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Mubasa iri, tinoshuma muenzaniso wekutanga weiyo inoyerera reactor yakaumbwa neiyo solid-state metal sheet lamination technique Ultrasonic Additive Manufacturing (UAM) ine yakanyatso kubatanidzwa zvikamu zvinokonzeresa uye zvinonzwa zvinhu. yakakosha 1,4-disubstituted 1,2,3-triazole makomisheni akagadzirwa zvakabudirira uye akagadziridzwa neCu-mediated Huisgen 1,3-dipolar cycloaddition reaction uchishandisa UAM chemistry set-up.Nekusimudzira iyo yakasarudzika zvivakwa zveUAM uye kuenderera kuyerera kwekugadzirisa, mudziyo unokwanisa kukonzeresa yekutarisa inoenderera mhinduro uye inoenderera.
Pamusana pekubatsira kwayo kwakakosha pamusoro pemuenzanisi wayo wakawanda, kuyerera kwemakemikari inzvimbo inokosha uye inokura mune zvose zvidzidzo zvedzidzo uye zvemaindasitiri nekuda kwekukwanisa kwayo kuwedzera kusarudzwa uye kushanda kwemakemikari synthesis.Izvi zvinowedzera kubva nyore nyore organic molecule formation1 kusvika kune mishonga yemishonga2,3 uye zvigadzirwa zvepanyama4,5,6.Kupfuura 50% yezvinoitika mumakemikari akanaka uye maindasitiri emishonga anogona kubatsirwa nekushandiswa kwekuenderera mberi kwekuyerera kwe7.
Mumakore achangopfuura, kwave nekukura kwemaitiro emapoka ari kutsvaga kutsiva zvechinyakare glassware kana kuyerera chemistry midziyo ine customizable additive kugadzira (AM) chemistry "reaction vessels"8.The iterative design, kukurumidza kugadzirwa, uye 3-dimensional (3D) kugona kwemaitiro aya anobatsira kune avo vanoda kugadzirisa midziyo yavo kune imwe seti yemaitiro, date, kana mashandisirwo emhando yepolyD-based based on this workedly-based based. kudhinda matekiniki akadai sterolithography (SL)9,10,11, fused deposition modeling (FDM)8,12,13,14 uye inkjet kudhinda 7, 15, 16. Kushaikwa kwekusimba uye kugona kwemichina yakadaro kuita zvakasiyana-siyana zvemakemikari reactions/analyses17, 18,18,801001900019000019. 19, 20 .
Nekuda kwekuwedzera kwekushandiswa kwekemikari inoyerera uye zvinhu zvakanaka zvine chekuita neAM, panoda kuwongorora nzira dzepamusoro dzinogonesa vashandisi kugadzira midziyo yekuyerera ine kemikari yakagadziridzwa uye yekuongorora maitiro.Idzi nzira dzinofanirwa kuita kuti vashandisi vasarudze kubva kune dzakasimba zvakanyanya kana dzinoshanda zvinhu zvinokwanisa kubata kwakasiyana-siyana mamiriro ekuita, ukuwo kufambisa nzira dzakasiyana-siyana dzekuongorora kudzora zvinobuda kubva pachigadzirwa.
Imwe nzira yekuwedzera yekugadzira iyo ine mukana wekugadzira tsika yemakemikari reactors ndeye Ultrasonic Additive Manufacturing (UAM) .Iyi yakasimba-state sheet lamination technique inoshandisa ultrasonic oscillations kune yakaonda simbi foil kuitira kuti vabatanidze pamwe chete layer by layer ine shoma yakawanda yekupisa uye high degree of plastic flow 21 , 22 , 23 .Kusiyana nemamwe mahybride anonyanya kuzivikanwa AM anonyanya kuzivikanwa neAM technologies anonyatsozivikanwa seAM technologies, anonyanya kuzivikanwa neAM muitiro, umo in-situ periodic computer numberal control (CNC) milling kana laser machining inotsanangura mambure echimiro chechikamu chakasungirirwa zvinhu 24, 25.Izvi zvinoreva kuti mushandisi haaganhurirwe nezvinetso zvine chekuita nekubvisa zvakasara zvekuvaka zvigadziriso kubva kune madiki emvura migero, izvo zvinowanzoitika nehupfu uye mvura yemvura AM system26,27,28. kusanganiswa kwezvinhu muchikamu chimwe chete.Kusarudzwa kwezvinhu zvakasanganiswa kunze kwekunyunguduka kunoreva kuti iyo mechanical uye makemikari zvinoda zvezvikumbiro zvakananga zvinogona kusangana zviri nani.Kuwedzera kune yakasimba state bonding, chimwe chiitiko chinosangana panguva ye ultrasonic bonding ndeyekuyerera kwepamusoro kwezvinhu zvepurasitiki pakudzika kwakadzika29,30,31,32,33.Ichi chinhu chakasiyana-siyana cheUAM chinogona kufambisa embedded metal layer. kuendeswa kweruzivo rwenguva-chaiyo kubva kuchishandiso kuenda kumushandisi kuburikidza neakasanganiswa analytics.
Basa revanyori rekare32 rakaratidza kukwanisa kweUAM maitiro ekugadzira metallic 3D microfluidic zvivako zvine maitiro akabatanidzwa ekunzwa.Iyi inyanzvi yekuongorora chete.Iri pepa rinopa muenzaniso wekutanga we microfluidic chemical reactor yakagadzirwa neUAM;chigadzirwa chinoshanda chisingatarisi chete asiwo chinokonzera kushandiswa kwemakemikari kuburikidza nekugadzirisa zvakagadziriswa zvinogadzirisa zvinhu.Chigadzirwa chacho chinobatanidza zvikomborero zvakawanda zvinosanganiswa neUAM teknolojia mukugadzirwa kwemakemikari e3D, zvakadai se: kukwanisa kushandura yakazara 3D magadzirirwo zvakananga kubva pakombiyuta-aid dhizaini (CAD) mienzaniso muzvigadzirwa;multi-material kugadzirwa kusanganisa yakakwira yekupisa conductivity uye catalytic zvinhu;Kuratidza kushanda kwe reactor, raibhurari yemishonga yakakosha 1,4-disubstituted 1,2,3-triazole compounds yakagadzirwa nemhangura-catalyzed Huisgen 1,3-dipolar dhizaini yesainzi inovhura nzira itsva yesainzi. mikana uye mikana yemakemikari kuburikidza nekutsvakurudza kwakasiyana-siyana.
Zvese zvinonyungudutsa uye reagents zvakatengwa kubva kuSigma-Aldrich, Alfa Aesar, TCI kana Fischer Scientific uye zvakashandiswa pasina kucheneswa zvisati zvaitika.1H uye 13C NMR spectra yakanyorwa pa400 MHz uye 100 MHz, zvichiteerana, yakawanikwa pachishandiswa JEOL ECS-400 400 400 MHz spectromita 400 MHz kana 400 MHz CD spectra l3 kana (CD3)2SO as solvent.Maitirwo ese akaitwa pachishandiswa Uniqsis FlowSyn flow chemistry platform.
UAM yakashandiswa kugadzira midziyo yese muchidzidzo ichi.Tekinoroji yakagadzirwa muna 1999, uye ruzivo rwayo rwehunyanzvi, mashandiro eparameters uye mafambisirwo kubva payakagadzirwa ichigona kudzidzwa kuburikidza neanotevera akadhindwa zvinhu34,35,36,37.Mudziyo (Mufananidzo 1) wakashandiswa pachishandiswa simba repamusoro-soro, 9kW SonicLayer UAM 4000 inoyerera yeU.SA. mudziyo waiva Cu-110 uye Al 6061.Cu-110 ine yakakwirira mhangura kugutsikana (zvishoma 99.9% mhangura), zvichiita mukwikwidzi akanaka nokuda kwemhangura-catalyzed reactions, uye saka rinoshandiswa se "inoshanda layer mukati microreactor.Al 6061 O inoshandiswa se "zvizhinji" zvinhu, zvakare Embedding layer inoshandiswa pakuongorora;Alloy anobatsira chikamu embedding uye annealed mamiriro akasanganiswa neCu-110 layer.Al 6061 O inyaya yakaratidzwa kuti inonyatsoenderana neUAM maitiro38, 39, 40, 41 uye yakaedzwa uye yakawanikwa Kemikari yakagadzikana nemareagents anoshandiswa mubasa iri.Musanganiswa weAl 6061 O neCu-110 unoonekwawo semusanganiswa wezvinhu unoenderana neUAM uye naizvozvo chinhu chakakodzera pachidzidzo ichi.38,42 Midziyo iyi yakanyorwa muTable 1 pazasi.
Matanho ekugadzira Reactor (1) Al 6061 substrate (2) Kugadzirwa kwechiteshi chepasi chakasetwa kufoiri yemhangura (3) Kuiswa kwe thermocouples pakati pema layer (4) Top chiteshi (5) Inlet uye outlet (6) Monolithic reactor.
Ihwo huzivi hwekugadzira nzira yemvura ndeyekushandisa nzira yakasvibiswa kuti iwedzere kureba kwemvura inofamba mukati me chip, uchichengetedza chip pahukuru hunogoneka.Kuwedzera kwechinhambwe kunodiwa kuti kuwedzere nguva yekubatanidza catalyst / reagent uye kupa zvibereko zvakanakisa zvechigadzirwa.Machipisi anoshandisa 90 ° bends pamagumo enzira yakananga kuti aite kuti iwedzere kusvibiswa kwepamusoro-soro yemvura inoputika (Kuti iwedzere kusvibiswa kwepamusoro-soro nekuwedzera kusanganiswa kwemvura4cataly) iyo inosanganiswa inogona kuwanikwa, dhizaini yekugadzira inoratidzira maviri reagent inlets akabatanidzwa paY-junction asati apinda muchikamu chekusanganiswa kwenyoka.Ikoni yechitatu, iyo inopindirana nehova pakati pekugara kwayo, inosanganiswa mukugadzirwa kwemangwana multistep reaction syntheses.
All channels ane square profile (hapana draft angles), mhedzisiro ye periodic CNC milling yakashandiswa kugadzira chiteshi geometry.The channel dimensions inosarudzwa kuti ive nechokwadi chepamusoro (ye microreactor) vhoriyamu kubuda, uku iri diki zvakakwana kuti ifambise kupindirana kwepasi (catalysts) yezvizhinji zvezvinwiwa zvirimo.Saizi yakakodzera inoenderana nevanyori' yapfuura ruzivo rwemetal-fluidic yemukati 7 dhizaini yemukati x7 maitiro ekupedzisira e-metal-fluidic. 750 µm uye vhoriyamu yakazara reactor yaive 1 ml.Chibatanidza chinosanganiswa (1/4″-28 UNF thread) chinosanganisirwa mukugadzira kuti zvibvumire kupindirana kuri nyore kwemudziyo nekutengesa kuyerera kwekemikisi michina.Saizi yechiteshi inoganhurwa nehupamhi hweiyo foil zvinhu, zvimiro zvayo zvemuchina, uye mapeji ekubatanidza anoshandiswa ne ultrasonics.Pane imwe hupamhi hwechinhu chakapihwa, izvo zvinhu zvino "sag" mugwara rakagadzirwa.Parizvino hapana chaiyo modhi yekuverenga uku, saka iyo yakakura chiteshi upamhi hwechinhu chakapihwa uye dhizaini inotemerwa kuyedza;mune iyi kesi, hupamhi hwe750 μm hahuzokonzeri sag.
Chimiro (square) chechiteshi chinotarirwa nekushandisa square cutter.Chimiro uye ukuru hwemigero inogona kuchinjwa nemichina yeCNC uchishandisa maturusi akasiyana-siyana ekucheka kuti awane kuyerera kwakasiyana-siyana uye maitiro.Muenzaniso wekugadzira curved shape channel uchishandisa 125 μm tool inogona kuwanikwa mubasa reMonaghan45.Kana iyo foil layer inoiswa pamusoro pegwara remafashioni (In the flat channel). basa, kuitira kuchengetedza symmetry yemugero, mutsara wekona wakashandiswa.
Panguva yekumbomira yakagara yarongwa mukugadzirwa, thermocouple tembiricha probes (Rudzi K) dzakaiswa zvakananga mukati memudziyo pakati pemapoka epamusoro neakadzika chiteshi (Mufananidzo 1 - Nhanho 3) .Idzi thermocouples dzinogona kutarisa kushanduka kwekushisa kubva -200 kusvika 1350 °C.
Iyo metal deposition process inoitwa nerunyanga rweUAM uchishandisa 25.4 mm yakafara, 150 micron gobvu simbi foil. Aya mapepa efoiri anosungirirwa mumutsara wemitsetse yakatarisana kuvhara nzvimbo yese yekuvaka;ukuru hwezvinhu zvakaiswa zvakakura kudarika chigadzirwa chekupedzisira sezvo nzira yekubvisa inobudisa chimiro chekupedzisira chemumbure.CNC machining inoshandiswa kugadzira michina yekunze uye yemukati yezvigadzirwa, zvichiita kuti pave nepamusoro pezvigadzirwa nematanho akaenzana nechishandiso chakasarudzwa uye CNC process parameters (inenge 1.6 μm Ra mumuenzaniso uyu) kurongeka kunochengetedzwa uye chikamu chakapedzwa chichasangana neCNC kupedza milling accuracy levels.Kufara kwegwara rinoshandiswa pamudziyo uyu idiki zvakakwana kuti ive nechokwadi chekuti foil haina "sag" mugero remvura, saka chiteshi chinochengetedza square cross-section.Possible gaps in foil material uye UAM process parameters dzakatemerwa experimentally neanogadzira partner (Fabrisonic LLC, USA).
Zvidzidzo zvakaratidza kuti diki elemental diffusion inoitika paUAM bonding interface 46, 47 pasina kuwedzera kupisa kwekupisa, saka kune zvishandiso zviri mubasa iri, Cu-110 layer inoramba yakasiyana neAl 6061 layer uye inoshanduka kamwe kamwe.
Isa pre-calibrated 250 psi (1724 kPa) back pressure regulator (BPR) kusvika pakubuda kwe reactor uye pombi mvura kuburikidza nereactor pachiyero che 0.1 kusvika 1 mL min-1. The reactor pressure yakatariswa uchishandisa FlowSyn yakavakirwa-mukati system pressure sensor kuti ione kuti iyo system inogona kuchengetedza inoramba ichiyerera inoyerera tembiricha inoyerera inoramba ichiyerera tembiricha inoyerera neyakagadzika tembiricha inoyerera. rmocouples akaiswa mukati me reactor uye ayo akaiswa mukati meFlowSyn chip heat plate.Izvi zvinowanikwa nekusiyanisa tembiricha yehotplate inorongwa pakati pe100 ne150 °C mu25 °C increments uye nekucherechedza chero misiyano pakati petembiricha dzakarongwa uye dzakarekodwa.
Iyo cycloaddition reaction conditions ye phenylacetylene uye iodoethane yakagadziridzwa (Scheme 1- Cycloaddition ye phenylacetylene uye iodoethane Scheme 1- Cycloaddition ye phenylacetylene uye iodoethane) .Iyi optimization yakaitwa neakazara factorial dhizaini yezviedzo (DOE uye reside reshiyo reshiyo) pachishandiswa tembiricha dhizaini yekuyedza (DOE) uye reside reshiyo reshiyo yekuongorora (DOE) 1:2.
Separate solutions of sodium azide (0.25 M, 4:1 DMF:H2O), iodoethane (0.25 M, DMF), uye phenylacetylene (0.125 M, DMF) zvakagadzirirwa.A 1.5 mL aliquot yemhinduro yega yega yakasanganiswa uye yakapombwa kuburikidza nereactor painoda kuyerera kwechiyero uye tembiricha seye triace yemhando yepezole inotangira mhinduro yakatorwa. by high performance liquid chromatography (HPLC) .Nokuda kwekuenderana kwekuongorora, maitiro ose akatorwa sampuli mushure mokunge musanganiswa wekuita wasiya reactor.Maparameter akasarudzwa kuti agadzirise anoratidzwa muTable 2.
Masampuli ese akaongororwa pachishandiswa Chromaster HPLC system (VWR, PA, USA) ine quaternary pombi, column oven, variable wavelength UV detector uye autosampler. The column was an Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 × 100 mm muhukuru, 5 µx 500 ° C muhukuru, 5 µd isocra m. 50 methanol: mvura pamwero wekuyerera we 1.5 mL.min-1.Ijection volume yaiva 5 µL uye detector wavelength yaiva 254 nm. The % peak area for the DOE sample yakaverengwa kubva kunzvimbo dzepamusoro dzezvakasara zvealkyne uye triazole zvigadzirwa chete.Jekiseni yechinhu chekutanga chepamusoro inobvumira kupinza kwekutanga.
Kubatanidza reyakita yekuongorora inobuda kuMODE DOE software (Umetrics, Malmö, Sweden) yakabvumira kunyatsoongororwa kwemaitiro emigumisiro uye kutsunga kwemamiriro ekugadzirisa maitiro eiyi cycloaddition.Kushandisa iyo yakagadzirwa-in optimizer uye kusarudza mazwi ose anokosha emuenzaniso unobereka seti yemaitiro ekugadzirisa akagadzirirwa kuwedzera chigadzirwa nzvimbo yepamusoro-soro apo kuderedza nzvimbo yepamusoro yechinhu chekutanga.
Iyo oxidation yemhangura yepamusoro mukati meiyo catalytic reaction chamber yakawanikwa pachishandiswa mhinduro yehydrogen peroxide (36%) inoyerera nemukamuri yekupindura (yekuyerera = 0.4 mL min-1, nguva yekugara = 2.5 min) isati yaitwa yeimwe neimwe triazole compound library.
Kana imwe nguva yakanyatsogadziriswa yemamiriro ezvinhu yakaonekwa, yakashandiswa kune zvakasiyana-siyana zveacetylene uye haloalkane derivatives kuti zvibvumire kuumbwa kweibhurari duku synthesis, nokudaro kusimbisa kukwanisa kushandisa mamiriro aya kune huwandu hwakawanda hwezvinogona kuita reagents (Mufananidzo 1) .2).
Gadzirira mhinduro dzakasiyana dze sodium azide (0.25 M, 4: 1 DMF:H2O), haloalkanes (0.25 M, DMF) uye alkynes (0.125 M, DMF) 3 mL aliquots yemhinduro yega yega yakasanganiswa uye kupomba kuburikidza ne reactor pa 75 µL.min-1 uye 150 °C yakanyungudutswa muhuwandu hwe vicel vhoriyamu ye150 °C. .Mushonga wemuenzaniso wakashambidzwa ne 3 × 10 mL yemvura. Zvikamu zvemvura zvakasanganiswa uye zvakabviswa ne 10 mL ye ethyl acetate;iyo organic layers yakabva yasanganiswa, yakashambidzwa ne 3 x 10 mL yebrine, yakaomeswa pamusoro peMgSO4 uye yakasefa, ipapo solvent yakabviswa mu vacuo.Masampuli akacheneswa ne column chromatography pa silica gel uchishandisa ethyl acetate isati yaongororwa nekubatanidzwa kweHPLC, 1H NMR, 13C HRH mass-NMR (high resolution mass NMR).
Maonero ose akawanikwa achishandisa Thermofischer precision Orbitrap resolution mass spectrometer neESI seyo ionization source.Sampuli dzose dzakagadzirirwa kushandisa acetonitrile se solvent.
TLC kuongororwa kwakaitwa paaluminium-backed silica plates.Plates dzakaonekwa neUV chiedza (254 nm) kana vanillin staining uye kupisa.
Mienzaniso yese yakaongororwa pachishandiswa VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) system ine autosampler, column oven binary pump and single wavelength detector.Ikolamu yakashandiswa yaiva ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Ltd,Scotland Aberones).
Majekiseni (5 µL) akagadzirwa zvakananga kubva ku diluted crude reaction musanganiswa (1:10 dilution) uye akaongororwa nemvura: methanol (50:50 kana 70:30), kunze kwemamwe masampuli anoshandisa 70:30 solvent system (inoratidzirwa senhamba yenyeredzi) pachiyero chekuyerera che 1.5 mL C / 2m th detect pa 4 ° 2m th detect. .
Iyo % peak nzvimbo yemuenzaniso yakaverengerwa kubva pakakwirira nzvimbo yeyakasara alkyne, chete chigadzirwa che triazole, uye jekiseni rechinhu chekutanga chakabvumira kuzivikanwa kwepamusoro akakodzera.
Mienzaniso yose yakaongororwa uchishandisa Thermo iCAP 6000 ICP-OES. Zvose zviyero zvekugadzirisa zvakagadzirirwa uchishandisa 1000 ppm Cu standard solution mu 2% nitric acid (SPEX Certi Prep) . Zvose zvakagadzirirwa mu 5% DMF uye 2% HNO3 mhinduro, uye sampuli dzose dzakaderedzwa sampuli DMF 20-H NO3.
UAM inoshandisa ultrasonic metal welding senzira yekubatanidza yesimbi foil material inoshandiswa kuvaka gungano rekupedzisira.Ultrasonic metal welding utilize a vibrating metal tool (inonzi nyanga kana ultrasonic horn) kuisa kumanikidza kune foil layer/yaimbova yakasanganiswa layer kuti isungirwe uku ichibvunda zvinhu. Kana kudzvinyirirwa uye kudengenyeka kunoshandiswa, maokisidhi ari pamusoro pezvinhu zvinogona kuputika.Kuenderera mberi kumanikidziro uye kudengenyeka kunogona kukonzera asperities yezvinhu zviputse 36 .Kubatana kwepedyo nekupisa kunokonzerwa nenharaunda uye kudzvinyirira zvino kunotungamirira kuhutano hwakasimba-nyika kusungirirwa pane zvinhu zvinosangana;inogonawo kubatsira kunamatira kuburikidza nekuchinja kwepamusoro pesimba48.Mamiriro ekugadzirisa maitiro anokunda matambudziko akawanda anokonzerwa nekushanduka kwekushisa kwekunyunguduka uye kupisa kwepamusoro mushure memigumisiro yakataurwa mune mamwe maitiro ekugadzira ekuwedzera.Izvi zvinobvumira kusungirirwa kwakananga (kureva, pasina kugadziriswa kwepamusoro, kuzadza kana kusungirirwa) kwezvikamu zvakawanda zvezvinhu zvakasiyana-siyana mune imwe chete yakasimbiswa chimiro.
Chinhu chechipiri chakanaka cheUAM ndiyo dhigirii yepamusoro yepurasitiki inoyerera inoonekwa mumidziyo yesimbi, kunyange pakudzika kwakadzika, kureva kuti pasi pemvura inonyunguduka yezvinhu zvesimbi.Kusanganiswa kwe ultrasonic oscillation uye kudzvinyirira kunokonzera kukwirira kwemuganhu wezviyo zvekuenda kune imwe nzvimbo uye recrystallization pasina kuwedzera kwekushisa kwakakura kunowanzobatanidzwa nezvinhu zvakawanda.Panguva yekuvakwa kwegungano rekupedzisira, ichi kuputika kwesimbi kunoputika, kuputika kwesimbi kunoputika kunogona kuputika uye kuputika kwesimbi. by layer.Elements dzakadai se optical fibers 49, reinforcements 46, electronics 50, uye thermocouples (iri basa) zvose zvakabudirira kuiswa muUAM zvigadziro kuti zvigadzire magungano anoshanda uye asingaiti.
Mubasa iri, ese ari maviri akasiyana ekubatanidza zvinhu uye kupindirana mikana yeUAM yakashandiswa kugadzira yekupedzisira inokonzeresa tembiricha yekutarisa microreactor.
Zvichienzaniswa nepalladium (Pd) uye mamwe anowanzo shandiswa simbi catalysts, Cu catalysis ine zvakawanda zvakanaka: (i) Ehupfumi, Cu inodhura zvishoma pane dzimwe simbi dzakawanda dzinoshandiswa mu catalysis uye naizvozvo inzira inoyevedza yemakemikari ekugadzira indasitiri (ii) Hurukuro hweCu-catalyzed cross-coupling reactions huri kuwedzera uye hunoita sehunopindirana,351,2,51,3,51,2,51,3,51,3,51,5,3,2,51,5,3,2,3,51,3,2,51,2,51,2,3,516, 2. zed reactions inoshanda zvakanaka pakusavapo kwemamwe ligands, Aya ma ligands anowanzo kuve akareruka uye asingadhure kana achidikanwa, nepo ayo anoshandiswa muPd chemistry anowanzo kuoma, anodhura, uye anonzwa mhepo (iv) Cu, inonyanya kuzivikanwa nekugona kwayo kusunga alkynes mu synthesis, Semuyenzaniso, bimetallic-catalyzed Sonogashiradhi ine cycload coupling uye cycload coupp (Cubasic coupdi) iyo arylation yeanoverengeka nucleophiles muUllmann-mhando maitiro.
Mienzaniso yeheterogenization yezviitiko zvose izvi ichangobva kuratidzwa muhupo hweCu (0) .Izvi zvinonyanya kukonzerwa neindasitiri yemishonga uye kuwedzera kwekutarisa kwesimbi inogadzirisa kugadzirisa uye kushandisa zvakare55,56.
Yakapayona naHuisgen muna 1960s57, iyo 1,3-dipolar cycloaddition reaction pakati peacetylene ne azide kusvika ku1,2,3-triazole inoonekwa seyakabatana kuratidzira kuita. Izvo zvinokonzeresa 1,2,3 triazole moieties inonyanya kufarirwa semundima yekushandiswa kwemishonga yemishonga yakasiyana-siyana uye 8 .
Kuita uku kwakazoonekwa zvakare apo Sharpless nevamwe vakaunza pfungwa ye "click chemistry" 59. Izwi rekuti "click chemistry" rinoshandiswa kurondedzera yakasimba, yakavimbika uye yakasarudzika seti yemaitiro ekukurumidza synthesis yemakomponi matsva uye combinatorial raibhurari kuburikidza neheteroatom linkage (CXC) 60 The synthetic yeaya maitiro ekugadziriswa kwemamiriro ezvinhu emvura inobuda, 60 kukwezva kwemvura kwakajeka kunobva ku6 uye kukwezva kwemvura kunobva ku6. 1.
The classical Huisgen 1,3-dipole cycloaddition haisi yechikamu che "click chemistry".Zvisinei, Medal and Sharpless vakaratidza kuti iyi azide-alkyne coupling chiitiko inopinda 107 kusvika 108 pamberi peCu(I) zvichienzaniswa neiyo uncatalyzed 1,3-dipolar chiyero chinoda 62ing celeration 62 celeration 3. mapoka kana mamiriro ekugadzirisa maitiro uye zvibereko pedyo nekutendeuka kwakakwana uye kusarudza ku1,4-disubstituted 1,2,3-triazoles (anti- 1,2,3-triazole) pane imwe nguva (Mufananidzo 3).
Mhedzisiro yeIsometric yeanowanzoitika uye yemhangura huisgen cycudeditions
Zvizhinji zvezvibvumirano zvinosanganisira kuderedzwa kwekugadzikana kweCu (II) zvinyorwa, zvakadai sekuderedzwa kweCuSO4 kana Cu (II) / Cu (0) yemhando yekubatanidza nemunyu we sodium.Kuenzaniswa nemamwe maitiro e-metal-catalyzed, kushandiswa kweCu (I) kune zvakakosha zvikuru zvekuve zvisingadhuri uye zviri nyore kubata.
Kinetic uye isotopic labeling zvidzidzo naWorrell et al.65 yakaratidza kuti, kana iri materminal alkynes, maviri akaenzana emhangura anobatanidzwa mukuita kuti reactivity yemorekuru imwe neimwe iende kuazide.Iyo nzira inorongwa inopfuurira kuburikidza neine nhengo nhanhatu dzesimbi mhete yendarira inoumbwa nekubatanidzwa kweazide ku σ-bonded copper acetylide ine π-bonded copper seyakagadzika deringi derivari ye copper yakagadzika. , inoteverwa neproton decomposition kupa zvigadzirwa zve triazole uye kuvhara iyo catalytic cycle.
Kunyange zvazvo mabhenefiti emidziyo yemakemikari ekuyerera akanyatso kunyorwa, pave paine chishuwo chekubatanidza maturusi ekuongorora mune aya masisitimu e-in-line, in-situ, process monitoring66,67.UAM yakaratidza kuva nzira yakakodzera yekugadzira uye kugadzira yakaoma kwazvo 3D inoyerera inoyerera yakagadzirwa necatalytically inoshanda, thermally conductive zvinhu zvine zvakananga embedded sensing elements (Firemus).
Aluminium-copper flow reactor yakagadzirwa ne ultrasonic additive kugadzira (UAM) ine yakaoma yemukati chiteshi chimiro, embedded thermocouples uye catalytic reaction chamber.Kuti uone mukati memvura nzira nzira, yakajeka prototype yakagadzirwa uchishandisa stereolithography inoratidzwa zvakare.
Kuve nechokwadi chekuti mareactor akagadzirwa kuitira ramangwana organic reactions, zvinonyungudutsa zvinoda kudziyisa zvakachengeteka pamusoro pekubikira;ivo vari kumanikidzika uye kutonhora kunoedzwa.Kuedzwa kwekumanikidza kwakaratidza kuti hurongwa hunochengetedza kugadzikana uye nguva dzose kudzvinyirira kunyange nekuwedzera kwemaitiro ekugadzirisa (1.7 MPa) .The hydrostatic test yakaitwa pakupisa kwekamuri uchishandisa H2O semvura.
Kubatanidza iyo yakamisikidzwa (Figure 1) thermocouple kune tembiricha data logger yakaratidza kuti thermocouple yaive 6 °C (± 1 °C) inotonhorera pane yakarongwa tembiricha paFlowSyn system. ffusivity yezvinhu zvinoshandiswa mukugadzirwa kwekugadzira.Iyi inopisa inopisa inopindirana uye naizvozvo inogona kuverengerwa mukugadzirwa kwemidziyo kuitira kuti kutonhora kwakarurama kusvike uye kuyerwa panguva yekupindura.Naizvozvo, ichi chekutsvaga chekutsvaga paIndaneti chinobatsira kutonga kwakasimba kwehutano hwekuita uye hunoita kuti huve hwakarurama hwekugadzirisa uye kuvandudza mamiriro ezvinhu.
Iyo reactor inoratidzwa mubasa iri ndiyo yekutanga muenzaniso wekushandiswa kweUAM tekinoroji mukugadzirwa kwemakemikari reactor uye inogadzirisa zvakati wandei zvinogumira zvakabatana ne AM/3D kudhindwa kwemidziyo iyi, senge: (i) kukunda matambudziko Akashumwa ane chekuita nemhangura kana aluminium alloy processing (ii) yakagadziridzwa mukati chiteshi kugadziriswa kana ichienzaniswa neupfu mubhedha fusion (PBF) maitiro akaomarara 6 laser inoyerera uye sarudza 6 laser inoyerera pamusoro pemidziyo2 uye sarudza SLM inoyerera zvinhu2 (SLM inoyerera) maitiro. (iii) Kuderedza kupisa kwekushisa, izvo zvinofambisa kusungirirwa kwakananga kwema sensors, izvo zvisingabviri muupfu hwebhedha tekinoroji, (v) inokunda hurombo husina kunaka hwemagetsi uye kunzwisiswa kwepolymer-based components components kune zvakasiyana-siyana zvakajairika organic solvents17,19.
Kushanda kweiyo reactor kwakaratidzwa nehuwandu hwemhangura-catalyzed alkyne azide cycloaddition reactions pasi pemamiriro ekuyerera anoramba achiyerera (Fig. 2) .Iyo ultrasonic-yakadhindwa yemhangura yemhangura inotsanangurwa muFigure 4 yakabatanidzwa nekutengesa kuyerera kwehurongwa uye yakashandiswa kugadzira maazides eraibhurari emhando dzakasiyana-siyana 1,4-disubstituted via3tricealedyl reaction uye tembiricha 1,4-disubstituted 1,4-disubstituted 1,4-disubstituted atricealedyl reaction ye-tembiricha ye-temperature ye-tricealedyl reaction uye 1. halides muhupo hwe sodium chloride (Mufananidzo 3) .Kushandiswa kwekuenderera mberi kwekuyerera kunoderedza kushushikana kwekuchengeteka kunogona kubuda mumabheji maitiro, sezvo izvi zvinogadzirisa zvinogadzirisa zvakanyanya uye zvine ngozi azide intermediates [317], [318] .Pakutanga, mhinduro yacho yakagadziridzwa nokuda kwe cycloaddition ye phenylaceline phenylaceline phenylaceline phenylaceline phenylaceline phenylaceline phenylaceline phenylaceline uye iodoethane) (ona Mufananidzo 5).
(Kumusoro kuruboshwe) Schematic yegadziriro inoshandiswa kubatanidza 3DP reactor muhutano hwekuyerera (kumusoro kurudyi) inowanikwa mukugadzirisa (pasi) chirongwa cheHuisgen cycloaddition 57 chirongwa pakati pe phenylacetylene uye iodoethane kuitira kugadzirisa uye kuratidza optimized parameters reaction conversion rate.
Nekudzora nguva yekugara yemareagents muchikamu chinokonzeresa cheiyo reactor uye nekunyatso tarisisa kudziya kwekuita neiyo yakanyatsobatanidzwa thermocouple probe, maitiro ekuita anogona kugadziriswa nekukurumidza uye nemazvo nenguva shoma uye kushandiswa kwezvinhu. Yakakurumidza kutsanangurwa kuti kushandurwa kwepamusoro kwakawanikwa kana nguva yekugara yemaminetsi gumi nemashanu uye tembiricha yekupindura ye150ro ° C yenguva yeMOD iyo inogona kushandiswa. uye tembiricha yekupindura inoonekwa seyakakosha modhi mazwi.Kumhanyisa iyo yakavakirwa-mukati optimizer uchishandisa aya akasarudzwa mazwi anoburitsa seti yemaitiro mamiriro akagadzirirwa kuwedzera chigadzirwa nzvimbo dzepamusoro apo ichideredza kutanga zvinhu nzvimbo dzepamusoro.Kunatsa uku kwakaburitsa 53% kutendeuka kweiyo triazole chigadzirwa, iyo yakanyatsoenderana nemuenzaniso kufanotaura kwe54%.
Zvichienderana nezvinyorwa zvinoratidza kuti mhangura (I) oxide (Cu2O) inogona kuita semhando inobudirira inokonzeresa pane zero-valent mhangura nzvimbo mune izvi mabatiro, kugona pre-oxidize reactor pamusoro isati yaita kuyerera kwekuyerera kwakaongororwa70,71.Maitiro pakati pe phenylacetylene ne iodoethane yakazoitwa zvakare pasi peiyo gadziriso yakakosha mumamiriro ezvinhu akanyanya kucherechedzwa. yezvinyorwa zvekutanga, izvo zvakaverengerwa kuva > 99% .Zvisinei, kutariswa neHPLC kwakaratidza kuti kutendeuka uku kwakaderedza zvakanyanya nguva yakawandisa yakarebesa kuita kusvika anenge maminetsi makumi mapfumbamwe, apo basa racho rakaonekwa richidzika uye kusvika pa "nzvimbo yakadzikama".Kucherechedza uku kunoratidza kuti chitubu chechiitiko che catalytic chinowanikwa kubva pamusoro pecopper oxide pane pane iyo substrazed metal inoumba zviri nyore uye Cute-oxivalent yesimbi. hazvisi zvidziviriro zvinodzivirira.Izvi zvinobvisa kudiwa kwekuwedzera mhangura yekubatsira (II) kunobva co-composition71.