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Kei te whakarerekē te hanga tāpiri i te huarahi e hoahoa ai, e hanga ai hoki ngā kairangahau me ngā kaipakihi i ngā taputapu matū hei whakatutuki i ā rātou hiahia motuhake. I roto i tēnei pepa, ka pūrongohia e mātou te tauira tuatahi o tētahi tauhohenga rere i hangaia e te whakakīkī hanga tāpiri ultrasonic (UAM) o tētahi rau whakarewa totoka me ngā wāhanga whakaterenga me ngā huānga pūoko kua whakauruhia tika. Ehara i te mea ka wikitoria noa te hangarau UAM i ngā herenga maha e pā ana ki te hanga tāpiri o ngā tauhohenga matū, engari ka whakawhānui ake hoki i ngā āheinga o aua taputapu. He maha ngā matū 1,4-disubstituted 1,2,3-triazole nui koiora kua oti te hanga me te arotau mā te tauhohenga cycloaddition Huisgen 1,3-dipolar Cu mā te whakamahi i te whare 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 e haere tonu ana me te whakarato urupare wā-tūturu hei aroturuki me te arotau i ngā tauhohenga.
Nā ōna painga nui ki tōna hoa papatipu, he mea 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 o ngā 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 taea te whai hua mai i te rere tonu7.
I ngā tau tata nei, kua piki haere te ia o ngā rōpū e rapu ana ki te whakakapi i ngā taputapu karāhe tuku iho, i ngā taputapu matū rere rānei, ki ngā "tauhohenga" matū urutau8. Ko te hoahoa auau, te hanga tere, me ngā āheinga toru-ahu (3D) o ēnei tikanga he mea whai hua mō te hunga e hiahia ana ki te whakarite i ā rātou taputapu mō 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 ahu mai ana i te polymer pērā i te stereolithography (SL)9,10,11, te Fused Deposition Modeling (FDM)8,12,13,14 me te tā waituhi waituhi7,15. , 16. Ko te kore pono me te kore 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 whakamahinga 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 tūhuratia ngā tikanga pai ake hei āwhina i ngā kaiwhakamahi ki te hanga i ngā oko tauhohenga rere me ngā kaha matū me te tātari kua whakapaitia. Me āhei ēnei tikanga i ngā kaiwhakamahi ki te whiriwhiri mai i te whānuitanga o ngā rauemi kaha teitei, rauemi mahi rānei e taea ai te mahi i raro i te whānuitanga o ngā āhuatanga tauhohenga, me te whakahaere hoki i ngā momo putanga tātari mai i te taputapu hei whakahohe i te aroturuki me te whakahaere i te tauhohenga.
Ko tētahi tukanga hanga tāpiri ka taea te whakamahi hei whakawhanake i ngā tauhohenga matū ritenga ko te Ultrasonic Additive Manufacturing (UAM). Ka whakamahia e tēnei tikanga whakapiri rau totoka ngā wiri ultrasonic ki ngā pepa whakarewa angiangi hei hono i a rātou paparanga i te paparanga me te iti o te wera rōrahi me te nui o te rere kirihou 21, 22, 23. Kāore i rite ki te nuinga o ngā hangarau AM, ka taea te whakauru tika i te UAM ki te whakaputa tango, e mōhiotia ana ko te tukanga hanga ranu, e whakatau ana te mira mana tau i roto i te wāhi (CNC) ā-wā, te tukatuka laser rānei i te āhua kupenga o te paparanga o te rauemi kua honoa 24, 25. Ko te tikanga o tēnei kāore te kaiwhakamahi e herea ki ngā raruraru e pā ana ki te tango i ngā rauemi hanga taketake toenga mai i ngā awa wai iti, he mea e tupu pinepine ana i roto i ngā pūnaha paura me te wai AM26,27,28. Ka horapa atu hoki tēnei herekoretanga hoahoa ki te whiriwhiri i ngā rauemi e wātea ana - ka taea e te UAM te hono i ngā huinga o ngā rauemi rite me ngā rauemi rerekē i roto i te taahiraa tukanga kotahi. Ko te whiriwhiri i ngā huinga rauemi i tua atu i te tukanga rewa ko te tikanga ka taea te whakatutuki pai ake i ngā whakaritenga miihini me te matū o ngā tono motuhake. Haunga te hononga totoka, ko tētahi atu āhuatanga e puta ana me te hononga 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 whakanoho i ngā huānga miihini/wera ki waenganui i ngā paparanga whakarewa me te kore e pakaru. Ka taea e ngā pūoko UAM kua whakauruhia te whakahaere i te tuku 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 kua whakauruhia. Hei aroturuki anake tēnei taputapu. E whakaatu ana tēnei tuhinga i te tauira tuatahi o tētahi tauhohenga matū moroiti i hangaia e UAM, he taputapu hohe e kore e whakahaere anake engari e whakaoho ana hoki i te hanganga matū me ngā rauemi whakaterenga 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 tētahi hoahoa 3D katoa mai i tētahi tauira hoahoa āwhina-rorohiko (CAD) ki tētahi hua; te hanga rauemi maha mō te whakakotahitanga o te kawe wera teitei me ngā rauemi whakaterenga, me ngā pūoko wera kua whakauruhia tika ki waenganui i ngā awa tauhohenga mō te whakahaere tika me te whakahaere i te pāmahana tauhohenga. 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 kua whakaterenga-parahi. E whakamārama ana tēnei mahi i te whakamahinga o te pūtaiao rauemi me te hoahoa āwhina-rorohiko ka taea te whakatuwhera i ngā huarahi hou mō te matū mā 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 purenga i mua. Ko ngā hihi 1H me te 13C NMR i tuhia i te 400 me te 100 MHz, ia, i whiwhihia i runga 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 te whakamahi 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 SonicLayer 4000® mahi taumaha 9 kW (Fabrisonic, Ohio, USA). Ko ngā rauemi i whiriwhiria mō te taputapu rere ko Cu-110 me Al 6061. He nui te parahi o Cu-110 (iti rawa 99.9% parahi), he pai mō ngā tauhohenga parahi whakakorikori, nō reira ka whakamahia hei "paparanga hohe i roto i te microreactor. Ka whakamahia te Al 6061 O hei rauemi "paparanga". , me te paparanga whakauru i whakamahia mō te tātari; te whakauru o ngā wāhanga koranu āwhina me te āhua whakamahana i te taha o te paparanga Cu-110. i kitea he pumau matū me ngā tauhohenga i whakamahia i roto i tēnei mahi. Ko te Al 6061 O i te taha o te Cu-110 e kiia ana hoki he huinga rauemi hototahi mō te UAM, nō reira he rauemi tika mō tēnei rangahau38,42. Kua whakarārangihia ēnei taputapu ki te Ripanga 1 i raro nei.
Ngā taahiraa hanga o te tauhohenga (1) Papa konumohe konumohe 6061 (2) Hanganga o te awaawa o raro mai i te pepa parahi (3) Whakaurunga o ngā takirua wera i waenga i ngā paparanga (4) Awaawa o runga (5) Tomokanga me te putanga (6) Tauhohenga monolithic.
Ko te whakaaro o te hoahoa awa wai he whakamahi i tētahi ara pikopiko hei whakanui ake i te tawhiti e haerehia ana e te wai i roto i te maramara, me te pupuri tonu i te rahi o te maramara e taea te whakahaere. He mea hiahia tēnei whakanui i te tawhiti hei whakanui ake i te wā whakapā o te matū whakakorikori-tauhohenga, ā, hei 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 whakapā o te wai ki te mata (whakakorikori). Hei whakarei ake i te whakaranu ka taea te whakatutuki, kei roto i te hoahoa o te tauhohenga ngā tomokanga tauhohenga e rua kua honoa ki tētahi hononga-Y i mua i te urunga ki te wāhanga koiri whakaranu. Ko te tomokanga tuatoru, e whiti ana i te rere i waenganui o tōna nohoanga, kei roto i te mahere mō ngā tauhohenga whakahiato maha-wāhanga a meake nei.
He tapawhā te āhua o ngā awa katoa (kāore he koki whakarara), koinei te hua o te mira CNC ā-wā i whakamahia hei hanga i te āhua o te awa. Ka whiriwhiria ngā āhua o te awa kia nui ai te hua rōrahi (mō te microreactor), engari kia iti ai hei whakahaere i te taunekeneke ki te 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 tauhohenga whakarewa-wai. Ko ngā āhua o roto o te awa 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 hanga-roto (miro 1/4″-28 UNF) kia ngāwari ai te hono atu o te taputapu ki ngā taputapu matū rere arumoni. Ka herea te rahi o te awa e te matotoru o te rauemi pepa konutea, ōna āhuatanga miihini, me ngā tawhā here e whakamahia ana me ngā ultrasonics. I tētahi whānui mō te rauemi kua hoatu, ka "peke" te rauemi ki roto i te awa i hangaia. Kāore he tauira motuhake mō tēnei tataunga i tēnei wā, nō reira ka whakatauhia te whānui mōrahi o te awa mō tētahi rauemi me tētahi hoahoa mā te whakamātautau, ā, 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 i runga i ngā mīhini CNC mā te whakamahi i ngā taputapu tapahi rerekē hei whiwhi i ngā tere rere me ngā āhuatanga rerekē. Kei Monaghan45 tētahi tauira o te hanga awa piko me te taputapu 125 µm. Ina pania te paparanga pepa konutea kia papatahi, ka whai mata papatahi (tapawhā) te paninga o te rauemi pepa konutea ki ngā awa. I roto i tēnei mahi, i whakamahia he āhua tapawhā hei pupuri i te ōritetanga o te awa.
I te wā o te whakamutua kua whakaritea i roto i te mahi whakaputa, ka hangaia tika ngā pūoko pāmahana takirua wera (momo K) ki roto i te taputapu i waenga i ngā rōpū hongere o runga me raro (Pikitia 1 – wāhanga 3). Ka taea e ēnei takirua wera te whakahaere i ngā huringa pāmahana mai i te -200 ki te 1350 °C.
Ka whakahaerehia te tukanga whakatakoto whakarewa e te haona UAM mā te whakamahi i te pepa whakarewa he 25.4 mm te whānui, ā, he 150 maikorona te matotoru. Ka honoa ēnei paparanga pepa whakarewa ki roto i tētahi raupapa o ngā rīpene tata hei kapi i te wāhi hanga katoa; he nui ake te rahi o te rauemi kua whakatakotoria i te hua whakamutunga i te mea ka hangaia e te tukanga tango te āhua ma whakamutunga. Ka whakamahia te mīhini CNC hei mīhini i ngā āhua o waho me roto o te taputapu, ka hua ake he mata o te taputapu me ngā awaawa e rite ana ki te taputapu kua tohua me ngā tawhā tukanga CNC (i tēnei tauira, tata ki te 1.6 µm Ra). Ka whakamahia ngā huringa rehu rauemi ultrasonic me te mīhini tonu, puta noa i te tukanga hanga o te taputapu hei whakarite kia mau tonu te tika o ngā āhuatanga, ā, ka tutuki te wāhanga kua oti i ngā taumata tika o te mira pai CNC. He iti te whānui o te awaawa e whakamahia ana mō tēnei taputapu kia kore ai te rauemi pepa whakarewa e "heke" i roto i te awaawa wai, nō reira he tapawhā te waahanga o te awaawa. I whakatauhia ngā āputa pea i roto i te rauemi pepa whakarewa me ngā tawhā o te tukanga UAM mā te whakamātautau e te hoa hanga (Fabrisonic LLC, USA).
Kua whakaatuhia e ngā rangahau he iti noa te horapa o ngā huānga i te atanga 46, 47 o te matū UAM me te kore he maimoatanga wera tāpiri, nō reira mō ngā taputapu o tēnei mahi ka noho rerekē tonu te paparanga Cu-110 mai i te paparanga Al 6061, ā, ka tino rerekē.
Tāutahia he kaiwhakahaere pēhanga whakamuri kua whakatikatikaina i mua (BPR) i te 250 psi (1724 kPa) i raro iho o te tauhohenga 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 taputapu whakawhiti pēhanga FlowSyn i hangaia ki roto i te pūnaha hei whakarite kia mau tonu te pēhanga pumau o te pūnaha. I whakamatautauria ngā pikinga pāmahana pea i roto i te tauhohenga rere mā te rapu i ngā rerekētanga i waenga i ngā takirua wera i hangaia ki roto i te tauhohenga me ngā takirua wera i hangaia ki roto i te pereti whakamahana o te maramara FlowSyn. Ka tutuki tēnei mā te whakarerekē i te pāmahana pereti wera kua whakaritea i waenga i te 100 me te 150 °C i roto i ngā pikinga 25 °C me te aroturuki 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.
Kua arotauhia ngā tikanga mō te 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 whakamahi i tētahi huarahi hoahoa whakamātautau tauwehe katoa (DOE), mā te whakamahi i te pāmahana me te wā noho hei 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 pupuhihia mā roto i te tauhohenga i te tere rere me te pāmahana e hiahiatia ana. I tangohia te urupare o te tauira hei ōwehenga o te horahanga tihi o te hua triazole ki te rauemi tīmatanga o te phenylacetylene, ā, i whakatauhia mā te whakamahi i te chromatography wai mahi teitei (HPLC). Mō te ōritetanga tātari, i tangohia ngā tauhohenga katoa i muri tonu 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), 4.6 x 100 mm, te rahi matūriki 5 µm, i puritia i te 40°C. Ko te whakarewa he isocratic methanol:wai 50:50 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. I tatauhia te % horahanga tihi mō te tauira DOE mai i ngā horahanga tihi o ngā hua alkyne me triazole toenga anake. Mā te whakaurunga o te rauemi tīmatanga ka taea te tautuhi i ngā tihi e rite ana.
Mā te whakakotahi i ngā hua o te tātaritanga tauhohenga me te pūmanawa MODDE DOE (Umetrics, Malmö, Sweden) i taea ai te tātaritanga au o ngā hua me te whakatau i ngā āhuatanga tauhohenga tino pai mō tēnei cycloaddition. Mā te whakahaere i te arotautanga kua hangaia me te whiriwhiri i ngā kupu tauira nui katoa ka hangaia he huinga āhuatanga tauhohenga kua hangaia hei whakanui ake i te horahanga tihi o te hua me te whakaiti i te horahanga tihi mō te rauemi whāngai acetylene.
I tutuki te waikura o te mata parahi i roto i te rūma tauhohenga whakakorikori mā te whakamahi i te otinga 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 pūhui triazole. whare pukapuka.
I te whakataunga o te huinga tikanga tino pai, ka whakamahia ēnei ki te whānuitanga o ngā matū acetylene me ngā matū haloalkane kia taea ai te kohikohi i tētahi whare pukapuka whakahiato iti, ā, ka whakatūria te āheinga ki te whakamahi i ēnei tikanga 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 konatunatua ngā wāhanga o te 3 ml o ia otinga, ā, i pupuhihia mā roto i te tauhohenga i te tere o te 75 µl/min me te pāmahana o 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 x 10 ml o te wai. I whakakotahihia ngā paparanga wai, ā, i tangohia ki te 10 ml ethyl acetate, kātahi ka whakakotahihia ngā paparanga rauropi, i horoia ki te 3 × 10 ml o te wai 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 silica gel mā te whakamahi i te ethyl acetate i mua i te tātari mā te whakakotahitanga o te HPLC, 1H NMR, 13C NMR me te ine papatipu taumira teitei (HR-MS).
I whiwhihia ngā irahiko katoa mā te whakamahi i te irahiko papatipu Thermofischer Precision Orbitrap 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 me te papa konumohe. I tirohia ngā pereti ki te mārama UV (254 nm) me 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) he taputapu aunoa, he papu rua me te oumu pou me tētahi pūoko ngaru kotahi. I whakamahia he pou ACE Equivalence 5 C18 (150 x 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 ko te tau whetu) i te tere rere o te 1.5 ml/min. I puritia te pou i te 40°C. Ko te roanga ngaru o te pūoko he 254 nm.
I tatauhia te % horahanga tihi o te tauira mai i te horahanga tihi o te toenga alkyne, te hua triazole anake, ā, nā te whakaurunga o te rauemi tīmatanga i taea ai te tautuhi i ngā tihi e rite 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 o te 5% DMF me te 2% HNO3, ā, i whakaranua ngā tauira katoa kia 20 ngā wā ki te otinga tauira o te DMF-HNO3.
Ka whakamahia e te UAM te whakarewa whakarewa ultrasonic hei tikanga hono i te pepa whakarewa 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 pepa whakarewa/paparanga kua whakatōpūtia i mua kia herea/kua whakatōpūtia i mua mā te wiri i te rauemi. Mō te mahi tonu, he āhua porotaka te sonotrode, ā, ka hurihuri i runga i te mata o te rauemi, ka piri 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 arahi ki te whakangaromanga o te taratara o te rauemi 36. Ko te whakapā tata ki te wera me te pēhanga ā-rohe ka arahi ki te here ā-wāhanga totoka i ngā atanga rauemi; ka taea hoki e ia te whakatairanga i te piri mā te whakarerekē i te kaha o te mata48. 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 hangarau hanga tāpiri. Mā tēnei ka taea te hononga tika (arā, me te kore whakarerekētanga mata, ngā whakakī, ngā piripiri rānei) o ētahi paparanga o ngā rauemi rerekē ki roto i te hanganga kotahi kua whakatōpūtia.
Ko te tuarua o ngā āhuatanga pai mō te CAM ko te nui o te rere o te 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 ngā wiri ultrasonic me te pēhanga ka puta he taumata teitei o te hekenga rohe witi ā-rohe me te whakahounga anō me te kore e piki ake te pāmahana nui e pā ana ki ngā rauemi papatipu. I te wā e hangaia ana 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 te muka whatu 49, te whakapakari 46, te hikohiko 50 me ngā thermocouples (i 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, i whakamahia ngā āheinga here rauemi rerekē me ngā āheinga whakauru UAM hei waihanga i tētahi microreactor tino pai mō te whakahaere pāmahana catalytic.
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 matū (ii) kei te whānui 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) Ka pai te mahi a ngā tauhohenga whakakorikori Cu i te korenga o ētahi atu ligands. He maha ngā wā he māmā te hanganga o ēnei ligands, ā, he iti te utu. ki te hiahiatia, engari ko ngā mea e whakamahia ana i roto i te matū Pd he maha ngā wā he uaua, he utu nui, ā, he aro ki te hau (iv) Ko te Cu, e mōhiotia whānuitia ana mō tōna kaha ki te hono i ngā alkynes i roto i te hanganga, pērā i te hononga whakakorikori bimetallic a Sonogashira me te cycloaddition me ngā azides (pāwhiri matū) (v) Ka taea hoki e te Cu te whakatairanga i te arylation o ētahi nucleophiles i roto i ngā tauhohenga momo-Ullmann.
Nō nā tata nei, kua whakaaturia ngā tauira o te rerekētanga o ēnei tauhohenga katoa i te aroaro o te 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.
Ko te tauhohenga cycloaddition 1,3-dipolar i waenga i te acetylene me te azide ki te 1,2,3-triazole, i whakaarohia tuatahitia e Huisgen i te tekau tau atu i 196057, e kiia ana he tauhohenga whakaaturanga tahi. Ko ngā maramara 1,2,3 triazole i puta mai he mea tino hirahira hei rongoā i roto i te kimi rongoā nā ō rātou tono koiora me te whakamahinga i roto i ngā momo rongoā 58.
I arohia anō 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 me te whiriwhiri mō te hanga tere o ngā pūhui hou me ngā whare pukapuka whakakotahi mā te whakamahi i te hononga heteroatomic (CXC)60. Ko te rongonui o ēnei tauhohenga nā te nui o ngā hua e pā ana ki a rātou. he māmā ngā āhuatanga, he ātete ki te hāora me te wai, ā, he māmā te wehenga hua61.
Kāore te cycloaddition Huisgen 1,3-dipole matarohia e taka ki roto i te kāwai "matū pāwhiri". Heoi, i whakaaturia e Medal me Sharpless ka pāngia tēnei huihuinga hononga azide-alkyne e te 107–108 i te aroaro o Cu(I) ki te whakataurite ki te tere tere o te cycloaddition 1,3-dipolar kore-catalytic 62,63. Kāore tēnei tikanga tauhohenga matatau e hiahia ki ngā rōpū tiaki, ki ngā āhuatanga tauhohenga kino rānei, ā, ka tata te hurihanga me te whiriwhiringa ki ngā 1,2,3-triazole kua whakakorea (anti-1,2,3-triazole) i roto i te 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 homai noa i ngā 1,4-disubstituted 1,2,3-triazoles, ko ngā cycloadditions Huisgen i whakakōkīhia ki te wera ka homai i te 1,4- me te 1,5-triazoles he ranunga 1:1 o ngā azole stereoisomers.
Ko te nuinga o ngā tikanga e pā ana ki te whakaiti i ngā pūtake pumau o te Cu(II), pērā i te whakaiti i te CuSO4, i te matū Cu(II)/Cu(0) rānei me ngā tote konutai. Ki te whakatauritea ki ētahi atu tauhohenga whakarewa, ko ngā painga matua o te whakamahinga o te Cu(I) he iti te utu, he ngāwari hoki te whakahaere.
Kua whakaatuhia e ngā rangahau kinetic me isotopic a Worrell et al. 65, mō ngā alkynes whakamutunga, e rua ngā parahi ōrite e uru ana ki te whakahohe i te tauhohenga o ia ngota ngota e pā ana ki te azide. Ka puta te tikanga kua whakaarohia mā roto i tētahi 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 hei hua o te whakahekenga mowhiti, ā, ka whai muri ko te wetewete proton hei hanga 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 wā-tūturu i roto i te tūnga66,67. Kua whakamātauhia te UAM hei tikanga pai mō te hoahoa me te hanga i ngā tauhohenga rere 3D tino uaua 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 hangaia ki roto, me te rūma tauhohenga whakatere. 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 matū mō ngā tauhohenga matū ā muri ake nei, me whakamahana haumaru ngā whakarewa ki runga ake i tō rātou pūnga kohua; ka whakamatautauria te pēhanga me te pāmahana. I whakaatuhia e te whakamātautau pēhanga he pumau, he pumau hoki te pēhanga o te pūnaha ahakoa te pēhanga teitei i roto i te pūnaha (1.7 MPa). I whakahaerehia ngā whakamātautau waipūmau i te pāmahana rūma mā te whakamahi i te H2O hei wai.
I te hononga o te thermocouple kua hangaia (Pikitia 1) ki te pūrakau raraunga pāmahana, i whakaatuhia ko te pāmahana o te thermocouple he 6 °C (± 1 °C) i raro iho i te pāmahana kua whakaritea i roto i te pūnaha FlowSyn. I te nuinga o te wā, ka rua te tere o te tauhohenga mā te pikinga o te pāmahana 10°C, nō reira, mā te rerekētanga pāmahana o ētahi nekehanga noa iho ka taea te whakarerekē nui i te tere o te tauhohenga. Nā te ngaronga pāmahana puta noa i te RPV tēnei rerekētanga nā te nui o te horapa wera o ngā rauemi e whakamahia ana i roto i te tukanga hanga. He pumau tēnei nekehanga wera, nō reira ka taea te whakaaro i te wā e whakatū ana i ngā taputapu kia tika ai te tae atu ki ngā pāmahana 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 whai wāhi ki te arotautanga tukanga tika ake me te whakawhanake i ngā āhuatanga tino pai. Ka taea hoki te whakamahi i ēnei pūoko ki te kite i ngā tauhohenga wera me te ārai i ngā tauhohenga koretake i roto i ngā pūnaha tauine nui.
Ko te tauhohenga e whakaaturia ana i roto i tēnei pepa 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 kitea e pā ana ki te tukatuka i te parahi, te koranu konumohe rānei (ii) te whakapai ake i te taumira o roto o te awaawa ki te whakataurite ki ngā tikanga rewa 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 pāmahana tukatuka iti iho, e āwhina ana i te hono tika o ngā pūoko, kāore 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 whakarewa waro noa17,19.
I whakaaturia te mahi a te tauhohenga mā te raupapa o ngā tauhohenga cycloaddition alkinazide kua whakakorikoria ki te parahi i raro i ngā tikanga rere tonu (Pikitia 2). Ko te tauhohenga parahi tāia ultrasonic e whakaaturia ana i te pikitia 4 i whakauruhia ki tētahi pūnaha rere arumoni, ā, i whakamahia hei hanga i tētahi whare pukapuka azide o ngā momo 1,4-disubstituted 1,2,3-triazoles mā te whakamahi i tētahi tauhohenga pāmahana whakahaeretia o te acetylene me ngā alkyl group halides i te aroaro o te konutai pūhaumāota (Pikitia 3). Mā te whakamahinga o te huarahi rere tonu ka whakaitihia ngā take 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 tētahi tauhohenga 3DP ki roto i tētahi pūnaha rere (matau o runga) i tangohia mai i te kaupapa arotau (o raro) o te kaupapa cycloaddition Huisgen 57 i waenga i te phenylacetylene me te iodoethane hei arotau me te whakaatu i ngā tawhā tere tahuritanga arotau o te tauhohenga.
Mā te whakahaere i te wā noho o ngā matū tauhohe i roto i te wāhanga whakatere o te tauhohenga, me te aroturuki āta i te pāmahana tauhohenga me te pūoko thermocouple whakauru tika, ka taea te arotau tere me te tika i ngā āhuatanga tauhohenga me te iti rawa o te wā me ngā rauemi. I kitea wawetia ko te tahuritanga teitei rawa i tutuki mā te whakamahi i te wā noho o te 15 meneti me te pāmahana tauhohenga o te 150°C. Ka kitea mai i te kauwhata tauwehenga o te pūmanawa MODDE e kiia ana ko te wā noho me te pāmahana tauhohenga he āhuatanga nui o te tauira. Mā te whakahaere i te arotau hanga-roto mā te whakamahi i ēnei āhuatanga kua tohua ka hangaia he huinga 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 tahuritanga 53% o te hua triazole, i tino rite ki te matapae a te tauira o te 54%.