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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 kusanganisa zvikamu zvinokonzeresa uye zvekunzwa zvinhu. mutsara wezvakakosha biologically 1,4-disubstituted 1,2,3-triazole makomisheni akagadzirwa zvinobudirira 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 kuenderera mberi nekutarisa maitiro uye optimization nguva yekupindura.
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 makemikari midziyo ine customizable additive kugadzira (AM) chemistry "reaction midziyo"8.The iterative dhizaini, kukurumidza kugadzirwa, uye 3-dimensional (3D) kugona kwemaitiro aya anobatsira kune avo vanoda kugadzirisa midziyo yavo kune yakatarwa seti yemabatiro, zuva, zvigadziriso, kana mamiriro ekushanda akasarudzika. polymer-based 3D 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 kwemidziyo yakadaro kuita zvakasiyana-siyana zvemakemikari maitiro / 18207 chiyero chikuru, 18207 kushandiswa kwe18207 yakakura. yeAM mune ino ndima17, 18, 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 metal foils kuitira kuti ibatanidze pamwe chete layer by layer ine zvishoma zvishoma zvekupisa uye high degree of plastic flow 21 , 22 , 23 .Kusiyana nemamwe AM-tech anogona kusanganiswa zvakananga, AInnologies anonyanya kuzivikanwa neAM anonyanya kuzivikanwa. seyakasanganiswa yekugadzira nzira, umo in-situ periodic komputa nhamba yekudzora (CNC) milling kana laser machining inotsanangura mambure chimiro cheiyo yakasungwa zvinhu 24, 25.Izvi zvinoreva kuti mushandisi haaganhurwe nezvinetso zvine chekuita nekubvisa zvakasara zvimisikidzo zvekuvaka kubva kune madiki emvura nzira, iyo inowanzova iyo ine hupfu uye yemvura machining inotsanangura iyo mambure chimiro cheiyo yakasungwa zvinhu 24, 25.Izvi zvinoreva kuti mushandisi haagumirwe nezvinetso zvine chekuita nekubvisa zvakasara zvimisikidzo zvekuvaka kubva kune madiki madiki emvura, izvo zvinowanzoitika neupfu uye mvura yemvura sarudzo inogona kuwedzera rusununguko AM26. bond thermally thermally and dissimilar material combinations in a single process step.Kusarudzwa kwezvinhu zvakasanganiswa kunze kwekunyunguduka kunoreva kuti iyo mechanical uye makemikari zvinoda yezvikumbiro zvakananga zvinogona kusangana nani.Kuwedzera kune yakasimba state bonding, chimwe chiitiko chakasangana panguva ye ultrasonic bonding ndeyekuyerera kwepamusoro kwezvigadzirwa zvepurasitiki pamatembiricha akadzikama29,30,31,31,32,33AM ekugadzirisa masimbi emushonga wesimbi. masensa asina kukuvadzwa.UAM yakamisikidzwa ma sensors anogona kufambisa kuburitswa 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; uye kuisa ma sensors ekupisa zvakananga pakati pehova dze reagent kuitira kunyatsoita tembiricha yekutarisisa uye kutonga.Kuratidza kushanda kweiyo reactor, raibhurari yemishonga yakakosha 1,4-disubstituted 1,2,3-triazole makomponi akagadzirwa nemhangura-catalyzed Huisgen 1,3-dipolar sainzi yakasimbisa mashandisirwo esainzi kombiyuta. dhizaini inogona kuvhura mikana mitsva uye mikana yekemesitiri kuburikidza nekutsvagisa kwakasiyana-siyana.
Zvese zvinonyungudutsa uye reagents zvakatengwa kubva kuSigma-Aldrich, Alfa Aesar, TCI kana Fischer Scientific uye zvakashandiswa pasina kucheneswa.1H uye 13C NMR spectra yakanyorwa pa400 MHz uye 100 MHz, zvichiteerana, yakawanikwa pachishandiswa JEOL ECS-400 400 400 MHz 400 MHz 400 MHz 400 MHz kana MHz II MHz. spectrometer uye CDCl3 kana (CD3)2SO se solvent.Maitirwo ese akaitwa pachishandiswa Uniqsis FlowSyn flow chemistry platform.
UAM yakashandiswa kugadzira midziyo yese muchidzidzo ichi.Tekinoroji yakaumbwa muna 1999, uye ruzivo rwayo rwehunyanzvi, mashandiro eparamita uye mafambisirwo kubva payakagadzirwa ichigona kudzidzwa kuburikidza neanotevera akatsikiswa zvinhu34,35,36,37.Mudziyo (Mufananidzo 1) wakashandiswa pachishandiswa simba repamusoro-soro, 9kW SonicLayer® UAM 4000 yeU.S.A.Sonic Layer 4000 yakasarudzwa. kugadzirwa kwechigadzirwa chekuyerera kwaive Cu-110 uye Al 6061.Cu-110 ine yakakwira mhangura yemukati (isingaite 99.9% mhangura), ichiita kuti ive mukwikwidzi akanaka wemhangura-catalyzed reactions, uye saka inoshandiswa se "inoshanda layer mukati me microreactor. Al 6061 O inoshandiswa se "zvizhinji" zvinhu zvinoshandiswa pakuongorora uye embedding layer; annealed condition yakasanganiswa neCu-110 layer. Al 6061 O inyaya yakaratidzwa kuti inonyatsoenderana neUAM process38, 39, 40, 41 uye yakaedzwa ikawanikwa yakagadzikana nemakemikari anoshandiswa mubasa iri. 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 yekugadzirisa / reagent yekubatana uye kupa zvibereko zvakanakisisa zvechigadzirwa.Machipisi anoshandisa 90 ° kubhenda pamagumo emugwagwa wakarurama kuti aite mukati mehutano hwekusangana nepamusoro pemvura inoputika4 inosanganiswa nepamusoro pemvura inosanganiswa nemhepo inoputika. (catalyst) .Kuti uwedzere kuwedzera kusanganiswa kunogona kuwanikwa, dhizaini yekugadzira inoratidzira maviri reagent inlets yakabatanidzwa paY-junction isati yapinda muchikamu chekusanganiswa kwenyoka.Ikoni yechitatu, iyo inopindirana nehafu yerukova kuburikidza nekugara 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) kubudiswa kwevhoriyamu, asi iduku zvakakwana kuti ifambise kupindirana kwepamusoro (catalysts) kwezvizhinji zvezvinwiwa zvirimo.Ukuru hwakakodzera hunobva pane zvakaitika kare zvevanyori zvemasimbi-fluidic emukati maitirwo e-metal-fluidic yekupedzisira. µm x 750 µm uye vhoriyamu yese reactor yaive 1 ml.Chibatanidza chinosanganiswa (1/4″—28 UNF thread) chinosanganisirwa mukugadzira kuti zvibvumire kupindirana kuri nyore kwemudziyo une zvekutengesa kuyerera chemistry 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 remafashi. (square) finish.Mubasa iri, kuitira kuchengetedza symmetry yechiteshi, 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 mukati memichina, zvichiita kuti pave nepamusoro pezvigadzirwa nematanho akaenzana nechombo chakasarudzwa uye CNC process parameters (inenge 1.6 μm Ra mumuenzaniso uyu) . iva nechokwadi chekururama kwedimensional inochengetedzwa uye chikamu chakapedzwa chichasangana neCNC kupedza milling accuracy levels.Iyo upamhi hwechiteshi inoshandiswa pamudziyo uyu idiki zvakakwana kuti ive nechokwadi chokuti foil haisi "sag" mumugero wemvura, saka mugero unochengetedza square cross-section.Possible gaps mu foil material uye UAM process parameters yakatemerwa experimentally neanogadzira mubatanidzwa, USA Fabrisonic.
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 pakabuda rereactor 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 inogara ichiyerera inoyerera tembiricha inoyerera inogara ichiyerera tembiricha inoyerera. kusiyana pakati pe thermocouples akaiswa mukati me reactor uye ayo akaiswa mukati me FlowSyn chip heat plate.Izvi zvinowanikwa nekusiyanisa tembiricha yehotplate inorongwa pakati pe100 ne150 °C mu25 °C increments uye nekucherechedza chero misiyano pakati pekushisa kwakarongwa uye kwakarekodhwa.Izvi zvakawanikwa uchishandisa UK datach, Pico8 uye Cambridge. inoperekedza PicoLog software.
The cycloaddition reaction conditions of phenylacetylene and iodoethane were optimized (Scheme 1- Cycloaddition ye phenylacetylene uye iodoethane Scheme 1- Cycloaddition ye phenylacetylene uye iodoethane) .Iyi optimization yakaitwa ne full factorial dhizaini yezviedzo (DOE reside the approaches), uchishandisa tembiricha yenguva yekuedza (DOE) alkyne:azide ratio pa1:2.
Separate solutions of sodium aazide (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 pane yaidiwa kuyerera kweyero uye tembiricha seye triak dunhu remhinduro yakatorwa. phenylacetylene kutanga zvinhu uye yakatemwa nepamusoro pekuita liquid chromatography (HPLC) .Kuti iwirirane yekuongorora, maitiro ese akatorwa sampuli mushure mekuita musanganiswa wasiya reactor.Iyo parameter yakasarudzwa kuti ishandiswe inoratidzwa muTafura 2.
Mienzaniso yese yakaongororwa pachishandiswa Chromaster HPLC system (VWR, PA, USA) inosanganisira pombi yequaternary, column oven, variable wavelength UV detector uye autosampler. The column was an Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 mm muhukuru, 5 µm saizi, 5 µm isocratic 50: 50 methanol: mvura pachiyero chekuyerera kwe1.5 mL.min-1. Irojekiti yejekiseni yaiva 5 µL uye detector wavelength yaiva 254 nm. The % peak area for the DOE sample yakaverengwa kubva kunzvimbo dzepamusoro dzealkyne dzakasara uye triazole yezvigadzirwa zvekutanga zvepeak injedent chete.
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 nereactor pa 75 µL.min-1 uye 150 °C yakaunganidzwa muhuwandu hwe150 ° C. ethyl acetate.Mushonga wemuenzaniso wakashambidzwa ne 3 × 10 mL yemvura. Mishonga yemvura yakasanganiswa uye yakabudiswa 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) akaitwa zvakananga kubva kune 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 che1.5 mL C / th th th th th. 254 nm.
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 horn or ultrasonic horn) kuisa dzvinyiriro kufoil layer/yaimbova yakasanganiswa layer kuti isungirwe uku ichibvunda zvinhu. kubatanidza nzvimbo yose.Kana kudzvinyirirwa uye kudengenyeka kunoshandiswa, maokisi ari pamusoro pezvinhu zvinogona kuputika.Kuenderera mberi kumanikidziro uye kudengenyeka kunogona kukonzera asperities yezvinhu kuti iparare 36 .Kushamwaridzana kwepedyo nekupisa kunokonzerwa nenharaunda uye kudzvinyirira zvino kunotungamirira kune yakasimba-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 yakakwirira yepurasitiki inoyerera inoonekwa mumidziyo yesimbi, kunyange pakudzika kwakadzika, kureva kuti pasi pemvura inonyunguduka yezvinhu zvesimbi.Kusanganiswa kwe ultrasonic oscillation uye kumanikidzika kunokonzera kukwirira kwemuganhu wezviyo zvemunharaunda uye recrystallization pasina kuwedzera kwekushisa kwakakura kunowanzobatanidzwa nezvinhu zvakawanda.Mukati yekuvakwa kwegungano rekupedzisira, ichi kuputika kwechikamu chinoputika chinogona kuputika uye kuputika kwezvikamu zvekupedzisira zvinogona kuputika. metal foil, layer by layer.Elements senge optical fibers 49, reinforcements 46, electronics 50, uye thermocouples (iri basa) zvese zvakaiswa zvinobudirira muUAM zvimiro kuti zvigadzire anoshanda uye asingaiti anoumba magungano.
Mubasa iri, ese ari maviri akasiyana ekubatanidza zvinhu uye kupindirana mikana yeUAM yakashandiswa kugadzira yekupedzisira inokonzeresa tembiricha yekutarisa microreactor.
Zvichienzaniswa ne palladium (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 yeindasitiri yekugadzira makemikari (ii) Rudzi rweCu-catalyzed cross-coupling reactions huri kuwedzera uye hunoita seine Pd51-based nzira, Cu-catalyzed reactions inoshanda zvakanaka pakushaikwa kwemamwe ligand, Aya ma ligands anowanzo kuve akapusa 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-catalyzedcling cyclingnogad chemistry) (v) Cu inokwanisawo kusimudzira kufambiswa kwema nucleophiles akati wandei muUllmann-type reactions.
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 neazide kusvika ku1,2,3-triazole inoonekwa seyakabatana kuratidzira kuita. Izvo zvinokonzeresa 1,2,3 triazole moieties inonyanya kufarira sendima yekushandiswa kwemishonga yemishonga yakasiyana mishonga yekurapa 58 .
Kuita uku kwakazoonekwa zvakare apo Sharpless nevamwe vakaunza pfungwa ye "click chemistry" 59. Izwi rokuti "click chemistry" rinoshandiswa kurondedzera yakasimba, yakavimbika uye yakasarudzwa seti yemaitiro ekukurumidza kusanganiswa kwemishonga mitsva uye combinatorial library kuburikidza neheteroatom linkage (CXC) 60 The synthetic yemamiriro ezvinhu aya anokonzerwa nemamiriro ezvinhu aya anokonzerwa nemamiriro ezvinhu akakwirira, kukwezva kwemvura kunobva, kukwezva kwemvura kwakabatana, uye kukwezva kwemvura kunobva kune nyore, kugadzirwa kweokisijeni. kupatsanurwa kuri nyore61.
The classical Huisgen 1,3-dipole cycloaddition haisi yeboka re "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 che cycload 62acceledi yakakosha. haidi mapoka ekudzivirira 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).
Isometric results of common and copper-catalyzed Huisgen cycloadditions.Cu(I)-catalyzed Huisgen cycloadditions inobereka chete 1,4-disubstituted 1,2,3-triazoles, asi thermally induced Huisgen cycloadditions inowanzo bereka 1,5-azo-1,4-uye-1,4-azo-1-uye-1,4-1-azo-1-uye-1,4-1-azo-1-azo-azoles-a-1,4-1-azo-1 musanganiswa. stereoisomers ye azoles.
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 ku azide.Iyo nzira inorongwa inopfuurira kuburikidza neine nhengo nhanhatu yendarira yesimbi ring inoumbwa nekubatanidzwa kweazide kune σ-bonded copper acetylide ine π-bonded copper seyakagadzika donor irigastable. mhete shrinkage, inoteverwa neproton decomposition kuti ipe zvigadzirwa zve triazole uye kuvhara iyo catalytic cycle.
Kunyange zvazvo mabhenefiti emidziyo yemakemikari ekuyerera akanyorwa zvakanaka, 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 kumanikidzwa uye kutonhora kunoedzwa.Kuedzwa kwekumanikidza kwakaratidza kuti hurongwa hunoramba huchigadzikana uye hunogara huchimanikidza 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. high thermal diffusivity of the materials used in the production process.This thermal drift inopindirana uye saka inogona kuverengerwa mukugadzirwa kwemidziyo kuti ive nechokwadi chekuti tembiricha dzakarurama dzinosvika uye kuyerwa panguva yekupindura.Naizvozvo, iyi online monitoring tool inogonesa kudzora kwakasimba kwekuita tembiricha uye inogonesa kunyatso gadzirisa maitiro uye kuvandudza mamiriro akakwana.Izvi sensors inodzivirira maitiro escale-masensi anogona kushandiswawo kudzivirira maitiro escale-masensa.
Iyo reactor inoratidzwa mubasa iri ndiyo yekutanga muenzaniso wekushandiswa kweUAM tekinoroji mukugadzirwa kwemakemikari reactors 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 yemukati chiteshi kugadzirisa kana ichienzaniswa nehupfu mubhedha fusion (PBF) maitiro ekuyerera akadai se6 (SLM) kuyerera kwezvinhu, SLM kuyerera, uye sarudza6 laser inoyerera. rough surface texture.
Kushanda kweiyo reactor kwakaratidzwa neyakatevedzana yemhangura-catalyzed alkyne azide cycloaddition reactions pasi pemamiriro 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 via3-tricealed reaction, 1,4-disubstituted 3-tricealed reaction, 1,4-disubstituted the-control, 1,4-disubstituted the-triceale-control reaction, uye alkyl mapoka halides muhupo hwe sodium chloride (Mufananidzo 3) .Kushandiswa kwenzira inoramba ichiyerera kunoderedza zvinetso zvekuchengetedza zvinogona kubuda mumatanho e-batch, sezvo izvi zvinogadzirisa zvinobudisa zvakanyanya uye zvine ngozi azide intermediates [317], [318] . Cycloaddition ye phenylacetylene 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 optimization uye kuratidza optimized parameters reaction conversion rate.
Nekudzora nguva yekugara yemareagents muchikamu chinokonzeresa cheiyo reactor uye kunyatso tarisisa tembiricha yekuita neyakasanganiswa yakananga thermocouple probe, maitiro ekuita anogona kugadziriswa nekukurumidza uye nemazvo nenguva shoma uye kushandiswa kwezvinhu. Yakakurumidza kutariswa kuti kushandurwa kwepamusoro kwakawanikwa kana nguva yekugara yemaminetsi gumi nemashanu uye tembiricha yekupindura ye150 ° C yeMOD inogona kushandiswa. nguva dzose dzekugara uye tembiricha yekuita zvinoonekwa seakakosha emhando yematemu.Kumhanyisa yakavakirwa-mukati optimizer uchishandisa aya akasarudzwa mazwi anoburitsa seti yemamiriro ekuita akagadzirirwa kuti awedzere chigadzirwa nzvimbo dzepamusoro apo ichideredza kutanga zvinhu peak nzvimbo.Kunatswa 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 pazero-valent mhangura yemhangura mune izvi maitirwo, kugona pre-oxidize rereactor surface isati yaita maitikiro ekuyerera kwakaongororwa70,71.Maitiro pakati pephenylacetylene neiodoethane yakazoitwa zvakare pasi pechigumisiro chepamusoro chakazoonekwa pasi pemamiriro ekugadzirisa akakosha. mukushandurwa kwezvinhu zvekutanga, izvo zvakaverengerwa kuva > 99% .Zvisinei, kutariswa neHPLC kwakaratidza kuti kutendeuka uku kwakaderedza zvakanyanya nguva yakawandisa yakarebesa kuita kusvika anenge maminetsi e90, apo basa racho rakaonekwa richidzika uye kusvika pa "steady state".Kucherechedza uku kunoratidza kuti chitubu chebasa rinokonzera rinowanikwa kubva pamusoro pemhangura yecopper-oxide. tembiricha yekuumba CuO neCu2O dzisiri zvidimbu zvinodzivirira.