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Gukora inyongeramusaruro birahindura uburyo abashakashatsi naba nganda bashushanya kandi bagakora ibikoresho bya shimi kugirango babone ibyo bakeneye byihariye.Muri iki gikorwa, turatanga urugero rwambere rwa reaction ya flux yakozwe na tekinike ikomeye ya reta yamashanyarazi yamashanyarazi Ultrasonic Additive Manufacturing (UAM) hamwe nibice bya catalitiki hamwe nibintu byunvikana.Ntabwo ikoranabuhanga rya UAM ryatsinze byinshi mubibuza gukora muburyo bwa tekinoloji. 1,4-idashidikanywaho 1,2,3-triazole ibice byahujwe neza kandi binonosorwa na Cu-yunganirwa na Huisgen 1,3-dipolar cycloaddition reaction ikoresheje chimie ya UAM.Mu gukoresha umutungo wihariye wa UAM no gutunganya ibicuruzwa bikomeje, igikoresho gishobora guhagarika ibisubizo bikomeje mugihe kandi gitanga ibitekerezo byukuri mugihe cyo gukurikirana no gukora neza.
Bitewe nibyiza byingenzi kurenza igice kinini cyacyo, chimie itemba nikintu cyingenzi kandi kigenda gikura haba mumashuri ndetse ninganda bitewe nubushobozi bwayo bwo kongera guhitamo no gukora neza muri synthesis ya chimique.Ibi biva mubintu byoroshye bya molekile kama1 bigera kumiti2,3 nibicuruzwa bisanzwe 4,5,6. Kurenga 50% byimyitwarire mubikorwa byiza bya chimique na farumasi birashobora kungukirwa no gukoresha itunganywa rihoraho7.
Mu myaka yashize, hagiye hagaragara amatsinda ashaka gusimbuza ibikoresho gakondo byibirahure cyangwa ibikoresho bya chimie bitemba hamwe nogukora ibicuruzwa byongeweho byongeweho (AM) chimie "reaction reaction" 8.Ibishushanyo mbonera, umusaruro wihuse, hamwe nubushobozi bwa 3-buke (3D) bwubuhanga bugirira akamaro abifuza guhitamo ibikoresho byabo kumurongo wihariye wa reaction, ibikoresho, cyangwa imiterere.Ku munsi, iki gikorwa cyibanze cyane kuri tekinoroji ya 3D ya polotike. .
Bitewe no gukoresha imiti ya chimie igenda yiyongera hamwe nibintu byiza bifitanye isano na AM, hakenewe ubushakashatsi bwubuhanga buhanitse butuma abayikoresha bahimba imiyoboro yimikorere ifite ubushobozi bwimiti nisesengura.Ubwo buhanga bugomba gutuma abayikoresha bahitamo ibikoresho bitandukanye bikomeye cyangwa imikorere ikora neza kugirango bakemure ibintu bitandukanye kugirango babone uburyo bwo gukurikirana no kugenzura.
Uburyo bumwe bwo kongeramo ibintu bifite ubushobozi bwo guteza imbere imashini zikoresha imiti ni Ultrasonic Additive Manufacturing (UAM) .Ubu buhanga bukomeye bwa shitingi ya lamination ikoresha ultrasonic oscillations ku byuma byoroheje kugira ngo ubihuze hamwe ku byiciro hamwe n’ubushyuhe buke buke ndetse n’ubushyuhe bwo hejuru bwa plasitike 21, 22, 23. (CNC) gusya cyangwa gutunganya lazeri bisobanura imiterere y'urusobekerane rw'urwego rw'ibikoresho bifatanyirijwe hamwe 24, 25.Ibyo bivuze ko uyikoresha atagarukira kubibazo bifitanye isano no kuvanaho ibikoresho byubaka byubatswe bisigaye mu miyoboro mito y'amazi, bikunze kugaragara kuri poro na sisitemu ya AM 26,27,28.Ubu bwisanzure bwo gushushanya nabwo bugera kubikorwa byo guhuza ibintu muburyo butandukanye bwo guhuza ibintu muburyo bwo guhuza ibintu muburyo butandukanye bwo guhuza ibintu muburyo butandukanye bwo guhuza ibintu muburyo bwo guhuza ibintu muburyo butandukanye bwo guhuza ibintu muburyo butandukanye bwo guhuza ibintu muburyo butandukanye bwo guhuza ibintu muburyo butandukanye. imiti isaba porogaramu yihariye irashobora kugerwaho neza. Usibye guhuza leta ikomeye, ikindi kintu cyagaragaye mugihe cyo guhuza ultrasonic ni umuvuduko mwinshi wibikoresho bya pulasitike ku bushyuhe buke ugereranije 29,30,31,32,33.Iyi miterere yihariye ya UAM irashobora koroshya kwinjiza ibikoresho bya mashini / ubushyuhe hagati yibyuma bitarangiritse.
Ibikorwa byabanditsi byashize32 byerekanaga ubushobozi bwibikorwa bya UAM byo gukora ibyuma bya 3D microfluidic ibyuma bifite ubushobozi bwo kumva.Iyi ni igikoresho cyo kugenzura gusa. Uru rupapuro rugaragaza urugero rwambere rwa reaction ya microfluidic yakozwe na UAM; igikoresho gikora kitagenzura gusa ahubwo gitera na synthesis ya chimique binyuze mubikoresho bya catalizator byubatswe. Igikoresho gihuza ibyiza byinshi bifitanye isano na tekinoroji ya UAM mugukora ibikoresho bya chimique 3D, nka: ubushobozi bwo guhindura ibishushanyo mbonera bya 3D byuzuye bivuye muburyo bwa mudasobwa (CAD) mubicuruzwa; ibihimbano-byinshi byo guhuza ubushyuhe bwinshi nubushyuhe bwa catalitiki; no gushyiramo ibyuma byerekana ubushyuhe hagati yimigezi ya reagent kugirango igenzure neza kandi igenzure neza.Kugaragaza imikorere ya reaktor, isomero ryibikoresho bya farumasi 1,4-bitavanze 1,2,3-triazole bivangwa na misile-catisale Huisgen 1,3-dipolar cycloaddition.Iyi mirimo irerekana uburyo ikoreshwa ryibikoresho bya siyanse hamwe nubushakashatsi bushya bwa mudasobwa.
Umuti wose hamwe na reagent byaguzwe muri Sigma-Aldrich, Alfa Aesar, TCI cyangwa Fischer Scientific kandi byakoreshejwe nta kweza mbere.1H na 13C NMR yerekanwe kuri 400 MHz na 100 MHz, byabonetse hakoreshejwe JEOL ECS-400 400 MHz ya spekrometrike cyangwa Bruker Avance II 400 MHz spekrometero na CDCl3 FlowSyn itemba ya chimie.
UAM yakoreshejwe mu guhimba ibikoresho byose muri ubu bushakashatsi.Ikoranabuhanga ryahimbwe mu 1999, kandi ibisobanuro bya tekinike, ibipimo ngenderwaho ndetse niterambere kuva ryivumburwa rishobora kwigwa hifashishijwe ibikoresho bikurikira byasohotse 34,35,36,37.Ibikoresho (Ishusho 1) byashyizwe mu bikorwa hakoreshejwe ingufu zidasanzwe cyane, 9kW SonicLayer 4000® UAM (Fabrisonic, OH, USA) Ibikoresho bya 110-ibikoresho bya 1106. ibirimo umuringa (byibuze 99,9% y'umuringa), bituma uba umukandida mwiza wibisubizo byumuringa, bityo ukaba ukoreshwa nk "urwego rukora muri microreactor. Al 6061 O ikoreshwa nkibikoresho" byinshi ", na Embedding layer ikoreshwa mu gusesengura; Alloy auxiliary component and condition annealed hamwe hamwe na Cu-110. Imiti ihamye hamwe na reagent zikoreshwa muriki gikorwa. Guhuza Al 6061 O na Cu-110 nabyo bifatwa nkibikoresho bihuza UAM bityo bikaba ibikoresho bibereye kuri ubu bushakashatsi 38,42 Ibi bikoresho biri kurutonde rwa 1 hepfo.
Ibyiciro byo guhimba reaction (1) Al 6061 substrate (2) Guhimba umuyoboro wo hasi washyizwe kumuringa wumuringa (3) Gushyiramo thermocouples hagati yimirongo (4) Umuyoboro wo hejuru (5) Kwinjira no gusohoka (6) reaction ya Monolithic.
Igishushanyo cya filozofiya yinzira yamazi nugukoresha inzira ihindagurika kugirango wongere intera ingendo zigenda muri chip, mugihe ugumije chip mubunini bushobora gucungwa. Uku kwiyongera kwintera ni byiza ko wongera igihe cya catalizator / reagent mugihe cyo gutanga umusaruro kandi utanga umusaruro mwiza wibicuruzwa. Igishushanyo mbonera kirimo ibintu bibiri bya reagent byahujwe kuri Y-ihuriro mbere yo kwinjira mu gice cyo kuvanga inzoka. Inlet ya gatatu, ihuza imigezi hagati y’aho ituye, yashyizwe mu gishushanyo mbonera cya synthèse ya multistep.
Imiyoboro yose ifite umwirondoro wa kare (nta mbanzirizamushinga), ibisubizo byigihe cyo gusya CNC byakoreshejwe mugukora umuyoboro wa geometrie.Ibipimo byumuyoboro byatoranijwe kugirango harebwe umusaruro mwinshi (kuri microreactor), mugihe ari nto bihagije kugirango byorohereze imikoranire yubutaka (catalizator) kubintu byinshi birimo amazi. 1 ml.Umuhuza uhuza (1/4 ″ —28 umugozi wa UNF) ushyizwe mubishushanyo mbonera kugirango habeho guhuza byoroshye ibikoresho nibikoresho bya chimie yubucuruzi. Ingano y'umuyoboro igarukira ku bunini bw'ibikoresho bya file, imiterere ya mashini, hamwe n'ibipimo byo guhuza hamwe na ultrasonics. Ku bugari bwihariye kubintu runaka, ibikoresho "bizunguruka" mumurongo wakozwe. Kugeza ubu nta moderi yihariye yo kubara, bityo ubugari ntarengwa bwumuyoboro kubintu byatanzwe hamwe nigishushanyo cyagenwe mubigeragezo; muriki kibazo, ubugari bwa 750 mm ntibuzatera sag.
Imiterere (kare) yumuyoboro igenwa no gukoresha ikariso ya kare. Imiterere nubunini bwimiyoboro irashobora guhindurwa nimashini za CNC ukoresheje ibikoresho bitandukanye byo gutema kugirango ubone igipimo cyimigendere itandukanye nibiranga.Urugero rwo gukora umuyoboro uhetamye ukoresheje igikoresho cya 125 μm urashobora kuboneka mubikorwa bya Monaghan45.Iyo igipande cya fayili gishyizwe muburyo bwa plan. guhuza umuyoboro, umurongo wa kare wakoreshejwe.
Mugihe cyo kuruhuka byateguwe mbere yo gukora, ubushakashatsi bwubushyuhe bwa termocouple (Ubwoko K) bwinjijwe neza mubikoresho hagati yitsinda ryo hejuru no hepfo (Ishusho 1 - Icyiciro cya 3) .Iyi mashanyarazi irashobora gukurikirana ihinduka ryubushyuhe kuva kuri 200 kugeza 1350 ° C.
Igikorwa cyo gushira ibyuma bikorwa nihembe rya UAM ukoresheje ubugari bwa mm 25.4, ubugari bwa micron 150 ya fayili.Iyi myenda ya file ihujwe nuruhererekane rw'imirongo yegeranye kugirango ikingire ahantu hose hubatswe; ubunini bwibikoresho byabitswe ni binini kuruta ibicuruzwa byanyuma kuko inzira yo gukuramo itanga umusaruro wanyuma wa net.Imashini ya CNC ikoreshwa mugukora imashini yimbere ninyuma yibikoresho, bikavamo kurangiza hejuru yibikoresho hamwe numuyoboro uhwanye nibikoresho byatoranijwe hamwe nibikoresho bya CNC (hafi 1,6 mkm Ra muri uru rugero) .Ibikoresho bikomeza gukorwa na ultrasonic ibikoresho byuzuzanya kandi bikarangira bikoreshwa muburyo bwo gutunganya ibikoresho bya CNC bikarangira bikoreshwa muburyo bwo gukora neza. urwego rwukuri.Ubugari bwumuyoboro ukoreshwa kuri iki gikoresho ni nto bihagije kugirango umenye neza ko ibikoresho bya fayili "bidacogora" mu muyoboro w’amazi, bityo umuyoboro ugakomeza kwambukiranya kare. Icyuho gishobora kuba kiri mu bikoresho bya fayili hamwe n’ibipimo bya UAM byagenwe mu igeragezwa n’umufatanyabikorwa ukora (Fabrisonic LLC, USA).
Ubushakashatsi bwerekanye ko ikwirakwizwa rito ryibanze riboneka kuri UAM ihuza interineti 46, 47 nta yandi mashanyarazi yongeyeho, kubikoresho rero muriki gikorwa, Cu-110 ikomeza gutandukana na Al 6061 kandi ihinduka gitunguranye.
Shyiramo mbere ya kalibibasi 250 psi (1724 kPa) igenzura umuvuduko winyuma (BPR) kugirango isohoke ya reaktor hanyuma uvoma amazi unyuze mumashanyarazi ku gipimo cya 0.1 kugeza kuri 1 mL min-1.Umuvuduko wa reakteri wakurikiranwe hifashishijwe icyuma gipima ingufu za FlowSyn kugirango ugenzure ko sisitemu ishobora gukomeza umuvuduko uri hagati yubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe nubushakashatsi bwakozwe mubushakashatsi bwerekana ko sisitemu ishobora kugumaho. byinjijwe muri plaque ya FlowSyn chip.Ibi bigerwaho muguhindura ubushyuhe bwa progaramu ya hotplate ya programme iri hagati ya 100 na 150 ° C mukwiyongera kwa 25 ° C no kwerekana itandukaniro riri hagati yubushyuhe bwateganijwe kandi bwanditse.Ibi byagezweho hifashishijwe amakuru ya tc-08 (PicoTech, Cambridge, UK) hamwe na software ya PicoLog.
Imiterere ya cycloaddition ya fenilacetylene na iodoethane yariyongereye (Scheme 1- Cycloaddition ya fenylacetylene na iodoethane Scheme 1- Cycloaddition ya fenilacetylene na iodoethane) .Iyi optimizasiyo yakozwe nubushakashatsi bwuzuye mugihe cyo kugereranya ubushyuhe hamwe nubushakashatsi, DOE) 1: 2.
Hateguwe ibisubizo bitandukanye bya sodium azide (0.25 M, 4: 1 DMF: H2O), iodoethane (0,25 M, DMF), na fenylacetylene (0.125 M, DMF). Amazi ya chromatografiya (HPLC) .Kuburyo bwo gusesengura, ibisubizo byose byatoranijwe nyuma yimvange ya reaction ivuye mumashanyarazi.Ibipimo byerekana ibipimo byatoranijwe kugirango bibe byiza byerekanwe kumeza 2.
Ingero zose zasesenguwe hifashishijwe sisitemu ya Chromaster HPLC (VWR, PA, USA) igizwe na pompe ya kane, ifuru yinkingi, impinduka ya wavelength UV detector na autosampler. Inkingi yari Equivalence 5 C18 (VWR, PA, USA), 4,6 × 100 mm z'ubunini, 5 µm ingano yubunini bwa metero 50. ingano yari 5 µL naho uburebure bwa detector bwari 254 nm. Agace k'impinga ya% ya sample ya DOE yabazwe uhereye kumpinga yibicuruzwa bisigaye bya alkyne na triazole gusa. Gutera ibikoresho byatangiye bituma habaho kumenya impinga zijyanye.
Guhuza isesengura rya reaktor kuri software ya MODDE DOE (Umetrics, Malmö, Suwede) yemereye isesengura ryimbitse ryibisubizo hamwe no kumenya uburyo bwiza bwo kwitwara neza kuri iyi cycloaddition.Gukoresha ibyubaka-optimizer no guhitamo amagambo yose yicyitegererezo bitanga uburyo bwo kubyitwaramo neza mugihe hagabanijwe ahantu hahanamye kubintu bya acetylene.
Okiside yumuringa wubuso mucyumba cya catalitiki reaction yagezweho hakoreshejwe igisubizo cya hydrogen peroxide (36%) inyura mucyumba cyitwaramo (umuvuduko = 0.4 mL min-1, igihe cyo gutura = 2,5 min) mbere yo guhuza buri somero ryibitabo bya triazole.
Bimaze kumenyekana neza ko ibintu bimeze neza, byashyizwe kumurongo wa acetylene na haloalkane kugirango bikusanyirize hamwe isomero rito ry'isomero, bityo hashyizweho ubushobozi bwo gukoresha ibyo bintu muburyo bwagutse bwa reagent (Ishusho 1) .2).
Tegura ibisubizo bitandukanye bya sodium azide (0.25 M, 4: 1 DMF: H2O), haloalkane (0,25 M, DMF) na alkynes (0,125 M, DMF). amazi. Ibice byamazi byahujwe bigakurwa hamwe na mL 10 ya acetate ya Ethyl; ibice kama noneho byahujwe, byogejwe na 3 x 10 mL ya brine, byumishwa hejuru ya MgSO4 hanyuma birayungurura, hanyuma umusemburo ukurwa muri vacuo. Ingero zahanaguwe na chromatografiya yinkingi kuri silika gel ikoresheje Ethyl acetate mbere yisesengura ryakozwe na HPLC, 1H NMR, 13C NMR hamwe na mass spectrometrie (HR-MS).
Ibyerekanwe byose byabonetse hakoreshejwe Thermofischer precision Orbitrap resolution mass spectrometer hamwe na ESI nkisoko ya ionisation. Ingero zose zateguwe hifashishijwe acetonitrile nka solve.
Isesengura rya TLC ryakorewe ku byapa bya silika bishyigikiwe na aluminiyumu. Isahani yagaragajwe n’urumuri rwa UV (254 nm) cyangwa vanillin irangi no gushyushya.
Ingero zose zasesenguwe hakoreshejwe Chromaster ya VWR (VWR International Ltd, Leighton Buzzard, UK) ifite ibikoresho bya autosampler, inkingi ya binary pompe hamwe na disiketi imwe yumurambararo. Inkingi yakoreshejwe yari ACE Equivalence 5 C18 (150 × 4,6 mm, Advanced Chromatography Technologies Ltd, Aberdeen, Scotland).
Inshinge (5 µL) zakozwe mu buryo butaziguye bivuye mu ruvangitirane ruvanze (1:10 dilution) hanyuma rusesengurwa n’amazi: methanol (50:50 cyangwa 70:30), usibye ingero zimwe na zimwe zikoresha sisitemu yo gukemura 70:30 (yerekana ko ari inyenyeri) ku kigero cya 1.5 mL / min. Inkingi yabitswe kuri 40 ° C.
Agace k'impinga ya% y'icyitegererezo yabazwe uhereye ku mpinga ya alkyne isigaye, gusa ibicuruzwa bya triazole, kandi gutera inshinge zatangiye byatumaga kumenya impinga zibishinzwe.
Ingero zose zasesenguwe hifashishijwe Thermo iCAP 6000 ICP-OES. Ibipimo byose bya kalibrasi byateguwe hifashishijwe igisubizo cya 1000 ppm Cu gisanzwe muri acide ya nitric 2% (SPEX Certi Prep) .Ibipimo byose byateguwe muri 5% DMF na 2% HNO3, kandi ibyitegererezo byose byashyizwemo inshuro 20 mubisubizo DMF-HNO3.
UAM ikoresha gusudira ibyuma bya ultrasonic nkubuhanga bwo guhuza ibikoresho bya fayili ikoreshwa mukubaka inteko ya nyuma. Gusudira ibyuma bya Ultrasonic bifashisha igikoresho cyinyeganyeza (cyitwa ihembe cyangwa ihembe rya ultrasonic) kugirango gikoreshe igitutu kumurongo wa foil / mbere cyahujwe kugirango gihuze mugihe cyo kunyeganyeza ibintu. ushyizwe mu bikorwa, okiside iri hejuru yibikoresho irashobora gucika. Umuvuduko ukomeje hamwe no kunyeganyega birashobora gutuma asperities yibintu isenyuka 36 .Guhuza byimazeyo nubushyuhe bwumuvuduko ukabije hamwe nigitutu noneho biganisha kumurongo ukomeye uhuza ibintu bifatika; irashobora kandi gufasha gufatira hamwe binyuze mumihindagurikire yingufu zubutaka48.Imiterere yuburyo bwo guhuza itsinze byinshi mubibazo bifitanye isano nubushyuhe bwimihindagurikire yubushyuhe hamwe nubushyuhe bwo hejuru nyuma yingaruka zavuzwe mubindi buhanga bwo gukora inyongeramusaruro.Ibyo bituma habaho guhuza bitaziguye (ni ukuvuga, nta guhindura isura, kuzuza cyangwa gufatira) ibice byinshi byibikoresho bitandukanye muburyo bumwe.
Ikintu cya kabiri cyiza kuri UAM ni urwego rwohejuru rwamazi ya plastike agaragara mubikoresho byuma, ndetse no mubushyuhe buke, ni ukuvuga munsi yumwanya wo gushonga wibikoresho byuma. Guhuza ihindagurika rya ultrasonic hamwe nigitutu bitera urwego rwo hejuru rwimuka rwimipaka yimuka no kongera kwinjizamo nta bushyuhe bwinshi bwiyongera busanzwe bujyanye nibice byinshi. nka fibre optique 49, ibishimangira 46, electronics 50, hamwe na thermocouples (iki gikorwa) byose byinjijwe neza muburyo bwa UAM kugirango habeho inteko ikora kandi yoroheje.
Muriyi mirimo, byombi ibintu bitandukanye bihuza hamwe na intercalation zishoboka za UAM byakoreshejwe mugukora microreactor ikurikirana ubushyuhe bwa catalitiki.
Ugereranije na palladium (Pd) hamwe nizindi zikoreshwa cyane mubyuma bya catalizike, Cu catalizike ifite ibyiza byinshi: (i) Mubukungu, Cu ntabwo ihenze ugereranije nibindi byuma byinshi bikoreshwa muri catalizike bityo rero ni amahitamo ashimishije mubikorwa byo gutunganya imiti (ii) Urutonde rwibikorwa bya Cu-catalizasique rwiyongera kandi bigaragara ko byuzuzanya muburyo bwa Pd bushingiye kuri ligande zakozwe na ligand. muburyo bworoshye kandi buhendutse niba ubishaka, mugihe ibikoreshwa muri chimie ya Pd akenshi usanga bigoye, bihenze, kandi byangiza ikirere (iv) Cu, cyane cyane bizwiho ubushobozi bwo guhuza alkine muri synthesis, Kurugero, bimetallic-catisale Sonogashira guhuza hamwe na cycloaddition hamwe na azide (kanda chimie) (v) Cu nayo irashobora guteza imbere arylation ya nucleophile nyinshi muburyo bwa Ullmann.
Ingero zo gutandukana kwa reaction zose ziherutse kugaragara imbere ya Cu (0) .Ibi ahanini biterwa ninganda zimiti no kwiyongera kwibanda kumyuma ya catalizator no kongera gukoresha 55,56.
Abapayiniya na Huisgen mu myaka ya za 1960, 57, reaction ya 1,3-dipolar cycloaddition reaction hagati ya acetylene na azide kugeza kuri 1,2,3-triazole ifatwa nkigikorwa cyo kwerekana imyiyerekano.Ibisubizo bivamo 1,2,3 triazole birashimishije cyane nka farumasi murwego rwo kuvumbura ibiyobyabwenge kubera gukoresha ibinyabuzima no gukoresha imiti itandukanye 58.
Iki gisubizo cyongeye kwibandwaho mugihe Sharpless nabandi batangizaga igitekerezo cya "kanda chimie" 59. Ijambo "kanda chimie" rikoreshwa mugusobanura uburyo bukomeye, bwizewe kandi bwatoranijwe bwerekana uburyo bwihuse bwihuse bwibintu bishya hamwe nububiko bwibitabo bukomatanya binyuze mumikoranire ya heteroatom (CXC) 60 Ubujurire bwa syntetique yibi bitekerezo bituruka kumusaruro mwinshi ufatika, ibintu byoroshye ni ibintu bitandukanijwe nibisanzwe6, ogisijeni hamwe n’amazi.
Ibyamamare bya Huisgen 1,3-dipole cycloaddition ntabwo biri mubyiciro bya "kanda chimie" .Nyamara, Medal na Sharpless berekanye ko iki gikorwa cyo guhuza azide-alkyne gihura na 107 kugeza kuri 108 imbere ya Cu (I) ugereranije na 1,3-dipolar cycloaddition ya 62,63 yihuta kandi ntigishobora gukenerwa kugirango habeho uburyo bwo gukemura ibibazo. 1,2,3-triazoles (anti-1,2,3-triazole) ku gipimo cyigihe (Ishusho 3).
Ibisubizo bya Isometricike ya cycloadditions ya Huisgen isanzwe hamwe numuringa.Cu (I) -yatangije cycloadditions ya Huisgen itanga 1,4 gusa-idashidikanywaho 1,2,3-triazole, mugihe cyisukari ya Huisgen iterwa nubushyuhe mubisanzwe itanga 1,4- na 1.5-triazole 1: 1 ivangwa na stereoisomers ya azoles.
Porotokole nyinshi zirimo kugabanya isoko ya Cu (II) ihamye, nko kugabanya amoko ya CuSO4 cyangwa Cu (II) / Cu (0) ifatanije nu munyu wa sodiumi. Ugereranije nibindi byuma byatewe na catalizike, gukoresha Cu (I) bifite ibyiza byingenzi byo kuba bihendutse kandi byoroshye kubyitwaramo.
Kinetic na isotopic labels ubushakashatsi bwakozwe na Worrell nabandi. 65 yerekanye ko, kubijyanye na alkynes ya terminal, ibice bibiri bingana numuringa bigira uruhare mugukora reaction ya buri molekile yerekeza kuri azide.Uburyo bwateganijwe buturuka kumpeta yumuringa igizwe nabanyamuryango batandatu igizwe no guhuza azide na σ-ihuza umuringa acetylide hamwe na π-umuringa uhoraho hamwe na progaramu ya troncrole. funga uruziga.
Mugihe ibyiza byibikoresho bya chimie bitemba byanditse neza, habaye icyifuzo cyo kwinjiza ibikoresho byisesengura muri sisitemu kugirango umurongo, aho uri, kugenzura inzira 66,67.UAM yerekanye ko ari uburyo bukwiye bwo gushushanya no gutanga ibyuma bigezweho bya 3D bigizwe na catalitiki, ibikoresho bitwara ibintu hamwe nubushakashatsi bwimbitse (Ishusho 4).
Imashini ya aluminium-umuringa yakozwe na ultrasonic yongeramo inganda (UAM) ifite imiterere yimbere yimbere, yashyizwemo na thermocouples hamwe na catalitiki reaction ya chambre.Ku iyerekwa ryinzira yimbere yimbere, prototype iboneye ikozwe na stereolithographe nayo irerekanwa.
Kugirango reakteri ihimbwe kugirango habeho ibinyabuzima bizaza, ibishishwa bigomba gushyuha neza hejuru yabyo; ni umuvuduko nubushyuhe byapimwe. Ikizamini cyumuvuduko cyerekanaga ko sisitemu ikomeza umuvuduko uhoraho kandi uhoraho nubwo hiyongereyeho umuvuduko wa sisitemu (1.7 MPa) .Ikizamini cya hydrostatike cyakorewe mubushyuhe bwicyumba hakoreshejwe H2O nkamazi.
Guhuza ibikorwa byashyizwemo (Ishusho 1) THERMOCOPLE KUBURYO BWA DEGRKOCOPLE YASOBANURA 6 ° C. umubiri kubera ubushyuhe burenze ibikoresho bikoreshwa muri uburyo bwo gukora.Iyi drift yumuriro irahoraho kandi irashobora rero kubarwa mugushiraho ibikoresho kugirango ubushyuhe nyabwo bugerweho kandi bupimwe mugihe cya reaction. Kubwibyo rero, iki gikoresho cyo kugenzura kumurongo cyorohereza kugenzura neza ubushyuhe bwimikorere kandi cyoroshya uburyo bunoze bwo gutezimbere no guteza imbere ibihe byiza. Izi sensor zirashobora kandi gukoreshwa kugirango hamenyekane ingaruka ziterwa no gukumira ibintu muri sisitemu nini nini.
Imashini yatanzwe muri iki gikorwa ni urugero rwa mbere rwo gukoresha ikoranabuhanga rya UAM mu guhimba imiti y’imiti kandi ikemura imbogamizi nyinshi zikomeye zifitanye isano n’icapiro rya AM / 3D ry’ibikoresho, nka: (i) gutsinda ibibazo bivugwa bijyanye no gutunganya umuringa cyangwa aluminiyumu (ii) byanonosoye imiyoboro y’imbere ugereranije n’uburyo bwo guhitamo ifu (PBM) uburyo bworoshye bwo gutunganya ibintu (SLM) 2569 guhuza ibyuma bifata ibyuma, bidashoboka muburyo bwa tekinoroji yuburiri bwa poro, (v) byatsinze imiterere mibi yubukanishi hamwe nubukangurambaga bwibikoresho bishingiye kuri polymer kubice bitandukanye byumusemburo rusange 17,19.
Imikorere ya reaction yagaragajwe nuruhererekane rwumuringa wa catalizike ya alkyne azide cycloaddition yerekana uko ibintu byifashe neza (Ishusho 2) .Icyuma cya ultrasonic cyacapishijwe umuringa cyerekanwe mubishushanyo cya 4 cyahujwe na sisitemu yo gutembera mubucuruzi kandi ikoreshwa muguhuza azide yibitabo ya 1,4-idashidikanywaho na 1,2,3-triazole ya selile ya acetylene na alky. uburyo bwo gukomeza gutemba bugabanya impungenge z'umutekano zishobora kuvuka mubikorwa byicyiciro, kuko iki gisubizo gitanga umuhuza wa azide wangiza cyane kandi uteje akaga [317],
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Mugucunga igihe cyo gutura cya reagent mugice cya catalitiki ya reaktor no gukurikiranira hafi ubushyuhe bwibisubizo hamwe nubushakashatsi bwa thermocouple butaziguye, imiterere yimyitwarire irashobora gutezimbere byihuse kandi neza hamwe nigihe gito hamwe nogukoresha ibikoresho.Byahise byemezwa ko ihinduka ryinshi ryabonetse mugihe cyo gutura kuminota 15 hamwe nubushyuhe bwikigereranyo cya 150 ° C byakoreshejwe muburyo bwa tekinike ya MODDE. yubatswe muri optimizer ukoresheje aya magambo yatoranijwe itanga urutonde rwibisubizo byateguwe kugirango hongerwe ahantu hahanamye cyane mugihe hagabanijwe gutangira ahantu hahanamye.Iyi optimizme yatanze ihinduka rya 53% ryibicuruzwa bya triazole, bihuye neza nicyitegererezo cya 54%.
Hashingiwe ku bitabo byerekana ko okiside y'umuringa (I) (Cu2O) ishobora gukora nk'ubwoko bukomeye bwa catalitiki ku buso bwa zeru-valent hejuru y'umuringa muri ibyo bitekerezo, ubushobozi bwo kubanziriza okiside hejuru ya reaktor mbere yo gukora reaction yo gutemba bwakozweho ubushakashatsi 70.71. Igisubizo hagati ya fenylacetylene na iodoethane cyongeye gukorwa mu gihe cyiza kandi umusaruro watangijwe ugereranywa n’umusaruro ugereranyije n’uko umusaruro wabonetse ugereranije. . umuringa wungirije (II) isoko yo gufatanya71.