Urakoze gusura Kamere.com.Verisiyo ya mushakisha ukoresha ifite inkunga ya CSS igarukira.Kuburambe bwiza, turagusaba ko ukoresha mushakisha ivuguruye (cyangwa ugahagarika uburyo bwo guhuza uburyo muri Internet Explorer).Hagati aho, kugirango tumenye gukomeza gushyigikirwa, tuzatanga urubuga rudafite imiterere na JavaScript.
Karuseli yerekana amashusho atatu icyarimwe.Koresha Utubuto na Ibikurikira kugirango unyuze mumashusho atatu icyarimwe, cyangwa ukoreshe utubuto twa slide kumpera kugirango wimuke unyuze mubice bitatu icyarimwe.
Inganda ziyongera zirimo guhindura uburyo abashakashatsi ninganda bashushanya kandi bagakora ibikoresho byimiti kugirango babone ibyo bakeneye.Muri iyi nyandiko, turatanga urugero rwambere rwibintu bitemba byakozwe na ultrasonic yongeramo inganda (UAM) kumurika urupapuro rukomeye hamwe nibice bya catalitiki hamwe nibintu byunvikana.Ikoranabuhanga rya UAM ntirishobora gusa kunesha imbogamizi nyinshi zijyanye no kongera inganda zikora imiti, ariko kandi ryagura cyane ubushobozi bwibikoresho nkibi.Umubare munini wibinyabuzima 1,4-udashidikanywaho 1,2,3-triazole ibice byahujwe neza kandi binonosorwa na Cu-yunganirwa na 1,3-dipolar Huisgen cycloaddition reaction ikoresheje ikigo cya chimie UAM.Ukoresheje imiterere yihariye ya UAM hamwe nogukomeza gutembera gutemba, igikoresho gishobora guhagarika ibisubizo bikomeza kimwe no gutanga ibitekerezo-nyabyo kugirango ukurikirane kandi utezimbere ibisubizo.
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.Ibi biva muburyo bwo gukora molekile yoroshye1 kugeza kumiti ya farumasi2,3 nibicuruzwa bisanzwe 4,5,6.Kurenga 50% byimyitwarire mubikorwa byiza bya chimique na farumasi birashobora kungukirwa no gutembera neza7.
Mu myaka yashize, hagiye hagaragara amatsinda ashaka gusimbuza ibikoresho gakondo byibirahure cyangwa ibikoresho bya chimie bitwara imiti "reaction" 8.Igishushanyo mbonera, gukora byihuse, hamwe nubushobozi butatu (3D) bwubu buryo ni ingirakamaro kubashaka guhitamo ibikoresho byabo kumurongo runaka wibisubizo, ibikoresho, cyangwa ibihe.Kugeza ubu, iki gikorwa cyibanze cyane cyane ku gukoresha tekinoroji ya 3D ishingiye kuri polymer nka stereolithography (SL) 9,10,11, Fused Deposition Modeling (FDM) 8,12,13,14 hamwe no gucapa inkjet7,15..
Bitewe no gukoresha imiti ya chimie yiyongera hamwe nibintu byiza bifitanye isano na AM, hakenewe ubushakashatsi bunoze buzafasha abayikoresha guhimba imiyoboro yimikorere ifite chimie nubushobozi bwo gusesengura.Ubu buryo bugomba kwemerera abakoresha guhitamo murwego rwimbaraga nyinshi cyangwa ibikoresho bikora bishobora gukora muburyo butandukanye bwibisubizo, kimwe no koroshya uburyo butandukanye bwo gusesengura ibintu bivuye mubikoresho kugirango bishoboke gukurikirana no kugenzura ibyakozwe.
Uburyo bumwe bwo kongera inyongeramusaruro zishobora gukoreshwa mugutezimbere imiti yimiti yihariye ni Ultrasonic Additive Manufacturing (UAM).Ubu buryo bukomeye bwerekana uburyo bwo kumurika uburyo bukoreshwa bwinyeganyeza za ultrasonic kumpande zicyuma kugirango zihuze hamwe kumurongo hamwe nubushyuhe buke bwa volumetricike hamwe nu rwego rwo hejuru rwamazi ya plastike 21, 22, 23. Bitandukanye nubundi buryo bwinshi bwa tekinoroji ya AM, UAM irashobora guhuzwa neza n’umusaruro ukuramo, uzwi nka gahunda yo gukora imvange, aho usanga uburyo bwo gukuramo ibintu biterwa no gusohora ibintu 24. ibisigisigi byumwimerere bisigaye biva mumiyoboro ntoya y'amazi, bikunze kugaragara muri poro na sisitemu y'amazi AM26,27,28.Ubu bwisanzure bwogushushanya kandi bugera no guhitamo ibikoresho bihari - UAM irashobora guhuza ibice byubushyuhe busa kandi butandukanye muburyo bumwe.Guhitamo ibintu bifatika birenze uburyo bwo gushonga bivuze ko ibisabwa bya mehaniki na chimique ibisabwa byihariye bishobora kuzuzwa neza.Usibye guhuza bikomeye, ikindi kintu kibaho hamwe no guhuza ultrasonic ni amazi menshi yibikoresho bya pulasitike ku bushyuhe buke ugereranije 29,30,31,32,33.Iyi miterere idasanzwe ya UAM ituma ibikoresho bya mashini / ubushyuhe bishyirwa hagati yicyuma nta byangiritse.Ibyuma bya UAM byashyizwemo birashobora korohereza itangwa ryamakuru-nyayo kuva kubikoresho kubakoresha binyuze mubisesenguye.
Ibikorwa byabanje gukorwa nabanditsi32 byerekanaga ubushobozi bwibikorwa bya UAM byo gukora ibyuma bya microfluidic 3D byuma bifite ubushobozi bwo kumva.Iki gikoresho kigamije gukurikirana gusa.Iyi ngingo irerekana urugero rwambere rwa microfluidic reaction ya chimique yakozwe na UAM, igikoresho gikora ntigenzura gusa ahubwo gitera na synthesis ya chimique hamwe nibikoresho bya catalitiki byubatswe.Igikoresho gihuza ibyiza byinshi bifitanye isano nubuhanga bwa UAM mugukora ibikoresho bya chimique 3D, nka: ubushobozi bwo guhindura igishushanyo cya 3D cyuzuye uhereye muburyo bwa mudasobwa (CAD) mubicuruzwa;Ibihimbano-byinshi byo guhuza ubushyuhe bwinshi nubushyuhe bwa catalitiki, kimwe na sensor yumuriro yashyizwe hagati yinzuzi zifatika kugirango igenzure neza kandi ikore ubushyuhe bwubushyuhe.Kugirango ugaragaze imikorere ya reaktor, isomero ryibikoresho bya farumasi 1,4-bidashidikanywaho 1,2,3-triazole ivanze ryashizwemo numuringa watangijwe na 1,3-dipolar Huisgen cycloaddition.Aka kazi karerekana uburyo ikoreshwa ryibikoresho siyanse nubushakashatsi bufashijwe na mudasobwa bishobora gufungura uburyo bushya n'amahirwe ya chimie binyuze mubushakashatsi butandukanye.
Umuti wose hamwe na reagent byaguzwe muri Sigma-Aldrich, Alfa Aesar, TCI, cyangwa Fischer Scientific kandi bikoreshwa nta kweza mbere.1H na 13C NMR yerekanwe kuri 400 na 100 MHz, byabonetse kuri ecran ya JEOL ECS-400 400 MHz cyangwa Bruker Avance II 400 MHz yerekanwe na CDCl3 cyangwa (CD3) 2SO nkibisubizo.Ibisubizo byose byakozwe hifashishijwe porogaramu ya chimie ya Uniqsis FlowSyn.
UAM yakoreshejwe muguhimba ibikoresho byose murubu bushakashatsi.Ikoranabuhanga ryavumbuwe mu 1999 nibisobanuro bya tekiniki, ibipimo byimikorere niterambere kuva ryivumburwa rishobora kwigwa hakoreshejwe ibikoresho byatangajwe 34,35,36,37.Igikoresho (Igishusho 1) cyashyizwe mubikorwa hakoreshejwe sisitemu iremereye 9 kW SonicLayer 4000® UAM (Fabrisonic, Ohio, USA).Ibikoresho byatoranijwe kubikoresho bitemba byari Cu-110 na Al 6061. Cu-110 ifite umuringa mwinshi (byibuze 99.9% y'umuringa), bigatuma iba umukandida mwiza kumuringa watangije reaction bityo ukaba ukoreshwa nk "urwego rukora imbere muri microreactor.Al 6061 O ikoreshwa nkibikoresho "byinshi"., kimwe na intercalation layer yakoreshejwe mu gusesengura;intercalation yibikoresho byingirakamaro hamwe na leta ihujwe hamwe na Cu-110.wasangaga ihagaze neza hamwe na reagent zikoreshwa muriki gikorwa.Al 6061 O ifatanije na Cu-110 nayo ifatwa nkibikoresho bihuza UAM bityo bikaba ibikoresho bibereye ubu bushakashatsi 38,42.Ibi bikoresho biri mu mbonerahamwe ya 1 ikurikira.
Intambwe yo guhimba reaktor (1) 6061 aluminium alloy substrate (2) Guhimba umuyoboro wo hasi uva kumuringa wumuringa (3) Kwinjiza thermocouples hagati yimirongo (4) Umuyoboro wo hejuru (5) Kwinjira no gusohoka (6) reaction ya Monolithic.
Filozofiya yerekana imiyoboro ya filozofiya ni ugukoresha inzira igoramye kugirango wongere intera igenda n'amazi imbere muri chip mugihe ukomeje ubunini bwa chip.Uku kwiyongera kwintera kwifuzwa kongera igihe cyo guhuza ibikorwa no gutanga umusaruro mwiza.Chip ikoresha 90 ° yunamye kumpera yinzira igororotse kugirango itere imvururu zivanze mubikoresho44 kandi byongere igihe cyo guhura kwamazi hamwe nubuso (catalizator).Kugirango turusheho kunoza kuvanga bishobora kugerwaho, igishushanyo cya reakteri kirimo inleti ebyiri zifatika zahujwe na Y-ihuza mbere yo kwinjira mu gice cyo kuvanga.Ubwinjiriro bwa gatatu, bwambukiranya imigezi hagati yubuturo bwabwo, bukubiye muri gahunda yigihe kizaza cyinshi.
Imiyoboro yose ifite imiterere ya kare (nta mfuruka ya taper), nigisubizo cyigihe cyo gusya CNC ikoreshwa mugukora umuyoboro wa geometrie.Ibipimo byumuyoboro byatoranijwe kugirango bitange umusaruro mwinshi (kuri microreactor) umusaruro mwinshi, nyamara ntoya bihagije kugirango byorohereze imikoranire nubuso (catalizator) kumazi menshi arimo.Ingano ikwiye ishingiye kubunararibonye bwabanditsi hamwe nibikoresho byuma-byamazi.Ibipimo byimbere byumuyoboro wanyuma byari 750 µm x 750 µm naho reaktor yose hamwe yari ml 1.Umuhuza wubatswe (1/4 ″ -28 Urudodo rwa UNF) ushyizwe mubishushanyo mbonera kugirango habeho guhuza byoroshye ibikoresho nibikoresho bya chimie yubucuruzi.Ingano yumuyoboro igarukira kubunini bwibikoresho bya file, imiterere yubukanishi, hamwe nuburinganire bukoreshwa na ultrasonics.Ku bugari runaka kubintu byatanzwe, ibikoresho "bizunguruka" mumurongo wakozwe.Kugeza ubu nta moderi yihariye yo kubara, bityo ubugari ntarengwa bwumuyoboro kubintu byatanzwe hamwe nigishushanyo cyagenwe mubigeragezo, muribwo ubugari bwa 750 µm butazatera sag.
Imiterere (kare) yumuyoboro igenwa hakoreshejwe kare.Imiterere nubunini bwimiyoboro irashobora guhinduka kumashini ya CNC ukoresheje ibikoresho bitandukanye byo gukata kugirango ubone ibipimo bitandukanye nibiranga.Urugero rwo gukora umuyoboro uhetamye hamwe na 125 µm igikoresho urashobora kubisanga muri Monaghan45.Iyo fayeri ikoreshwa neza, ikoreshwa ryibikoresho bya fayili kumuyoboro bizaba bifite ubuso (kare).Muriyi mirimo, impande enye yakoreshejwe kugirango ibungabunge umuyoboro.
Mugihe cyo kuruhuka byateganijwe mubikorwa, ibyuma byubushyuhe bwa termocouple (ubwoko bwa K) byubatswe mubikoresho hagati yitsinda ryo hejuru no hepfo (Ishusho 1 - icyiciro 3).Izi thermocouples zirashobora kugenzura ihinduka ryubushyuhe kuva -200 kugeza 1350 ° C.
Igikorwa cyo gushira ibyuma bikorwa nihembe rya UAM ukoresheje icyuma cya 25.4 mm z'ubugari na microne 150 z'ubugari.Ibice bya file byahujwe murukurikirane rw'imirongo yegeranye kugirango ikingire ahantu hose hubatswe;ubunini bwibikoresho byabitswe ni binini kuruta ibicuruzwa byanyuma nkuko inzira yo gukuramo ikora imiterere yanyuma.Imashini ya CNC ikoreshwa mugukora imashini yimbere ninyuma yibikoresho, bikavamo kurangiza hejuru yibikoresho hamwe numuyoboro uhuye nigikoresho cyatoranijwe hamwe nibikoresho bya CNC (mururugero, hafi 1,6 µm Ra).Gukomeza, guhoraho kwa ultrasonic ibikoresho byo gutera no kuzenguruka bikoreshwa mugikorwa cyogukora ibikoresho kugirango harebwe niba ibipimo bifatika bikomeza kandi igice cyarangiye cyujuje urwego rwiza rwa CNC.Ubugari bwumuyoboro ukoreshwa kuri iki gikoresho ni nto bihagije kugirango umenye neza ko ibikoresho bya fayili “bidacogora” mu muyoboro w’amazi, bityo umuyoboro ufite igice cyambukiranya kare.Ibyuho bishoboka mubikoresho bya file hamwe nibipimo bya UAM byagenwe mubigeragezo numufatanyabikorwa (Fabrisonic LLC, USA).
Ubushakashatsi bwerekanye ko kuri interineti 46, 47 yikigo cya UAM habaho gukwirakwiza ibintu bike hatabayeho kongera ubushyuhe, bityo kubikoresho biri muriki gikorwa Cu-110 ikomeza kuba itandukanye na Al 6061 kandi ihinduka kuburyo bugaragara.
Shyiramo progaramu ya progaramu ya progaramu ya progaramu (BPR) kuri 250 psi (1724 kPa) kumanuka wa reaktor hanyuma uvoma amazi unyuze mumashanyarazi ku gipimo cya 0.1 kugeza kuri ml 1 min-1.Umuvuduko wa reakteri wakurikiranwe hifashishijwe transducer ya FlowSyn yubatswe muri sisitemu kugirango sisitemu ishobore gukomeza umuvuduko uhoraho.Ibishobora kuba ubushyuhe bwimyanya mumashanyarazi byapimwe mugushakisha itandukaniro riri hagati ya thermocouples yubatswe mumashanyarazi na thermocouples yubatswe mumasahani ashyushye ya chip ya FlowSyn.Ibi bigerwaho muguhindura ubushyuhe bwa porogaramu yashyizwe hagati ya 100 na 150 ° C mukwiyongera kwa 25 ° C no gukurikirana itandukaniro riri hagati yubushyuhe bwateganijwe kandi bwanditse.Ibi byagezweho hifashishijwe amakuru ya tc-08 (PicoTech, Cambridge, UK) hamwe na software ya PicoLog iherekeza.
Ibisabwa kugirango cycloaddition reaction ya fenylacetylene na iodoethane itezimbere (Scheme 1-Cycloaddition ya fenylacetylene na iodoethane, Scheme 1-Cycloaddition ya fenylacetylene na iodoethane).Uku gutezimbere kwakozwe hifashishijwe igishushanyo mbonera cyubushakashatsi (DOE), ukoresheje ubushyuhe nigihe cyo gutura nkibihinduka mugihe ukosora alkyne: igipimo cya azide kuri 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).Miliyoni 1.5 ya aliquot ya buri gisubizo yaravanze hanyuma ivanwa muri reaktor ku gipimo cyifuzwa n'ubushyuhe.Igisubizo cyicyitegererezo cyafashwe nkikigereranyo cyubuso bwibicuruzwa bya triazole nibikoresho byatangiye bya fenylacetylene kandi byemejwe hakoreshejwe chromatografiya ikora neza (HPLC).Kugirango isesengura rihamye, ibisubizo byose byafashwe ako kanya nyuma yo kuvanga reaction ivuye muri reaction.Ibipimo byatoranijwe kugirango bitezimbere bigaragara mu mbonerahamwe ya 2.
Ingero zose zasesenguwe hakoreshejwe sisitemu ya Chromaster HPLC (VWR, PA, USA) igizwe na pompe ya kane, ifuru yinkingi, impinduka ya UV yumurongo wa UV na autosampler.Inkingi yari ihwanye na 5 C18 (VWR, PA, Amerika), 4,6 x 100 mm, ingano ya 5 µm, ikomeza kuri 40 ° C.Umuti wari methanol ya gitewokarasi: amazi 50:50 kumuvuduko wa 1.5 ml · min-1.Ingano yatewe inshinge 5 μl naho uburebure bwa detector bwari 254 nm.Agace k'impinga ya% ya sample ya DOE yabazwe uhereye kumpinga yibisigisigi bya alkyne na triazole gusa.Kwinjiza ibikoresho byo gutangira bituma bishoboka kumenya impinga zijyanye.
Guhuza ibisubizo by'isesengura rya reaktor hamwe na software ya MODDE DOE (Umetrics, Malmö, Suwede) yemereye isesengura ryimbitse ryibisubizo no kugena uburyo bwiza bwo kwitwara kuri iyi cycloaddition.Gukoresha ibyubatswe neza no guhitamo amagambo yingenzi yicyitegererezo bituma habaho uburyo bwo kwitwara bugamije kwagura ubuso bwibicuruzwa mugihe hagabanijwe ubuso bwibiryo bya acetylene.
Oxidisation yubuso bwumuringa mubyumba bya catalitiki reaction yagezweho hifashishijwe igisubizo cya hydrogen peroxide (36%) inyura mucyumba cyitwaramo (umuvuduko wa 0.4 ml min-1, igihe cyo gutura = 2,5 min) mbere yo guhuza buri kigo cya triazole.isomero.
Bimaze kugenwa neza ko ibintu bimeze neza, byakoreshwaga ku nkomoko ya acetylene na haloalkane kugira ngo yemererwe gukusanya isomero rito rya synthesis, bityo hashyizweho uburyo bwo gukoresha ibi bintu ku buryo bwagutse bushobora kugaragara (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).Aliquots ya ml 3 ya buri gisubizo yaravanze hanyuma ivomerwa muri reaction ku gipimo cya 75 µl / min n'ubushyuhe bwa 150 ° C.Ingano yose yakusanyirijwe muri vial hanyuma ivangwa na ml 10 ya Ethyl acetate.Igisubizo cyicyitegererezo cyogejwe hamwe na 3 x 10 ml yamazi.Ibice by'amazi byahujwe hanyuma bivanwamo ml 10 ya Ethyl acetate, hanyuma ibice kama kama birahuzwa, byogejwe na brine ya 3 × 10, byumishwa hejuru ya MgSO 4 hanyuma birayungurura, hanyuma umusemburo ukurwa muri vacuo.Ingero zahanaguwe na silika gel inkingi ya chromatografi ikoresheje Ethyl acetate mbere yisesengura ryakozwe na HPLC, 1H NMR, 13C NMR hamwe na misa nini cyane (HR-MS).
Ibyerekanwe byose byabonetse hakoreshejwe Thermofischer Precision Orbitrap mass spectrometer hamwe na ESI nkisoko ya ionisation.Ingero zose zateguwe hifashishijwe acetonitrile nka solvent.
Isesengura rya TLC ryakorewe ku isahani ya silika hamwe na substrate ya aluminium.Isahani yagaragajwe nu mucyo wa UV (254 nm) cyangwa vanillin irangi no gushyushya.
Ingero zose zasesenguwe hakoreshejwe sisitemu ya Chromaster ya VWR (VWR International Ltd, Leighton Buzzard, UK) ifite moteri ya autosampler, pompe ya binary ifite itanura ryinkingi hamwe nicyuma kimwe cyerekana uburebure.Hifashishijwe inkingi ya ACE 5 C18 (150 x 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.Uburebure bwumurongo wa detector ni 254 nm.
Agace k'impinga ya% y'icyitegererezo yabazwe uhereye ku mpinga ya alkyne isigaye, ibicuruzwa bya triazole gusa, kandi kwinjiza ibikoresho byatangiye byatumye bishoboka kumenya impinga zihuye.
Ingero zose zasesenguwe hakoreshejwe Thermo iCAP 6000 ICP-OES.Ibipimo byose bya kalibrasi byateguwe hifashishijwe 1000 ppm Cu igisubizo gisanzwe muri acide ya nitric 2% (SPEX Certi Prep).Ibipimo byose byateguwe mugisubizo cya 5% DMF na 2% HNO3, kandi ibyitegererezo byose byavomwe inshuro 20 hamwe nicyitegererezo cya DMF-HNO3.
UAM ikoresha ibyuma byo gusudira ultrasonic nkuburyo bwo guhuza icyuma gikoreshwa mugukora inteko yanyuma.Gusudira ibyuma bya Ultrasonic bifashisha igikoresho cyinyeganyeza (cyitwa ihembe cyangwa ihembe rya ultrasonic) kugirango ushire igitutu kuri file / mbere yahujwe kugirango uhuze / mbere uhujwe no kunyeganyeza ibikoresho.Kubikorwa bikomeza, sonotrode ifite ishusho ya silindrike kandi izunguruka hejuru yibikoresho, ifata ahantu hose.Iyo hashyizweho igitutu no kunyeganyega, okiside hejuru yibikoresho irashobora gucika.Umuvuduko uhoraho hamwe no kunyeganyega birashobora gutuma habaho gusenya ububi bwibintu 36.Guhuza hafi nubushyuhe bwaho hamwe nigitutu noneho biganisha kumurongo ukomeye uhuza ibintu bifatika;irashobora kandi guteza imbere ubumwe muguhindura ingufu zubutaka48.Imiterere yuburyo bwo guhuza itsinze byinshi mubibazo bifitanye isano nubushyuhe bwimiterere ihindagurika hamwe ningaruka zubushyuhe bwo hejuru buvugwa mubindi buhanga bwinganda ziyongera.Ibi biremera guhuza bitaziguye (nukuvuga nta guhindura isura, kuzuza cyangwa gufatira) ibice byinshi byibikoresho bitandukanye muburyo bumwe.
Ikintu cya kabiri cyiza kuri CAM ni urwego rwo hejuru rwamazi ya plastike agaragara mubikoresho byuma ndetse no mubushyuhe buke, ni ukuvuga munsi yumushonga wibikoresho byuma.Gukomatanya kwinyeganyeza ultrasonic hamwe nigitutu bitera urwego rwo hejuru rwimipaka yimipaka yimuka no kongera kwisubiramo nta bushyuhe bugaragara bwiyongereye busanzwe bujyanye nibikoresho byinshi.Mugihe cyo kurema inteko yanyuma, iki kintu gishobora gukoreshwa mugushiramo ibintu bikora kandi byoroshye hagati yicyuma cya fayili, umurongo ku kindi.Ibintu nka fibre optique 49, gushimangira 46, ibikoresho bya elegitoroniki 50 hamwe na thermocouples (iki gikorwa) byinjijwe neza muburyo bwa UAM kugirango habeho inteko ikora kandi yoroheje.
Muri iki gikorwa, ubushobozi butandukanye bwo guhuza hamwe nubushobozi bwa UAM bwakoreshejwe mugukora microreactor nziza yo kugenzura ubushyuhe bwa catalitiki.
Ugereranije na palladium (Pd) hamwe nizindi zikoreshwa cyane mubyuma byuma, Cu catalizike ifite ibyiza byinshi: (i) Mu bukungu, Cu ihendutse kuruta ibindi byuma byinshi bikoreshwa muri catalizike bityo rero bikaba ari uburyo bushimishije mu nganda z’imiti (ii) intera ya Cu-catalizike ihuza imipaka iraguka kandi bigaragara ko hari bimwe byuzuzanya na Pd51, 52, 53 zishingiye ku bikorwa bya ligand.Iyi ligande akenshi iba yubatswe muburyo bworoshye kandi buhendutse.niba ubyifuza, mugihe ikoreshwa muri chimie ya Pd akenshi iba igoye, ihenze, kandi yunvikana ikirere (iv) Cu, cyane cyane izwiho ubushobozi bwo guhuza alkine muri synthesis, nka bimetallic ya Sonogashira ya catisale hamwe na cycloaddition hamwe na azide (kanda chimie) (v) Cu irashobora kandi guteza imbere arylation ya nucleophile muburyo bwa Ullmann.
Vuba aha, ingero za heterogenisation yibi bitekerezo byose imbere ya Cu (0) zerekanwe.Ibi ahanini biterwa ninganda zimiti no kwiyongera kwibanda mugusubirana no gukoresha ibyuma bitanga ibyuma 55,56.
1,3-dipolar cycloaddition reaction hagati ya acetylene na azide kugeza kuri 1,2,3-triazole, yatanzwe bwa mbere na Huisgen mumwaka wa 1960s57, ifatwa nkigikorwa cyo kwerekana icyerekezo.Ibice bivamo 1,2,3 bya triazole birashimishije cyane nka farumasi muguvumbura ibiyobyabwenge bitewe nibinyabuzima byabo ndetse no gukoresha muburyo butandukanye bwo kuvura 58.
Iki gisubizo cyongeye kwitabwaho mugihe Sharpless nabandi batangije igitekerezo cya "kanda chimie" 59.Ijambo "kanda chimie" rikoreshwa mugusobanura ibintu bikomeye kandi byatoranijwe byerekana uburyo bwo guhuza byihuse ibice bishya hamwe nububiko bwibitabo bukomatanya ukoresheje heteroatomic bonding (CXC) 60.Ubuvanganzo ngengabihe bwibisubizo biterwa numusaruro mwinshi ujyanye nabo.ibintu biroroshye, kurwanya ogisijeni namazi, kandi gutandukanya ibicuruzwa biroroshye61.
Ibisanzwe 1,3-dipole Huisgen cycloaddition ntabwo iri mubyiciro "kanda chimie".Nyamara, Medal na Sharpless berekanye ko iki gikorwa cyo guhuza azide-alkyne kibaho 107-108 imbere ya Cu (I) ugereranije nihuta ryinshi ryikigereranyo cya catalitike 1,3-dipolar cycloaddition 62,63.Ubu buryo bwateye imbere ntabwo busaba kurinda amatsinda cyangwa imiterere ikaze kandi itanga ihinduka ryuzuye hamwe no guhitamo 1,4,3-triazoles (anti-1,2,3-triazoles) mugihe (Ishusho 3).
Isometric ibisubizo byibisanzwe hamwe numuringa-catisale Huisgen cycloadditions.Cu (I) -yasesenguye cycloadditions ya Huisgen itanga 1,4-idasubirwaho 1,2,3-triazole, mugihe cycloadditions ya Huisgen yatewe nubushuhe mubisanzwe itanga 1,4- na 1.5-triazole ivanze na 1: 1 ya azole stereoisomers.
Porotokole nyinshi zirimo kugabanya amasoko ahamye ya Cu (II), nko kugabanya CuSO4 cyangwa Cu (II) / Cu (0) ifatanije numunyu wa sodium.Ugereranije nibindi byuma byatangije reaction, gukoresha Cu (I) bifite ibyiza byingenzi byo kuba bihendutse kandi byoroshye kubyitwaramo.
Inyigisho za Kinetic na isotopic na Worrell n'abandi.65 berekanye ko kubijyanye na alkynes ya terminal, ibice bibiri bingana n'umuringa bigira uruhare mugukora reaction ya buri molekile kubijyanye na azide.Uburyo buteganijwe butambuka binyuze mu mpeta esheshatu z'icyuma z'umuringa zakozwe no guhuza azide na σ-ihuza umuringa acetylide hamwe na π-umuringa uhuza nkumuterankunga uhamye.Ibikomoka ku muringa triazolyl bikozwe biturutse ku kugabanuka kwimpeta bikurikirwa no kubora kwa proton kugirango bibe ibicuruzwa bya triazole no gufunga uruziga rwa catalitiki.
Mugihe ibyiza byibikoresho bya chimie bitemba byanditse neza, habaye icyifuzo cyo kwinjiza ibikoresho byisesengura muri sisitemu yo kugenzura ibikorwa nyabyo mugihe cya 66,67.UAM yerekanye ko ari uburyo bukwiye bwo gushushanya no gukora reakteri ya 3D igoye cyane ituruka ku bikorwa bya catalitiki, ibikoresho bitwara amashyuza hamwe nibintu byinjira byinjira (Ishusho 4).
Imashini ya aluminium-umuringa yakozwe na ultrasonic yongeyeho inganda (UAM) ifite imiterere yimbere yimbere, yubatswe muri thermocouples hamwe nicyumba cya reaction ya catalitiki.Kugirango ugaragaze inzira yimbere yimbere, prototype ibonerana yakozwe hakoreshejwe stereolithography nayo irerekanwa.
Kugirango reakteri ikorwe kugirango habeho reaction kama, ibishishwa bigomba gushyuha neza hejuru yabyo;ni igitutu n'ubushyuhe byapimwe.Igeragezwa ryumuvuduko ryerekanaga ko sisitemu ikomeza umuvuduko uhamye kandi uhoraho nubwo haba hari umuvuduko mwinshi muri sisitemu (1.7 MPa).Ibizamini bya Hydrostatike byakorewe mubushyuhe bwicyumba hakoreshejwe H2O nkamazi.
Guhuza ibyubatswe (Ishusho 1) thermocouple hamwe nubushyuhe bwamakuru yerekana ubushyuhe bwerekanye ko ubushyuhe bwa termocouple bwari 6 ° C (± 1 ° C) munsi yubushyuhe bwateganijwe muri sisitemu ya FlowSyn.Mubisanzwe, ubwiyongere bwa 10 ° C bwikubye kabiri igipimo cyibisubizo, bityo itandukaniro ryubushyuhe bwa dogere nkeya gusa rishobora guhindura igipimo cyibisubizo.Iri tandukaniro riterwa no gutakaza ubushyuhe muri RPV kubera gukwirakwiza ubushyuhe bwinshi bwibikoresho bikoreshwa mubikorwa byo gukora.Uku gutwarwa nubushyuhe burigihe kandi birashobora kwitabwaho mugihe washyizeho ibikoresho kugirango ubushyuhe nyabwo bugerweho kandi bupimwe mugihe cya reaction.Rero, iki gikoresho cyo kugenzura kumurongo cyorohereza kugenzura neza ubushyuhe bwimikorere kandi bigira uruhare muburyo bunoze bwo gutezimbere no guteza imbere ibihe byiza.Izi sensor zirashobora kandi gukoreshwa mugutahura reaction zidasanzwe no gukumira guhunga muri sisitemu nini.
Imashini itangwa muriyi mpapuro ni urugero rwambere 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) Kunesha ibibazo byagaragaye bijyanye no gutunganya umuringa cyangwa aluminiyumu (ii) byanonosoye imiyoboro y’imbere imbere ugereranije n’ubushyuhe bwo gutembagaza (PBF) uburyo bworoshye bwo gutunganya ibishishwa (SLM) 25,69 Po. birashoboka muburyo bwa tekinoroji yuburiri, (v) kunesha imiterere yubukanishi no kwiyumvisha ibintu bishingiye kuri polymer kubintu bitandukanye bisanzwe byangiza 17,19.
Imikorere ya reakteri yerekanwe nuruhererekane rwumuringa-catisale alkinazide cycloaddition reaction mugihe gikomeza gutemba (Ishusho 2).Ultrasonic yacapishijwe umuringa reakteri yerekanwe mugitabo.4 yahujwe na sisitemu yubucuruzi kandi ikoreshwa mugushushanya isomero rya azide ya 1,4-itagabanijwe 1,2,3-triazoles ikoresheje ubushyuhe bugenzurwa nubushyuhe bwa acetylene na alkyl gride halide imbere ya sodium chloride (Ishusho 3).Gukoresha uburyo buhoraho bwo gutemba bigabanya ibibazo byumutekano bishobora kuvuka mubikorwa, kubera ko iki gisubizo gitanga umuhuza wa azide wangiza cyane kandi uteje akaga [317], [318].Ku ikubitiro, reaction yariyongereye kugirango cycloaddition ya fenylacetylene na iodoethane (Scheme 1 - Cycloaddition ya fenylacetylene na iodoethane) (reba Ishusho 5).
.
Mugucunga igihe cyo gutura mumashanyarazi mugice cya catalitiki ya reaktor no kugenzura neza ubushyuhe bwimikorere hamwe na sensor ya thermocouple sensor, imiterere yimyitwarire irashobora kwihuta kandi neza neza hamwe nigihe gito nibikoresho.Byagaragaye vuba ko ihinduka ryinshi ryagezweho hakoreshejwe igihe cyo gutura cyiminota 15 nubushyuhe bwa reaction ya 150 ° C.Birashobora kugaragara uhereye kuri coefficient ya software ya MODDE ko igihe cyo gutura hamwe nubushyuhe bwa reaction bifatwa nkibintu byingenzi byurugero.Gukoresha ibyubatswe byubaka ukoresheje ibi bintu byatoranijwe bituma habaho uburyo bwo kubyitwaramo bwagenewe kugwiza ibicuruzwa ahantu hahanamye mugihe hagabanijwe gutangira ibintu byo hejuru.Uku gutezimbere byatanze ihinduka rya 53% ryibicuruzwa bya triazole, bihuye neza nicyitegererezo cya 54%.