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Kuwedzera kugadzira kuri kushandura nzira iyo vaongorori nevemaindasitiri vanogadzira nekugadzira michina yemakemikari kuti isangane nezvavanoda.Mubepa rino, tinoshuma muenzaniso wekutanga weyekuyerera reactor yakaumbwa neultrasonic additive kugadzira (UAM) lamination yesimbi yakasimba sheet ine yakanyatsobatanidzwa catalytic zvikamu uye zvinonzwa zvinhu.UAM tekinoroji haingokunda akawanda ezvipimo zvazvino zvine chekuita nekuwedzera kugadzirwa kwemakemikari reactor, asi zvakare inowedzera zvakanyanya kugona kwemidziyo yakadaro.Nhamba ye biologically yakakosha 1,4-disubstituted 1,2,3-triazole mishonga yakagadziriswa uye yakagadziridzwa neCu-mediated 1,3-dipolar Huisgen cycloaddition reaction uchishandisa UAM chemistry nzvimbo.Uchishandisa zvakasarudzika zvivakwa zveUAM uye kuenderera kuyerera kwekugadzirisa, chishandiso chinokwanisa kukonzeresa maitiro anoenderera mberi uye nekupa chaiyo-nguva mhinduro yekutarisa uye kugadzirisa maitiro.
Nekuda kwemabhenefiti ayo akakosha pamusoro peayo akawanda anoenderana naye, kuyerera chemistry inzvimbo yakakosha uye inokura mune zvese zvedzidzo uye maindasitiri zvigadziriso nekuda kwekugona kwayo kuwedzera kusarudzwa uye kugona kwemakemikari synthesis.Izvi zvinotangira pakugadzirwa kweakareruka organic molecules1 kuenda kumishonga komisheni2,3 uye zvakasikwa zvigadzirwa4,5,6.Pamusoro pe50% yemaitiro mumaindasitiri akanaka emakemikari uye emishonga anogona kubatsirwa nekuenderera kuyerera7.
Mumakore achangopfuura, kwave nemaitiro ari kukura emapoka ari kutsvaga kutsiva echinyakare glassware kana kuyerera kemisitiri michina ine inochinjika kemikari "reactor"8.Iyo iterative dhizaini, nekukurumidza kugadzira, uye matatu-dimensional (3D) kugona kwemaitiro aya anobatsira kune avo vanoda kugadzirisa maturusi avo kune imwe seti yemabatiro, zvishandiso, kana mamiriro.Kusvika pari zvino, basa iri rakanangana zvakanyanya nekushandiswa kwepolymer-based 3D kudhinda matekiniki akadai sesterolithography (SL)9,10,11, Fused Deposition Modeling (FDM)8,12,13,14 uye inkjet kudhinda7,15., 16. Kusavimbika uye kukwanisa kwezvishandiso zvakadaro kuita zvakasiyana-siyana zvemakemikari maitiro / kuongorora17, 18, 19, 20 chinhu chikuru chinogadzirisa kushandiswa kwakakura kwe AM mundima iyi17, 18, 19, 20.
Nekuda kwekuwedzera kwekushandiswa kwekemikari yekuyerera uye zvinhu zvakanaka zvine chekuita neAM, nzira dziri nani dzinoda kuongororwa izvo zvinobvumira vashandisi kugadzira midziyo yekuyerera inoyerera ine yakagadziridzwa chemistry uye analytical kugona.Idzi nzira dzinofanirwa kubvumira vashandisi kuti vasarudze kubva mumhando yesimba repamusoro kana zvinhu zvinoshanda zvinokwanisa kushanda pasi pemamiriro akasiyana-siyana ekuita, pamwe nekufambisa nzira dzakasiyana-siyana dzekuongorora kubuda kubva pachigadzirwa kuti zvigone kutarisa uye kutonga kwekuita.
Imwe nzira yekuwedzera yekugadzira iyo inogona kushandiswa kugadzira tsika yemakemikari reactors ndeye Ultrasonic Additive Manufacturing (UAM).Iyi yakasimba-state sheet lamination method inoshandisa ultrasonic vibrations kune dzakatetepa simbi foils kuti dzizvibatanidze pamwe chete layer by layer ine shoma volumetric heat uye yakakwirira degree yepurasitiki inoyerera 21, 22, 23. Kusiyana nemamwe akawanda AM matekinoroji, UAM inogona kusanganiswa zvakananga ne subtractive production, inozivikanwa seyakasanganiswa yekugadzira maitiro, umo periodic in-situ in-situ yen-situ yekugadzika kudzora kwenhamba ye2 laser layer) 25. Izvi zvinoreva kuti mushandisi haangogumiri kumatambudziko ane chokuita nekubviswa kwezvinhu zvakasara zvechivako kubva kumatanho maduku emvura, izvo zvinowanzoitika muupfu uye maitiro emvura AM26,27,28.Rusununguko rwekugadzira urwu runowedzerawo kusarudzo yezvinhu zviripo - UAM inogona kubatanidza musanganiswa wezvinhu zvinopisa zvakafanana uye zvisina kufanana mune imwe nhanho yekuita.Sarudzo yemusanganiswa wezvinhu kupfuura nzira yekunyunguduka inoreva kuti izvo zvemakanika uye makemikari zvinodiwa zvemashandisirwo chaiwo anogona kusangana zvirinani.Pamusoro pekubatana kwakasimba, chimwe chiitiko chinoitika ne ultrasonic bonding ndiyo yakakwira fluidity yemidziyo yepurasitiki pane yakaderera tembiricha29,30,31,32,33.Ichi chakasarudzika chimiro cheUAM chinobvumira mechini / zvinopisa zvinhu kuti zviiswe pakati pesimbi zvidimbu pasina kukuvara.Yakamisikidzwa UAM sensors inogona kufambisa kuburitswa kwechokwadi-nguva ruzivo kubva kune mudziyo kuenda kumushandisi kuburikidza neakasanganiswa analytics.
Basa rakapfuura nevanyori32 rakaratidza kugona kweUAM maitiro ekugadzira esimbi 3D microfluidic zvimiro zvine akadzamirirwa kunzwa kugona.Mudziyo uyu ndewekutarisa chete.Ichi chinyorwa chinopa muenzaniso wekutanga weiyo microfluidic kemikari reactor yakagadzirwa neUAM, chishandiso chinoshanda chisingangodzore chete asiwo chinokonzeresa kugadzirwa kwekemikari nezvinhu zvakabatanidzwa zvinokonzeresa.Chishandiso ichi chinosanganisa zvakati wandei zvakabatana neUAM tekinoroji mukugadzira 3D kemikari michina, senge: kugona kushandura yakazara 3D dhizaini zvakananga kubva kune komputa-inobatsirwa dhizaini (CAD) muchigadzirwa;Multi-material kugadzirwa kwemusanganiswa wepamusoro wekupisa conductivity uye catalytic zvinhu, pamwe neanopisa sensors akaiswa zvakananga pakati pehova dzinoita kuti dzinyatso kudzora uye kutonga kwekuita tembiricha.Kuratidza kushanda kweiyo reactor, raibhurari yemishonga yakakosha 1,4-disubstituted 1,2,3-triazole compounds yakagadzirwa nemhangura-catalyzed 1,3-dipolar Huisgen cycloaddition.Iri basa rinoratidza kuti kushandiswa kwezvinhu zvesainzi uye dhizaini-inobatsirwa nekombuta kunogona kuvhura mikana mitsva nemikana yekemistry kuburikidza nekutsvagisa kwakasiyana-siyana.
Zvese zvinonyungudutsa uye reagents zvakatengwa kubva kuSigma-Aldrich, Alfa Aesar, TCI, kana Fischer Scientific uye yakashandiswa pasina kucheneswa kwekutanga.1H uye 13C NMR spectra yakarekodhwa pa400 uye 100 MHz, zvichiteerana, yakawanikwa paJEOL ECS-400 400 MHz spectrometer kana Bruker Avance II 400 MHz spectrometer ine CDCl3 kana (CD3)2SO se solvent.Maitiro ese akaitwa pachishandiswa Uniqsis FlowSyn flow chemistry platform.
UAM yakashandiswa kugadzira midziyo yese muchidzidzo ichi.Iyo tekinoroji yakaumbwa muna 1999 uye ruzivo rwayo rwehunyanzvi, maparamendi ekushanda uye budiriro kubva payakagadzirwa inogona kudzidzwa uchishandisa zvinotevera zvakaburitswa zvinyorwa34,35,36,37.Iyo mudziyo (Fig. 1) yakashandiswa uchishandisa basa rinorema 9 kW SonicLayer 4000® UAM system (Fabrisonic, Ohio, USA).Zvinhu zvakasarudzwa nokuda kwechigadzirwa chekuyerera chaiva Cu-110 uye Al 6061. Cu-110 ine mhangura yakawanda yemhangura (isinganyanyi 99.9% mhangura), zvichiita kuti ive mumiriri akanaka wemhangura yakagadziriswa maitiro uye naizvozvo inoshandiswa se "chinyorwa chinoshanda mukati me microreactor.Al 6061 O inoshandiswa se "yakawanda" zvinhu., uyewo intercalation layer inoshandiswa pakuongorora;kupindirana kweanobatsira alloy zvikamu uye annealed state musanganiswa neCu-110 layer.yakawanikwa yakagadzikana mumakemikari nemareagents anoshandiswa mubasa iri.Al 6061 O pamwe chete neCu-110 inoonekwawo semusanganiswa wezvinhu unofambirana neUAM uye naizvozvo chinhu chakakodzera pachidzidzo chino38,42.Midziyo iyi yakanyorwa muTable 1 pazasi.
Matanho ekugadzira Reactor (1) 6061 aluminium alloy substrate (2) Kugadzirwa kwegwara rezasi kubva pafoiri yemhangura (3) Kuiswa kwe thermocouples pakati pezvikamu (4) Mugero wepamusoro (5) Inlet nekubuda (6) Monolithic reactor.
Iyo fluid chiteshi dhizaini dhizaini ndeye kushandisa nzira inoshungurudza kuwedzera chinhambwe chinofambwa nemvura mukati meiyo chip uchichengeta inogoneka chip size.Uku kuwedzera kwechinhambwe kunodiwa kuwedzera catalyst-reactant kuonana nguva uye kupa yakanakisa chigadzirwa goho.Iwo machipisi anoshandisa 90 ° kubhenda kumigumo yenzira yakatwasuka kukonzeresa kusanganisa kusanganisa mukati memudziyo44 uye kuwedzera nguva yekubatana kwemvura nepamusoro (catalyst).Kuti uwedzere kuwedzera kusanganiswa kunogona kuwanikwa, dhizaini yeiyo reactor inosanganisira maviri reactant inlets akasanganiswa muY-kubatana asati apinda muchikamu chekusanganisa coil.Mukova wechitatu, unoyambuka kuyerera kwepakati nepakati pekugara, unosanganisirwa muchirongwa chenguva yemberi yakawanda-nhanho synthesis reactions.
Zvese zviteshi zvine sikweya mbiri (hapana taper angles), inova mhedzisiro ye periodic CNC milling inoshandiswa kugadzira chiteshi geometry.Zviyero zvechiteshi zvinosarudzwa kuti zvipe yakakwira (yemicroreactor) goho revhoriyamu, asi ridiki zvakakwana kuti rifambise kudyidzana nepamusoro (catalysts) yezvinwiwa zvakawanda zvirimo.Hukuru hwakakodzera hunobva pane zvakaitika kare zvevanyori nesimbi-mvura yekuita midziyo.Zviyero zvemukati zvemugero wekupedzisira zvaive 750 µm x 750 µm uye yakazara reactor volume yaive 1 ml.Iyo yakavakirwa-mukati yekubatanidza (1/4 ″-28 UNF shinda) inosanganisirwa mudhizaini kubvumira kupindirana kuri nyore kwechishandiso nekutengesa kuyerera chemistry michina.Saizi yechiteshi inoganhurirwa nehupamhi hweiyo foil zvinhu, iyo mechanical zvivakwa, uye iyo bonding parameters inoshandiswa ne ultrasonics.Pahumwe hupamhi hwezvinhu zvakapihwa, zvinhu zvino "sag" muchiteshi chakagadzirwa.Parizvino hapana chaiyo modhi yekuverenga uku, saka iyo yakakura chiteshi hupamhi hwechinhu chakapihwa uye dhizaini inotemerwa kuyedza, mune iyo mamiriro ehupamhi hwe750 µm haizokonzeresa sag.
Chimiro (square) chechiteshi chinogadziriswa uchishandisa square cutter.Chimiro uye saizi yematanho anogona kuchinjwa paCNC michina uchishandisa akasiyana ekucheka maturusi kuti awane akasiyana ekuyerera mareti uye maitiro.Muenzaniso wekugadzira chiteshi chakakomberedzwa chine 125 µm chishandiso chinogona kuwanikwa muMonaghan45.Kana iyo foil layer ikashandiswa yakadzikama, kushandiswa kweiyo foil zvinhu kune migero kuchava ne flat (square) pamusoro.Mubasa iri, square contour yakashandiswa kuchengetedza chiteshi symmetry.
Munguva yakarongwa kumbomira mukugadzirwa, thermocouple tembiricha sensors (mhando K) inovakwa zvakananga muchishandiso pakati pemapoka epamusoro neakadzika chiteshi (Fig. 1 - nhanho 3).Aya thermocouples anogona kudzora tembiricha shanduko kubva -200 kusvika 1350 °C.
Iyo metal deposition process inoitwa nerunyanga rweUAM uchishandisa simbi foil 25.4 mm yakafara uye 150 microns gobvu.Aya akaturikidzana efoil akabatanidzwa munhevedzano yemitsetse yepedyo kuvhara nzvimbo yese yekuvaka;saizi yechinhu chakaiswa chakakura kupfuura chigadzirwa chekupedzisira sezvo nzira yekubvisa ichigadzira chimiro chekupedzisira chakachena.CNC machining inoshandiswa kuchina ekunze uye emukati contours yemidziyo, zvichikonzera kupera kwepamusoro kwemidziyo nematashi anoenderana nechakasarudzwa chishandiso uye CNC maitiro paramita (mumuenzaniso uyu, ingangoita 1.6 µm Ra).Inoenderera, inoenderera, inoenderera mberi ultrasonic zvinhu zvekupfapfaidza uye machining cycles anoshandiswa mukati mekugadzirwa kwechigadzirwa kuti ive nechokwadi chekuti dimensional kurongeka kunochengetedzwa uye chikamu chakapedzwa chinosangana neCNC yakanaka milling chaiyo mazinga.Hupamhi hwechiteshi chinoshandiswa pachishandiso ichi idiki zvakakwana kuti ive nechokwadi chekuti foil hai "sag" mugero remvura, saka chiteshi chine square cross chikamu.Mikana inokwanisika mune iyo foil zvinhu uye maparamita eiyo UAM maitiro akatemerwa kuyedza neanogadzira shamwari (Fabrisonic LLC, USA).
Zvidzidzo zvakaratidza kuti painterface 46, 47 yeUAM compound pane zvishoma kupararira kwezvinhu pasina kuwedzera kupisa kupisa, saka kune zvigadzirwa mubasa iri Cu-110 layer inoramba yakasiyana neAl 6061 layer uye inoshanduka zvikuru.
Isa pre-calibrated back pressure regulator (BPR) pa 250 psi (1724 kPa) pasi pereactor uye pomba mvura kuburikidza nereactor pachiyero che 0.1 kusvika 1 ml min-1.Iyo reactor pressure yakatariswa pachishandiswa FlowSyn pressure transducer yakavakirwa musystem kuti ive nechokwadi chekuti system yacho inogona kuchengetedza yakadzikama.Anogona tembiricha magradients muyekuyerera reactor akaedzwa nekutsvaga chero misiyano pakati pemathermocouples akavakirwa mu reactor uye thermocouples akavakirwa mundiro yekudziya yeFlowSyn chip.Izvi zvinowanikwa nekushandura tembiricha yakarongwa yehotplate iri pakati pe100 ne150 °C mu25 °C increments uye kuongorora chero mutsauko pakati petembiricha dzakarongwa uye dzakarekodhwa.Izvi zvakawanikwa pachishandiswa tc-08 data logger (PicoTech, Cambridge, UK) uye inoperekedza PicoLog software.
Mamiriro ezvinhu e cycloaddition reaction ye phenylacetylene uye iodoethane inogadziriswa (Scheme 1-Cycloaddition ye phenylacetylene uye iodoethane, Scheme 1-Cycloaddition ye phenylacetylene uye iodoethane).Iyi optimization yakaitwa pachishandiswa yakazara factorial dhizaini yekuyedza (DOE) nzira, uchishandisa tembiricha uye nguva yekugara sezvinosiyana uchigadzirisa alkyne:azide ratio pa1: 2.
Mishonga yakasiyana yeazide sodium (0.25 M, 4: 1 DMF: H2O), iodoethane (0.25 M, DMF), uye phenylacetylene (0.125 M, DMF) yakagadzirwa.A 1.5 ml aliquot yemhinduro yega yega yakasanganiswa uye kupomba kuburikidza nereactor pachiyero chaidiwa chekuyerera uye tembiricha.Mhinduro yemuenzaniso yakatorwa sereshiyo yenzvimbo yepamusoro yechigadzirwa che triazole kune yekutanga zvinhu phenylacetylene uye yakatemwa kushandisa yakakwira performance liquid chromatography (HPLC).Kuti kuongororwa kuenderana, maitiro ese akatorwa pakarepo mushure mekuita musanganiswa wasiya reactor.Iwo parameter akasarudzirwa optimization anoratidzwa muTafura 2.
Ese masampuli akaongororwa pachishandiswa Chromaster HPLC system (VWR, PA, USA) ine quaternary pombi, column oven, variable wavelength UV detector uye autosampler.Koramu yacho yaive Equivalence 5 C18 (VWR, PA, USA), 4.6 x 100 mm, 5 µm particle size, inochengetwa pa40°C.The solvent was isocratic methanol:mvura 50:50 pamwero wekuyerera we 1.5 ml · min-1.Iro jekiseni vhoriyamu yaive 5 μl uye detector wavelength yaive 254 nm.Iyo % nzvimbo yepamusoro yemuenzaniso weDOE yakaverengerwa kubva kunzvimbo dzepamusoro dzezvakasara zvealkyne uye triazole zvigadzirwa chete.Kuiswa kwezvinhu zvekutanga kunoita kuti zvikwanise kuziva nhongonya dzinoenderana.
Kubatanidza mhedzisiro yekuongorora reactor neMODE DOE software (Umetrics, Malmö, Sweden) yakabvumira kunyatsoongorora maitiro emhedzisiro uye kutsunga kweakanyanya kuita mamiriro eiyo cycloaddition.Kumhanyisa iyo yakavakirwa-mukati optimizer uye kusarudza ese akakosha emhando mazwi anogadzira seti yemamiriro ekuita akagadzirirwa kukwidziridza nzvimbo yepamusoro yechigadzirwa uku ichidzikisa nzvimbo yepamusoro yeacetylene feedstock.
Oxidation yemhangura yemhangura muimba ye catalytic reaction yakawanikwa uchishandisa hydrogen peroxide solution (36%) inoyerera kuburikidza nekamuri yekupindura (kuyerera kwehuwandu = 0.4 ml min-1, nguva yekugara = 2.5 min) isati yatanga kuumbwa kweimwe triazole compound.library.
Kana imwe nguva yakanyatsogadziriswa yemamiriro ezvinhu yakange yagadziriswa, yakashandiswa kune zvakasiyana-siyana zveacetylene uye haloalkane derivatives kuti zvibvumire kuumbwa kweraibhurari duku yekugadzira, nokudaro kuisa mukana wekushandisa mamiriro aya kune yakawanda yakawanda yezvingaita reagents (Fig. 1).2).
Gadzirira mhinduro dzakasiyana dze sodium aside (0.25 M, 4: 1 DMF: H2O), haloalkanes (0.25 M, DMF), uye alkynes (0.125 M, DMF).Aliquots ye3 ml yemhinduro yega yega yakasanganiswa uye kupomba kuburikidza nereactor pamwero we75 µl/min uye tembiricha ye150°C.Vhoriyamu yose yakaunganidzwa mubhobho uye yakasvibiswa ne 10 ml ye ethyl acetate.Sample solution yakagezwa ne 3 x 10 ml yemvura.Mishonga yemvura yakasanganiswa uye yakabviswa ne 10 ml ethyl acetate, ipapo zvisikwa zvakasanganiswa zvakasanganiswa, zvakashambidzwa ne 3 × 10 ml brine, yakaomeswa pamusoro peMgSO 4 uye yakasvibiswa, ipapo solvent yakabviswa mu vacuo.Samples dzakacheneswa ne silica gel column chromatography ichishandisa ethyl acetate isati yaongororwa nemusanganiswa weHPLC, 1H NMR, 13C NMR uye yakakwirira resolution mass spectrometry (HR-MS).
Yese spectra yakawanikwa uchishandisa Thermofischer Precision Orbitrap mass spectrometer ine ESI seyo ionization sosi.Masampuli ese akagadzirwa achishandisa acetonitrile se solvent.
Ongororo yeTLC yakaitwa pamahwendefa esilica ane aluminium substrate.Iwo mahwendefa akaonekwa aine UV mwenje (254 nm) kana vanillin tsvina uye kudziyisa.
Mienzaniso yese yakaongororwa pachishandiswa VWR Chromaster system (VWR International Ltd., Leighton Buzzard, UK) ine autosampler, pombi yebhinari ine mbiru yevheni uye imwe chete wavelength detector.An ACE Equivalence 5 C18 column (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland) yakashandiswa.
Majekiseni (5 µl) akagadzirwa zvakananga kubva kune yakanyungudutswa crude reaction musanganiswa (1:10 dilution) uye yakaongororwa nemvura: methanol (50:50 kana 70:30), kunze kwemamwe masampuli anoshandisa 70:30 solvent system (inotaridzwa seyenyeredzi nhamba) pakuyerera kwe1.5 ml/min.Koramu yacho yakachengetwa pa40°C.Iyo yavelength ye detector ndeye 254 nm.
Iyo % peak nzvimbo yemuenzaniso yakaverengerwa kubva pakakwirira nzvimbo yeyakasara alkyne, iyo triazole chigadzirwa chete, uye kuunzwa kwezvinhu zvekutanga kwakaita kuti zvikwanise kuona mapikisi anoenderana.
Masampuli ese akaongororwa achishandisa Thermo iCAP 6000 ICP-OES.Ese zviyero zvecalibration akagadzirwa pachishandiswa 1000 ppm Cu yakajairwa mhinduro mu2% nitric acid (SPEX Certi Prep).Yese zviyero zvakagadzirirwa mumhinduro ye5% DMF uye 2% HNO3, uye ese masampuli akaderedzwa ka20 nemuenzaniso mhinduro yeDMF-HNO3.
UAM inoshandisa ultrasonic metal welding senzira yekubatanidza simbi foil inoshandiswa kugadzira gungano rekupedzisira.Ultrasonic metal welding inoshandisa simbi inodedera (inonzi nyanga kana ultrasonic horn) kuisa kumanikidza kune foil/yaimbova yakasanganiswa layer kuti isungirwe/yakambobatanidzwa nekuzunguza zvinhu.Nekuenderera mberi kwekushanda, sonotrode ine chimiro checylindrical uye inoputika pamusoro pepamusoro pezvinhu, gluing nzvimbo yose.Kana kudzvinyirirwa uye kuzununguka kuchiiswa, maokisi ari pamusoro pechinhu anogona kutsemuka.Kugara kudzvinyirirwa uye kudengenyeka kunogona kutungamirira kukuparadzwa kwekuoma kwezvinhu 36.Kuvhara kudhumhana nekupisa kwenzvimbo uye kudzvanywa zvino kunotungamira kune yakasimba chikamu chisungo pane zvinhu zvinosangana;inogonawo kukurudzira kubatana nekushandura simba repamusoro48.Mamiriro ekubatanidza maitiro anokunda akawanda ematambudziko ane chekuita nekushanduka kunyungudika tembiricha uye yakakwirira tembiricha mhedzisiro inotaurwa mune mamwe ekuwedzera ekugadzira tekinoroji.Izvi zvinobvumira kubatana kwakananga (kureva pasina kuchinjika kwepasi, mafirita kana zvinonamira) zvezvikamu zvakati wandei zvezvinhu zvakasiyana muchimiro chimwe chakabatanidzwa.
Chechipiri chakanakira CAM idhigirii repamusoro rekuyerera kwepurasitiki inocherechedzwa mumidziyo yesimbi kunyangwe pakudziya kwakaderera, kureva pazasi pekunyungudika kwezvinhu zvesimbi.Iko kusanganiswa kweiyo ultrasonic vibrations uye kumanikidza kunokonzera yakakwira mwero wenzvimbo yezviyo muganho wekufamba uye recrystallization pasina kukosha kwakawedzera tembiricha yakajairika yakabatana neakawanda zvinhu.Munguva yekugadzirwa kwegungano rekupedzisira, chiitiko ichi chinogona kushandiswa kunyudza zvinhu zvinoshanda uye zvisingaite pakati pezvikamu zvesimbi foil, layer by layer.Zvinhu zvakadai se optical fiber 49, kusimbisa 46, zvemagetsi makumi mashanu uye thermocouples (iyi basa) zvakabatanidzwa zvakabudirira muUAM zvimiro kuti zvigadzire magungano anoshanda uye asingaiti.
Mubasa iri, zvese zvakasiyana zvekusunga zvinhu uye UAM intercalation kugona kwakashandiswa kugadzira yakanaka microreactor ye catalytic tembiricha kutonga.
Zvichienzaniswa ne palladium (Pd) nezvimwe zvinowanzo shandiswa simbi zvinokonzeresa, Cu catalysis ine zvakati wandei zvakanakira: (i) Pahupfumi, Cu inochipa pane dzimwe simbi dzakawanda dzinoshandiswa mu catalysis uye naizvozvo inzira inoyevedza yeindasitiri yemakemikari (ii) huwandu hweCu-catalyzed cross-coupling reactions huri kuwedzera uye hunoita sehumwe hunoenderana ne5catary ,5calogies,5calogies 51,51,51,51,3,51,3,51,51,51,51,51,51,51,51,51,51,5,3,51,3. talyzed reactions inoshanda zvakanaka kana pasina mamwe ligand.Aya ma ligand anowanzo kuve akapusa uye asingadhure.kana zvichidiwa, asi izvo zvinoshandiswa muPd chemistry zvinowanzoomera, zvinodhura, uye zvinonzwa mhepo (iv) Cu, inonyanya kuzivikanwa nekukwanisa kwayo kubatanidza alkynes mu synthesis, yakadai seSonogashira's bimetallic catalyzed coupling uye cycloaddition ne azides (click chemistry) (v) Cu inogonawo kukurudzira aryphilelation yeimwe nucleotype reaction.
Munguva pfupi yapfuura, mienzaniso yeheterogenization yezvese maitiro aya pamberi peCu (0) yakaratidzwa.Izvi zvinonyanya kukonzerwa neindasitiri yemishonga uye kukura kuri kuita kudzoreredza nekushandisazve simbi inokonzeresa55,56.
Iyo 1,3-dipolar cycloaddition reaction pakati peacetylene uye azide kune 1,2,3-triazole, yakatanga kutaurwa naHuisgen mu1960s57, inoonekwa seyakabatana kuratidzira maitiro.Izvo zvinokonzerwa ne1,2,3 triazole zvimedu zvinonyanya kufarira se pharmacophore mukutsvaga zvinodhaka nekuda kwekushandiswa kwavo kwehupenyu uye kushandiswa mumishonga yakasiyana-siyana yekurapa 58.
Kuita uku kwakawana kutariswa patsva apo Sharpless nevamwe vakaunza pfungwa ye "tinya chemistry"59.Izwi rekuti "tinya chemistry" rinoshandiswa kutsanangura akasimba uye akasarudzika seti yemabatiro ekukurumidza kusanganiswa kwemakomponi matsva uye ekubatanidza maraibhurari achishandisa heteroatomic bonding (CXC)60.Iko kukwezva kwekugadzirwa kwemaitiro aya kunokonzerwa negoho guru rakabatana nazvo.mamiriro ari nyore, kuramba okisijeni nemvura, uye kupatsanurwa kwechigadzirwa kuri nyore61.
Iyo classical 1,3-dipole Huisgen cycloaddition haiwire muchikamu che "tinya chemistry".Nekudaro, Medal uye Sharpless yakaratidza kuti iyi azide-alkyne coupling chiitiko inopinda 107-108 pamberi peCu (I) zvichienzaniswa nekukasira kukuru muyero yekusaita-catalytic 1,3-dipolar cycloaddition 62,63.Iyi yepamusoro-soro yekugadzirisa maitiro haidi kuchengetedza mapoka kana maitiro akaoma uye inopa inenge yakakwana kutendeuka uye kusarudza ku1,4-disubstituted 1,2,3-triazoles (anti-1,2,3-triazoles) nekufamba kwenguva (Fig. 3).
Isometric mhedzisiro yezvakajairwa uye mhangura-catalyzed Huisgen cycloadditions.Cu(I) -catalyzed Huisgen cycloadditions inopa chete 1,4-disubstituted 1,2,3-triazoles, nepo thermally induced Huisgen cycloadditions inowanzopa 1,4- uye 1,5-triazoles musanganiswa 1:1 we azole stereoisomers.
Mazhinji maprotocol anosanganisira kudzikiswa kwenzvimbo dzakagadzikana dzeCu(II), sekuderedzwa kweCuSO4 kana Cu(II)/Cu(0) kompani pamwe chete nesodium salt.Kuenzaniswa nedzimwe simbi dzakagadziridzwa maitiro, kushandiswa kweCu(I) kune mabhenefiti makuru ekuve isingadhure uye nyore kubata.
Kinetic uye isotopic zvidzidzo naWorrell et al.65 vakaratidza kuti kana iri materminal alkynes, maviri akaenzana emhangura anobatanidzwa mukuita kuti reactivity yeimwe neimwe molecule ine chekuita neazide.Iyo yakarongwa nzira inopfuurira kuburikidza nenhanhatu-mitezo yemhangura yesimbi mhete yakaumbwa nekubatanidzwa kweazide kune σ-yakasungwa copper acetylide ine π-yakasungwa mhangura seyakagadzikana donor ligand.Copper triazolyl derivatives inogadzirwa semhedzisiro yering contraction inoteverwa neproton decomposition kuita zvigadzirwa zve triazole uye kuvhara kutenderera kwecatalytic.
Nepo mabhenefiti ekuyerera chemistry zvishandiso akanyatso kunyorwa, pave paine chishuwo chekubatanidza maturusi ekuongorora mune aya masisitimu eiyo chaiyo-nguva process yekutarisa mu situ66,67.UAM yakaratidza kuva nzira yakakodzera yekugadzira nekugadzira yakaoma kwazvo 3D kuyerera reactors kubva kune catalytically inoshanda, thermally conductive zvinhu zvine zvakananga embedded sensing zvinhu (Fig. 4).
Aluminium-copper flow reactor inogadzirwa ne ultrasonic additive kugadzira (UAM) ine yakaoma yemukati chiteshi chimiro, yakavakirwa-mukati thermocouples uye catalytic reaction chamber.Kuona nzira dzemvura dzemukati, mufananidzo wakajeka wakagadzirwa uchishandisa sterolithography inoratidzwa zvakare.
Kuti ive nechokwadi chekuti mareactor anogadzirwa kuitira ramangwana organic reactions, zvinonyungudutsa zvinofanirwa kudziya zvakachengeteka pamusoro penzvimbo yavo yekuvira;vari kumanikidzwa uye tembiricha akaedzwa.Kuedzwa kwekumanikidza kwakaratidza kuti sisitimu inochengetedza yakagadzikana uye inogara ichimanikidza kunyangwe pakakwirira kumanikidzwa muhurongwa (1.7 MPa).Hydrostatic bvunzo dzakaitwa pakamuri tembiricha uchishandisa H2O semvura.
Kubatanidza yakavakirwa-mukati (Mufananidzo 1) thermocouple kune tembiricha data logger yakaratidza kuti tembiricha ye thermocouple yaive 6 °C (± 1 °C) pasi peiyo tembiricha yakarongwa muFlowSyn system.Kazhinji, kuwedzera kwe10 ° C kwekushisa kunowedzera kaviri chiyero chekuita, saka mutsauko wekushisa wemadhigirii mashoma unogona kushandura chiyero chekuita zvakanyanya.Musiyano uyu unokonzerwa nekurasikirwa kwekushisa mukati meRPV yese nekuda kweiyo yakanyanya kupisa diffusivity yezvinhu zvinoshandiswa mukugadzira maitiro.Uku kudonha kwekupisa kunogara uye nekudaro kunogona kuverengerwa pakumisikidza michina kuti ive nechokwadi chekuti tembiricha yasvika uye kuyerwa panguva yekuita.Nekudaro, ichi online chekutarisa chishandiso chinogonesa kudzora kwakasimba kwekuita tembiricha uye inobatsira kune yakanyatsojeka maitiro optimization uye kusimudzira mamiriro akakwana.Aya masensa anogona zvakare kushandiswa kuona exothermic reactions uye kudzivirira kutiza maitiro mumahombe masisitimu.
Iyo reactor inoratidzwa mubepa rino 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 anozivikanwa ane chekuita nekugadziriswa kwemhangura kana aruminiyamu alloy (ii) yakagadziridzwa yemukati chiteshi kugadzirisa kana ichienzaniswa nehupfu mubhedha kunyunguduka (PBive6 kuyerera kwelaser) 2 nzira dzekunyungudika (PSL 5) kunyunguduka kwemubhedha (PFive6) 5. 26 (iii) kuderera kwekushisa kwekushisa, iyo inofambisa zvakananga kubatanidza sensors, izvo zvisingakwanisi muhutano hwebhedha yehupfu, (v) kukunda hurombo hwemagetsi ekugadzirisa zvinhu uye kunzwisisika kwezvikamu zvepolymer-based kune zvakasiyana-siyana zvinowanzoita organic solvents17,19.
Kushanda kweiyo reactor kwakaratidzwa nehuwandu hwemhangura-catalyzed alkinazide cycloaddition reactions pasi pemamiriro ekuenderera mberi ekuyerera (Fig. 2).Iyo ultrasonic yakadhindwa yemhangura reactor inoratidzwa mufig.4 yakabatanidzwa nekutengesa kuyerera kwehurongwa uye yakashandiswa kugadzira raibhurari yeazide yakasiyana-siyana 1,4-disubstituted 1,2,3-triazoles uchishandisa tembiricha inodzorwa maitiro eacetylene uye alkyl boka halides muhupo hwe sodium chloride (Fig. 3).Kushandiswa kwekuenderera mberi kwekuyerera kunoderedza nyaya dzekuchengetedza dzinogona kumuka mumatanho e-batch, sezvo kuita uku kunobudisa zvakanyanya uye zvine ngozi azide intermediates [317], [318].Pakutanga, mhinduro yacho yakagadziridzwa ye cycloaddition ye phenylacetylene uye iodoethane (Scheme 1 - Cycloaddition ye phenylacetylene uye iodoethane) (ona Fig. 5).
(Kumusoro kuruboshwe) Schematic yegadziriro inoshandiswa kubatanidza 3DP reactor mumhepo inoyerera (kumusoro kurudyi) yakawanikwa kubva kune yakagadziridzwa (pasi) chirongwa cheHuisgen 57 cycloaddition scheme pakati pe phenylacetylene uye iodoethane kuitira optimization uye kuratidza yakagadziridzwa yekushandura chiyero chemaitiro ekuita.
Nekudzora nguva yekugara yeanoita reactants muchikamu chinokonzeresa cheiyo reactor uye nekunyatso tarisisa tembiricha yekuita neyakasanganiswa yakananga thermocouple sensor, maitiro ekuita anogona kukurumidza uye nemazvo akagadziridzwa neishoma yenguva uye zvinhu.Yakakurumidza kuwanikwa kuti kutendeuka kwepamusoro kwakawanikwa uchishandisa nguva yekugara yemaminetsi gumi nemashanu uye tembiricha yekuita 150 ° C.Iyo inogona kuoneka kubva kune coefficient plot yeMODE software kuti zvese nguva yekugara uye tembiricha yekuita zvinoonekwa seakakosha mamiriro emuenzaniso.Kumhanyisa yakavakirwa-mukati optimizer uchishandisa aya akasarudzwa mamiriro anogadzira seti yemamiriro ekuita akagadzirirwa kukwirisa chigadzirwa nzvimbo dzepamusoro apo ichidzikira kutanga zvinhu nzvimbo dzepamusoro.Kunatsiridza uku kwakaburitsa 53% shanduko yechigadzirwa chetriazole, icho chainyatsoenderana nekufanotaura kwe54%.