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Gukora inyongeramusaruro birahindura uburyo abashakashatsi ninganda bashushanya kandi bagakora ibikoresho byimiti kugirango babone ibyo bakeneye byihariye.Muri uyu murimo, 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 mubibazo byingirakamaro byingirakamaro.1 -ibikoresho bya triazole byashizwemo neza kandi binonosorwa na Cu-yunganirwa na Huisgen 1,3-dipolar cycloaddition reaction ikoresheje chimique ya UAM.Gukoresha uburyo bwihariye bwa UAM hamwe no gutunganya ibicuruzwa bikomeza, igikoresho gishobora guhagarika ibisubizo bikomeje mugihe gitanga kandi 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 (AM) chimie "reaction yamashanyarazi" 8.Igishushanyo mbonera, umusaruro wihuse, hamwe nubushobozi bwa 3-3D (3D) bwubuhanga bugirira akamaro abifuza guhitamo ibikoresho byabo muburyo bwihariye bwa reaction, ibikoresho, cyangwa imiterere.Ku munsi, iki gikorwa cyibanze kuri tekinike ya SL / 910. kwerekana osition (FDM) 8,12,13,14 hamwe no gucapa inkjet 7, 15, 16. Kubura imbaraga nubushobozi bwibikoresho nkibi byo gukora imiti itandukanye ya reaction / analyse17, 18, 19, 20 nikintu gikomeye kibuza abantu gushyira mubikorwa AM muri uru rwego17, 18, 19, 20.
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 cyane ndetse no ku rugero rwo hejuru rwa plasitike 21, 22, 23 .Ntabwo bimeze nk'ibindi bikoresho bya tekinoroji ya AMC, UAM irashobora gukoreshwa mu buryo butaziguye no gukora imashini zikoresha imashini zikoreshwa na mudasobwa. gutunganya cyangwa lazeri bisobanura imiterere y'urusobekerane rw'ibikoresho bifatanyirijwe hamwe 24, 25.Ibyo bivuze ko uyikoresha atagarukira kubibazo bifitanye isano no kuvana ibikoresho byubatswe byubatswe bisigaye mu miyoboro ntoya y'amazi, bikunze kugaragara kuri poro na sisitemu ya AM 26,27,28.Ubu bwisanzure bwibishushanyo nabwo bugera no muburyo bwo guhitamo ibintu muburyo butandukanye bwo guhuza ibikoresho muburyo bwo guhitamo ibintu muburyo butandukanye bwo guhuza ibikoresho muburyo bwo guhitamo ibintu muburyo bumwe bwo guhuza ibikoresho muburyo bwo guhitamo ibintu muburyo butandukanye bwo guhuza ibikoresho. Usibye guhuza bikomeye kwa leta, 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 ibintu bya mashini / ubushyuhe hagati yicyuma kitarangiritse.Icyuma gishyizwemo na UAM gishobora koroshya itangwa ryamakuru nyayo kuva kubikoresho kugeza kubukoresha binyuze mubisesenguye byuzuye.
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 byarakoreshejwe bitabanje kwezwa.1H na 13C NMR yerekanwe kuri 400 MHz na 100 MHz, byabonetse hakoreshejwe JEOL ECS-400 400 MHz spectrometer cyangwa Bruker Avance II 400 MHz spekrometero na CDCl3 urubuga.
UAM yakoreshejwe mu guhimba ibikoresho byose muri ubu bushakashatsi.Ikoranabuhanga ryavumbuwe 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 (ibikoresho bya Fabriconic, OH, USA). 9.9% y'umuringa), ubigira umukandida mwiza kubitekerezo bya catalizike, bityo bigakoreshwa nk "urwego rukora muri microreactor.Al 6061 O ikoreshwa nkibikoresho "byinshi", na Embedding layer ikoreshwa mu gusesengura;Gukoresha ibice byingirakamaro byinjizwamo hamwe nuburyo bufatanije hamwe na Cu-110.Al 6061 O ni ibikoresho byagaragaye ko bihuye cyane na UAM inzira38, 39, 40, 41 kandi byarageragejwe kandi bisanga imiti ihamye hamwe na reagent zikoreshwa muriki gikorwa.Gukomatanya Al 6061 O na Cu-110 nabyo bifatwa nkibikoresho bihuza UAM bityo bikaba ibikoresho bibereye 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 ni ugukoresha inzira ihindagurika kugirango wongere intera itembera ingendo muri chip, mugihe kugumisha chip mubunini bushobora gucungwa. Uku kwiyongera kwintera kwifuzwa kongera igihe cyo guhuza catalizator / reagent no gutanga umusaruro mwiza wibicuruzwa. reagent inlet ihujwe kuri Y-ihuriro mbere yo kwinjira mu gice cyo kuvanga inzoka. Inlet ya gatatu, ihuza imigezi igice cyayo ituye, ishyirwa mubishushanyo mbonera bizaza.
Imiyoboro yose ifite umwirondoro wa kare (nta mbanzirizamushinga), ibisubizo byigihe cyo gusya kwa CNC byakoreshejwe mugukora umuyoboro wa geometrie.Ibipimo byumuyoboro byatoranijwe kugirango habeho umusaruro mwinshi (kuri microreactor), mugihe ari bito bihagije kugirango byorohereze imikoranire yubutaka (catalizator) kubintu byinshi birimo amazi.Ubunini bukwiye bwari bushingiye ku byuma byashize hamwe na 750m. umuhuza uhuriweho (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 icyuma cya kare. Imiterere nubunini bwimiyoboro irashobora guhindurwa nimashini za CNC ukoresheje ibikoresho bitandukanye byo gutema kugirango ubone igipimo cyimiterere itandukanye nibiranga.Urugero rwo gukora umuyoboro wuburyo bugoramye ukoresheje igikoresho cya mμm 125 ushobora kuboneka mubikorwa bya Monaghan45.Iyo igipande cya fayili gishyizwe muburyo bwa tekinike. , kare kare.
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;ingano yibikoresho byabitswe ni binini kuruta ibicuruzwa byanyuma kuko inzira yo gukuramo itanga ishusho yanyuma ya net.Imashini ya CNC ikoreshwa mugukora imashini yo hanze ninyuma yibikoresho, bikavamo kurangiza hejuru yibikoresho hamwe numuyoboro uhwanye nibikoresho byatoranijwe hamwe nibikoresho bya CNC (hafi 1,6 μm Ra muri uru rugero) ubugari bwumuyoboro ukoreshwa kuri iki gikoresho ni gito 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 cyerekana ingufu za FlowSyn kugirango ugenzure neza ko sisitemu ishobora gukomeza umuvuduko uri hagati yubushakashatsi bwashyizwemo nubushakashatsi bwashyizwemo nubushakashatsi bwakozwe nubushakashatsi bwakozwe mubushakashatsi bwerekana ko ibintu byose byashyizwemo ingufu zashizwemo. yn chip yo gushyushya isahani.Ibi bigerwaho muguhindura ubushyuhe bwa progaramu ya hotplate iri hagati ya 100 na 150 ° C mukwiyongera kwa 25 ° C no kwerekana itandukaniro riri hagati yubushyuhe bwateganijwe kandi bwanditse.Ibi byagezweho hifashishijwe tc-08 yandika amakuru (PicoTech, Cambridge, UK) hamwe na software ya PicoLog.
Imiterere ya cycloaddition ya fenilacetylene na iodoethane yariyongereye (Scheme 1- Cycloaddition ya phenylacetylene na iodoethane Scheme 1- Cycloaddition ya fenylacetylene na iodoethane) .Iyi optimizasiyo yakozwe nigipimo cyuzuye cyibipimo (DOE) uburyo bwo kugereranya ibipimo bya tekinike (DOE).
Hateguwe ibisubizo bitandukanye bya sodium azide (0.25 M, 4: 1 DMF: H2O), iyodehane (0,25 M, DMF), na fenylacetylene (0.125 M, DMF). HPLC.
Ingero zose zasesenguwe hifashishijwe sisitemu ya Chromaster HPLC (VWR, PA, USA) igizwe na pompe ya kane, ifuru yinkingi, impinduka yumurambararo wa UV detector na autosampler.Inkingi yari Equivalence 5 C18 (VWR, PA, USA), 4,6 × 100 mm mubunini, 5 µm ingano yubunini bwa 1.5L. kandi uburebure bwa detector bwari 254 nm.Ubuso bwa% hejuru yicyitegererezo cya DOE bwabazwe uhereye kumpinga yibicuruzwa bisigaye bya alkyne na triazole gusa. Gutera ibikoresho byatangiye bituma hamenyekana 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 alkine (0,125 M, DMF). ous ibice byahujwe kandi bivanwamo mL 10 ya acilique 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 fayili / mbere cyahujwe kugirango gihuze mugihe cyo kunyeganyeza ibintu. hejuru yibikoresho birashobora gucika. Umuvuduko ukomeje hamwe no kunyeganyega birashobora gutuma asperities yibintu isenyuka 36 .Guhuza byimazeyo nubushyuhe buterwa nubutaka hamwe nigitutu noneho biganisha kumurongo 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 rwo hejuru rwamazi ya plastike agaragara mubikoresho byuma, ndetse no mubushyuhe buke, ni ukuvuga munsi yumushonga wibikoresho byibyuma. Guhuza ihindagurika rya ultrasonic hamwe nigitutu bitera urwego rwo hejuru rwimuka rwimipaka yimuka no kongera kwinjizamo nta bushyuhe bunini bwiyongera kubisanzwe hamwe nibice bya tekinike.Ibice bya fibre hamwe nibice byinshi. , ibishimangira 46, ibikoresho bya elegitoroniki 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 nubundi buryo bukoreshwa mubyuma byifashishwa, catalizike ya Cu ifite ibyiza byinshi: (i) Mu bukungu, Cu ihenze cyane kuruta ibindi byuma byinshi bikoreshwa muri catalizike bityo rero ni amahitamo ashimishije mu nganda zitunganya imiti (ii) Urutonde rwibikorwa bya Cu-catalizasique rwiyongera kandi bigaragara ko byuzuzanya muburyo bwa Pd bushingiye ku mikorere ya ligand. ensive niba ubishaka, mugihe izikoreshwa muri chimie ya Pd akenshi iba igoye, ihenze, kandi yunvikana nikirere (iv) Cu, cyane cyane izwiho 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 bifitemo inyungu 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 108 imbere ya Cu (I) ugereranije na 1,3-dipolar cycloaddition itagabanije 62,63 byihuta byihuta kandi bidatanga umusaruro ushimishije. azoles (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 ihujwe na acetylide y'umuringa hamwe na π-ihujwe n'umuringa utanga umusaruro wa tronike ya tronc. .
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 ibyashizwemo (Igicapo 1) thermocouple hamwe nubushakashatsi bwamakuru yubushyuhe bwerekanye ko thermocouple yari ifite ubukonje bwa 6 ° C (± 1 ° C) kurenza ubushyuhe bwateganijwe kuri sisitemu ya FlowSyn.Ubusanzwe, kwiyongera kwa 10 ° C bituma habaho gukuba kabiri igipimo cyibisubizo, bityo itandukaniro ryubushyuhe bwa dogere nkeya gusa rishobora gukoreshwa cyane nubushyuhe bukabije bwibintu biterwa nubushyuhe bukabije bitewe nubushyuhe bukabije bwibintu biterwa nubushyuhe bukabije bitewe nubushyuhe bukabije bwibintu biterwa nubushyuhe bukabije bwibintu biterwa nubushyuhe bukabije bwibintu biterwa nubushyuhe bukabije bitewe nubushyuhe bukabije bitewe nubushyuhe bukabije bwibintu biterwa nubushyuhe bukabije. gutwarwa nubushyuhe bwe birahoraho kandi birashobora rero kubarwa mubikoresho byashizweho kugirango harebwe ubushyuhe nyabwo bugerwaho kandi bupimwe mugihe cyo kubyitwaramo.Nuko rero, iki gikoresho cyo kugenzura kumurongo cyorohereza kugenzura neza ubushyuhe bwimikorere kandi bikorohereza 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 byavuzwe bivugwa bijyanye no gutunganya umuringa cyangwa aluminiyumu (ii) byanonosoye imiyoboro y’imbere ugereranije n’ubushyuhe bwo guhuza ifu (PBM) uburyo bworoshye bwo gutunganya ibintu (SLM) 2569 ibyo ntibishoboka muburyo bwa tekinoroji yuburiri, (v) itsinze imiterere mibi yubukanishi hamwe nubukangurambaga bwibikoresho bishingiye kuri polymer kubice bitandukanye byumusemburo rusange 17,19.
Imikorere ya reaktor yerekanwe nuruhererekane rwumuringa wa catisale alkyne azide cycloaddition reaction mugihe gikomeza gutemba (Ishusho 2) .Icyuma cya ultrasonic cyacapishijwe umuringa cyasobanuwe mubishushanyo cya 4 cyahujwe na sisitemu yo gutembera mubitabo bya azide ya 1,4-idashidikanywaho ya mitiweli ya acidelene. ates impungenge z'umutekano zishobora kuvuka mubikorwa, kuko iki gisubizo gitanga umuhuza wa azide wangiza cyane kandi uteje akaga [317],
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Mugenzura igihe cyo gutura kwa reagent mugice cya catalitiki ya reaktor no gukurikiranira hafi ubushyuhe bwimyitwarire hamwe nubushakashatsi bwa thermocouple butaziguye, imiterere yimyitwarire irashobora gutezimbere vuba kandi neza hamwe nigihe gito nogukoresha ibikoresho.Byahise byemezwa ko ihinduka ryinshi ryabonetse mugihe cyo gutura kuminota 15 hamwe nubushyuhe bwa reaction ya tekinoroji ya MODDE. er ukoresheje aya magambo yatoranijwe ibyara urwego rwibisubizo byateganijwe kugirango hongerwe ahantu hahanamye cyane mugihe hagabanijwe gutangirira ahantu hahanamye.Iyi optimizme yatanze ihinduka rya 53% ryibicuruzwa bya triazole, bihuye neza nicyitegererezo cya 54%.
Hashingiwe ku bitabo byerekana ko oxyde y'umuringa (I) (Cu2O) ishobora gukora nk'ubwoko bukomeye bwa catalitiki ku muringa wa zeru-valent hejuru y’umuringa muri ubwo buryo, 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 bihe byiza kandi umusaruro wabonetse ugereranywa. owever, igenzurwa na HPLC ryerekanye ko iri hinduka ryagabanije cyane igihe cyigihe cyo kubyitwaramo kugeza igihe kingana niminota 90, aho igikorwa cyasaga nkaho kiringaniye kandi kikagera kuri "gihamye" .Iyi nyigo yerekana ko inkomoko yibikorwa bya catalitiki iboneka mumisemburo yumuringa wa zeru aho kuba insimburangingo ya zeru ikenerwa kugirango ikorwe na Cu2 na Cu2O. 71.