noa nga nekehanga ka taea te whakarerekē nui i te tere o te tauhohenga. Ko te ngaronga o te pāmahana puta noa i te tinana tauhohenga te take o tēnei rerekētanga nā te nui o te horapa wera o ngā rauemi e whakamahia ana i roto i te tukanga hanga. He rite tonu tēnei nekehanga wera, nō reira ka taea te whakaaro i roto i te tatūnga taputapu kia tino tutuki ai ngā pāmahana tika me te ine i te wā o te tauhohenga. Nō reira, ka āwhina tēnei taputapu aroturuki ipurangi i te whakahaere pakari o te pāmahana tauhohenga, ā, ka āwhina i te arotautanga tukanga tika ake me te whakawhanake i ngā āhuatanga tino pai. Ka taea hoki te whakamahi i ēnei pūoko ki te tautuhi i ngā exotherms tauhohenga me te ārai i ngā tauhohenga rere i roto i ngā pūnaha tauine nui.
Ko te tauhohenga e whakaaturia ana i roto i tēnei mahi te tauira tuatahi o te whakamahinga o te hangarau UAM ki te hanga i ngā tauhohenga matū, ā, e aro ana ki ētahi herenga nui e pā ana ki te tānga AM/3D o ēnei taputapu, pērā i: (i) te wikitoria i ngā raruraru kua pūrongohia e pā ana ki te tukatuka parahi, konumohe rānei (ii) te whakapai ake i te taumira o roto o te hongere ki te whakataurite ki ngā tikanga hanumi moenga paura (PBF) pērā i te rewa laser whiriwhiri (SLM)25,69 Te rere ngoikore o ngā rauemi me te kakano mata taratara26 (iii) Te whakaiti i te pāmahana tukatuka, e āwhina ana i te hononga tika o ngā pūoko, e kore e taea i roto i te hangarau moenga paura, (v) te wikitoria i ngā āhuatanga miihini ngoikore me te aro o ngā wāhanga polymer ki ngā momo whakarewa waro noa17,19.
I whakaaturia te mahi a te tauhohenga mā te raupapa o ngā tauhohenga cycloaddition alkyne azide i whakakorikoria ki te parahi i raro i ngā tikanga rere tonu (Pikitia 2). Ko te tauhohenga parahi i tāia ki te ultrasonic i whakaahuatia i roto i te Pikitia 4 i whakauruhia ki tētahi pūnaha rere arumoni, ā, i whakamahia hei hanga i ngā azide whare pukapuka o ngā momo 1,4-disubstituted 1,2,3-triazoles mā te tauhohenga pāmahana-whakahaere o te acetylene me ngā rōpū alkyl halides i te aroaro o te konutai pūhaumāota (Pikitia 3). Mā te whakamahi i tētahi huarahi rere tonu ka whakaiti i ngā āwangawanga haumaru ka puta ake i roto i ngā tukanga puranga, nā te mea ka puta mai i tēnei tauhohenga he takawaenga azide tino tauhohe me te morearea [317], [318]. I te tīmatanga, i arotauhia te tauhohenga mō te cycloaddition o te phenylacetylene me te iodoethane (Kaupapa 1 – Cycloaddition o te phenylacetylene me te iodoethane) (tirohia te Pikitia 5).
(Maui o runga) Kauwhata o te whakatakotoranga i whakamahia hei whakauru i te tauhohenga 3DP ki roto i te pūnaha rere (matau o runga) i whiwhihia i roto i te kaupapa arotau (raro) o te kaupapa Huisgen cycloaddition 57 i waenga i te phenylacetylene me te iodoethane mō te arotau me te whakaatu i te tere tahuritanga tauhohenga tawhā kua arotauhia.
Mā te whakahaere i te wā noho o ngā matū i roto i te wāhanga whakakorikori o te tauhohenga me te aroturuki tata i te pāmahana tauhohenga me te tirotiro thermocouple whakauru tika, ka taea te arotau tere me te tika i ngā āhuatanga tauhohenga me te iti o te wā me te whakamahinga rauemi. I kitea wawetia ko ngā huringa teitei rawa i whiwhihia i te wā i whakamahia ai te wā noho o te 15 meneti me te pāmahana tauhohenga o te 150 °C. Mai i te kauwhata tauwehenga o te pūmanawa MODDE, ka kitea ko te wā noho me te pāmahana tauhohenga he kupu tauira nui. Mā te whakahaere i te arotau hanga-roto ma te whakamahi i ēnei kupu kua tohua ka puta he huinga o ngā āhuatanga tauhohenga kua hangaia hei whakanui ake i ngā horahanga tihi hua me te whakaiti i ngā horahanga tihi rauemi tīmatanga. Nā tēnei arotautanga i hua ake he huringa 53% o te hua triazole, i tino rite ki te matapae tauira o te 54%.
I runga i ngā tuhinga e whakaatu ana ka taea e te waikura parahi(I) (Cu2O) te mahi hei momo whakatere whai hua i runga i ngā mata parahi kore-valent i roto i ēnei tauhohenga, i tirotirohia te kaha ki te whaka-waikura i mua i te mata o te tauhohenga i mua i te whakahaere i te tauhohenga i roto i te rere70,71. I muri mai ka whakahaerehia anō te tauhohenga i waenga i te phenylacetylene me te iodoethane i raro i ngā āhuatanga tino pai, ā, i whakaritea ngā hua. I kitea ko tēnei whakaritenga i hua ake ai he pikinga nui o te huringa o te rauemi tīmatanga, i tatauhia ki te >99%. Heoi, i whakaatuhia e te aroturukitanga mā te HPLC he tino whakaitihia e tēnei huringa te wā tauhohenga roa rawa tae noa ki te 90 meneti pea, ā, i reira ka puta te mahi ki te taurite me te eke ki te "āhua pumau". E kī ana tēnei kitenga ko te pūtake o te mahi whakatere i whiwhi mai i te waikura parahi mata kaua ki te papa parahi kore-valent. Ka ngāwari te whaka-waikura i te konganuku Cu i te pāmahana rūma hei hanga CuO me Cu2O ehara i te mea he paparanga tiaki-whaiaro. Mā tēnei ka whakakorea te hiahia ki te tāpiri i tētahi pūtake parahi(II) āwhina mō te hanganga tahi71.