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Kugadzira zvinhu zvinowedzera kuri kuchinja nzira iyo vaongorori nevashandi vemaindasitiri vanogadzira nekugadzira michina yemakemikari kuti ienderane nezvinodiwa zvavo. Mubasa iri, tinopa muenzaniso wekutanga we "flow reactor" yakagadzirwa ne "solid-state metal sheet lamination technique" Ultrasonic Additive Manufacturing (UAM) ine zvikamu zve "catalytic" zvakasanganiswa zvakananga uye zvinhu zvinonzwa. Tekinoroji yeUAM haingogumiri pakukunda zvakawanda zvezvipingamupinyi zviripo pari zvino zvine chekuita nekugadzirwa kwezvinhu zvinowedzera zvemakemikari, asi inowedzerawo zvakanyanya kugona kwemidziyo yakadaro. Makomputa e1,2,3-triazole akakosha akagadzirwa neCu-mediated Huisgen 1,3-dipolar cycloaddition reaction achishandisa UAM chemistry set-up. Nekushandisa hunhu hwakasiyana hweUAM uye continuous flow processing, mudziyo uyu unokwanisa kukonzera maitiro anoenderera mberi uku uchipawo mhinduro chaiyo yekutarisa nekugadzirisa maitiro.
Nekuda kwezvakanaka zvayo zvikuru kupfuura zvimwe zvinhu zvakawanda, kemikari yekuyerera kwemvura inzvimbo yakakosha uye iri kukura mune zvedzidzo neindasitiri nekuda kwekukwanisa kwayo kuwedzera kusarudzwa uye kushanda zvakanaka kwekugadzirwa kwemakemikari. Izvi zvinotangira pakuumbwa kwemamorekuru eorganic1 kusvika kumakemikari emishonga2,3 uye zvigadzirwa zvechisikigo4,5,6. Zvinopfuura 50% zvezviitiko muindasitiri yemakemikari akanaka uye yemishonga zvinogona kubatsirwa nekushandiswa kwekugadzirisa kuyerera kunoramba kuripo7.
Mumakore achangopfuura, kwave netsika iri kukura yemapoka ari kutsvaga kutsiva midziyo yegirazi yechinyakare kana michina yemakemikari inoyerera ne "midziyo yereaction" inogadziriswa (AM) chemistry.8. Dhizaini inoenderana, kugadzirwa nekukurumidza, uye kugona kwe3-dimensional (3D) kwemaitiro aya zvinobatsira kune avo vanoda kugadzirisa midziyo yavo kuita seti chaiyo yereaction, midziyo, kana mamiriro. Kusvika pari zvino, basa iri rave rakanyanya kutarisa pakushandiswa kwetekinoroji dze3D dzekudhinda dzakavakirwa papolymer dzakadai se stereolithography (SL)9,10,11, fused deposition modeling (FDM)8,12,13,14 uye inkjet printing 7, 15, 16. Kushaikwa kwesimba uye kugona kwemidziyo yakadaro kuita akasiyana-siyana emakemikari reaction/analyses17, 18, 19, 20 chinhu chikuru chinotadzisa kushandiswa kweAM zvakanyanya mumunda uyu17, 18, 19, 20.
Nekuda kwekuwedzera kwekushandiswa kwemakemikari ekuyerera kwemvura uye hunhu hwakanaka hune chekuita neAM, pane chikonzero chekutsvaga matekiniki epamusoro anogonesa vashandisi kugadzira midziyo yemagetsi ine hunyanzvi hwemakemikari nekuongorora. Matekiniki aya anofanira kugonesa vashandisi kusarudza kubva pazvinhu zvakasiyana-siyana zvakasimba kana zvinoshanda zvinokwanisa kubata mamiriro akasiyana-siyana ekuita, ukuwo zvichibatsirawo mhando dzakasiyana dzekuongorora kubva mumudziyo kuti zvibvumire kutarisa nekugadzirisa maitiro.
Imwe nzira yekugadzira zvinhu ine mukana wekugadzira ma reactor emakemikari akagadzirwa nemaoko ndeye Ultrasonic Additive Manufacturing (UAM). Iyi nzira ye solid-state sheet lamination inoshandisa ultrasonic oscillations kuma foil esimbi matete kuitira kuti azvibatanidze pamwe chete layer by layer nekudziisa kushoma uye plastic flow yakawanda 21, 22, 23. Kusiyana nedzimwe nzira dzakawanda dzeAM, UAM inogona kubatanidzwa zvakananga ne subtractive manufacturing, inozivikanwa se hybrid manufacturing process, umo in-situ periodic computer numerical control (CNC) milling kana laser machining inotsanangura chimiro che layer yezvinhu zvakasungwa 24, 25. Izvi zvinoreva kuti mushandisi haaganhurirwi nematambudziko ane chekuita nekubvisa residual raw build material kubva mudiki fluid channels, izvo zvinowanzoitika neupfu ne liquid AM systems26, 27, 28. Rusununguko urwu rwekugadzira runosvikawo kune sarudzo dzezvinhu zviripo - UAM inogona kubatanidza zvinhu zvakafanana nekupisa uye zvakasiyana muchikamu chimwe chete chemaitiro. Kusarudzwa kwezvinobatanidzwa kupfuura melt process zvinoreva kuti zvinodiwa zve mechanical ne chemical zvemashandisirwo chaiwo zvinogona kuzadzikiswa zviri nani. Kuwedzera kune solid state bonding, imwe Chinhu chinosangana nacho panguva yekubatanidza kwe ultrasonic ndiko kuyerera kwakanyanya kwezvinhu zvepurasitiki patembiricha yakaderera 29, 30, 31, 32, 33. Ichi chinhu chakasiyana cheUAM chinogona kubatsira kupinza zvinhu zvemakanika/kupisa pakati pesimbi pasina kukuvara. Masensa akabatanidzwa eUAM anogona kubatsira kuendeswa kweruzivo rwenguva chaiyo kubva kumushandisi kubva kumuchina kuenda kumushandisi kuburikidza nekuongorora kwakabatanidzwa.
Basa revanyori rekare32 rakaratidza kugona kwemaitiro eUAM kugadzira zvivakwa zvesimbi zve3D microfluidic zvine kugona kwakabatana kwekunzwa. Ichi chishandiso chekutarisa chete. Pepa rino rinopa muenzaniso wekutanga we microfluidic chemical reactor yakagadzirwa neUAM; chishandiso chinoshanda chisingangotarise chete asiwo chinokurudzira kugadzirwa kwemakemikari kuburikidza nezvinhu zve catalyst zvakabatanidzwa. Chishandiso ichi chinobatanidza mabhenefiti akati wandei ane chekuita neUAM tekinoroji mukugadzira zvishandiso zve3D chemical, zvakaita se: kugona kushandura magadzirirwo akazara e3D zvakananga kubva kumamodeli ekugadzira anobatsira pakombiyuta (CAD) kuita zvigadzirwa; kugadzirwa kwezvinhu zvakawanda kusanganisa high thermal conductivity uye catalytic materials; uye kuisa masensa ekupisa zvakananga pakati pemvura dzinoshandiswa kuti pave nekuongororwa kwakarurama kwekupisa kwekuita uye kudzora. Kuratidza mashandiro ereactor, raibhurari yemakomputa e1,4-dissubtituted 1,2,3-triazole akakosha mumishonga akagadzirwa neHuisgen 1,3-dipolar cycloaddition ine mhangura. Basa iri rinoratidza kuti kushandiswa kwesainzi yezvinhu uye dhizaini inobatsirwa nekombuta kunogona kuvhura mikana mitsva nemikana yekemikari kuburikidza nekutsvagisa kwakasiyana-siyana.
Zvese zvinonyungudutsa uye ma reagents zvakatengwa kubva kuSigma-Aldrich, Alfa Aesar, TCI kana Fischer Scientific uye zvakashandiswa pasina kucheneswa kare. 1H uye 13C NMR spectra zvakanyorwa pa400 MHz uye 100 MHz, zvichiteerana, zvakawanikwa uchishandisa JEOL ECS-400 400 MHz spectrometer kana Bruker Avance II 400 MHz spectrometer uye CDCl3 kana (CD3)2SO se solvent. Zvese zvinoitwa uchishandisa Uniqsis FlowSyn flow chemistry platform.
UAM yakashandiswa kugadzira michina yese muchidzidzo ichi. Tekinoroji iyi yakagadzirwa muna 1999, uye ruzivo rwayo rwehunyanzvi, maparamita ekushanda uye budiriro kubva pakugadzirwa kwayo zvinogona kudzidzwa kuburikidza nezvinhu zvinotevera zvakaburitswa34,35,36,37. Mudziyo uyu (Mufananidzo 1) wakagadzirwa uchishandisa simba rakawanda, 9kW SonicLayer 4000® UAM system (Fabrisonic, OH, USA). Zvinhu zvakasarudzwa pakugadzira mudziyo wekuyerera zvaive Cu-110 uye Al 6061. Cu-110 ine huwandu hwakawanda hwemhangura (99.9% mhangura), zvichiita kuti ive yakanaka kune copper-catalyzed reactions, uye nekudaro inoshandiswa se "active layer mukati me microreactor. Al 6061 O inoshandiswa se "bulk" material, zvakare Embedding layer inoshandiswa pakuongorora; Alloy assistant component embedding uye annealed condition yakabatana neCu-110 layer. Al 6061 O inyaya yakaratidzwa kuti inoenderana zvakanyanya neUAM processes38, 39, 40, 41 uye yakaedzwa ikawanikwa kuti yakasimba mumakemikari nema reagents anoshandiswa mubasa iri. Kusanganiswa kweAl 6061 O neCu-110 kunoonekwawo semusanganiswa wezvinhu zvinoenderana neUAM uye nokudaro chinhu chakakodzera chidzidzo ichi. 38,42 Midziyo iyi yakanyorwa muTafura 1 pazasi.
Matanho ekugadzira reactor (1) Al 6061 substrate (2) Kugadzirwa kwenzira yepasi yakaiswa pa copper foil (3) Kuisa thermocouples pakati pezvikamu (4) Nzira yepamusoro (5) Kupinda nekubuda (6) Monolithic reactor.
Pfungwa yekugadzira nzira yemvura ndeyekushandisa nzira yakamanikana kuwedzera daro rinofamba mvura mukati mechip, ukuwo ichichengetedza chip iri pahukuru hunogoneka. Kuwedzera uku kwedaro kunodiwa kuti kuwedzere nguva yekudyidzana kwe catalyst/reagent uye kupa goho rakanaka rezvigadzirwa. Chip dzinoshandisa 90° bends kumagumo enzira yakatwasuka kuti dzikonzere kusanganiswa kwakashata mukati memudziyo44 uye kuwedzera nguva yekubatana kwemvura nepamusoro (catalyst). Kuti zviwedzere kusanganiswa kunogona kuwanikwa, dhizaini ye reactor ine ma reagent inlets maviri akabatanidzwa paY-junction isati yapinda muchikamu chekusanganisa che serpentine. Inlet yechitatu, iyo inoyambuka rwizi pakati penzvimbo yayo yekugara, inosanganisirwa mukugadzirwa kwe multistep reaction syntheses dzemangwana.
Machaneli ese ane chimiro chesikweya (hapana maenga edhirowa), mhedzisiro yekushandiswa kweCNC kugadzira geometry yechaneli. Zviyero zvechaneli zvinosarudzwa kuti zvive nechokwadi chekuti huwandu hwepamusoro (hwe microreactor) hunobuda, ukuwo hudiki zvakakwana kuti hubatsire kudyidzana kwepamusoro (catalysts) yemvura zhinji dzirimo. Saizi yakakodzera yakavakirwa pane zvakaitika kare zvevanyori nemidziyo yesimbi-fluidic ye reaction. Zviyero zvemukati zvechaneli yekupedzisira zvaive 750 µm x 750 µm uye huwandu hwese hwe reactor hwaive 1 ml. Chinobatanidza chakabatanidzwa (1/4″—28 UNF thread) chinosanganisirwa mudhizaini kuti chibvumire kupindirana kuri nyore kwemudziyo nemidziyo yemakemikari yekuyerera kwemhepo. Saizi yechaneli inoganhurirwa nehukobvu hwechinhu chefoil, hunhu hwayo hwemakanika, uye ma parameter ekubatanidza anoshandiswa ne ultrasonics. Pahupamhi hwakati hwechinhu chakapihwa, chinhu chacho chicha "sag" muchaneli yakagadzirwa. Pari zvino hapana modhi chaiyo yekuverenga uku, saka upamhi hwechaneli hwechinhu chakapihwa nedhizaini inoonekwa nekuyedza; muchiitiko ichi, upamhi hwe750 μm hahuzokonzere kudonha.
Chimiro (sikweya) chechiteshi chinoonekwa nekushandisa muchina wekucheka sikweya. Chimiro nehukuru hwechiteshi zvinogona kuchinjwa nemichina yeCNC inoshandisa maturusi akasiyana ekucheka kuti iwane mwero wekuyerera kwakasiyana uye hunhu. Muenzaniso wekugadzira chiteshi chechimiro chakakombama uchishandisa chishandiso che125 μm unogona kuwanikwa mubasa raMonaghan45. Kana jira refoil rakaiswa nenzira yakarongwa, pamusoro pezvinhu zvefoil pamusoro pechiteshi pachava nemagumo akatsetseka (sikweya). Mubasa iri, kuitira kuchengetedza kuenzanisa kwechiteshi, mutsetse wesikweya wakashandiswa.
Munguva yekumbomira kwakagadzirwa kare, ma "thermocouple temperature probes" (Type K) anoiswa zvakananga mukati memudziyo pakati pemapoka e "channel" epamusoro neepasi (Mufananidzo 1 - Danho rechitatu). Ma "thermocouples" aya anogona kutarisa shanduko dzetembiricha kubva pa -200 kusvika 1350 °C.
Maitiro ekuisa simbi anoitwa nenyanga yeUAM uchishandisa foil yesimbi ine upamhi hwe25.4 mm, ine ukobvu hwe150 micron. Aya mafoil layers anobatanidzwa muzvikamu zvakatevedzana zviri pedyo kuti afukidze nzvimbo yese yekuvaka; saizi yezvinhu zvakachengetwa yakakura kupfuura chigadzirwa chekupedzisira sezvo maitiro ekubvisa achigadzira chimiro chekupedzisira chenet. CNC machining inoshandiswa kugadzira contours dzekunze nedzemukati dzemidziyo, zvichiita kuti kupedzisa kwemidziyo nemachannels akaenzana nemidziyo yakasarudzwa uye maCNC process parameters (inenge 1.6 μm Ra mumuenzaniso uyu). Kuisa zvinhu zvinogadzirwa ne ultrasonic uye machining cycles zvinoenderera mberi zvinoshandiswa mukati memaitiro ekugadzira michina kuitira kuve nechokwadi chekuti divi rakarurama rinochengetwa uye chikamu chakapedzwa chichasangana nemazinga eCNC finish milling accuracy. Upamhi hwechiteshi chinoshandiswa pamudziyo uyu hudiki zvakakwana kuti uve nechokwadi chekuti foil material haitsvedzeri mu fluid channel, saka channel inochengetedza sikweya cross-section. Mipata inogona kuitika mu foil material uye maUAM process parameters yakaongororwa nekuyedza nemumwe mugadziri (Fabrisonic LLC, USA).
Zvidzidzo zvakaratidza kuti kupararira kudiki kwezvikamu kunoitika paUAM bonding interface 46, 47 pasina kuwedzerwa kwekupisa, saka pamidziyo iri mubasa iri, Cu-110 layer inoramba yakasiyana neAl 6061 layer uye inochinja kamwe kamwe.
Isa chinodzora kumanikidzwa kwesimba remagetsi che250 psi (1724 kPa) chakagadziriswa kare (BPR) kusvika pakubuda kwereactor wopomba mvura nepakati pereactor nechiyero che0.1 kusvika 1 mL min-1. Kumanikidzwa kwereactor kwakatariswa uchishandisa FlowSyn built-in system pressure sensor kuti uone kuti system inogona kuchengetedza kumanikidzwa kwakasimba nguva dzose. Kugona kwekupisa mukati me flow reactor kwakaedzwa nekuona mutsauko uripo pakati pe thermocouples dzakaiswa mukati me reactor nedziri mukati meFlowSyn chip heating plate. Izvi zvinoitwa nekuchinja tembiricha ye hotplate inorongwa pakati pe100 ne150 °C mu25 °C increments uye nekucherechedza mutsauko uripo pakati petembiricha dzakarongwa nedzakanyorwa. Izvi zvakaitwa uchishandisa tc-08 data logger (PicoTech, Cambridge, UK) uye software yePicoLog inoperekedza.
Maitiro ekuita cycloaddition ephenylacetylene ne iodoethane akagadziriswa (Scheme 1- Cycloaddition yephenylacetylene ne iodoethane Scheme 1- Cycloaddition yephenylacetylene ne iodoethane). Kugadzirisa uku kwakaitwa nenzira yakazara yekugadzira factorial yekuedza (DOE), uchishandisa tembiricha nenguva yekugara sema parameter anochinja, uku uchigadzirisa alkyne:azide ratio pa1:2.
Mhinduro dzakasiyana dze sodium azide (0.25 M, 4:1 DMF:H2O), iodoethane (0.25 M, DMF), uye phenylacetylene (0.125 M, DMF) dzakagadzirwa. 1.5 mL aliquot yemhinduro yega yega yakasanganiswa ndokupombwa ne reactor pachiyero chekuyerera kwemvura netembiricha yaidiwa. Mhinduro yemuenzaniso yakatorwa sechikamu chepamusoro che triazole product kune phenylacetylene starting material uye yakatsanangurwa ne high performance liquid chromatography (HPLC). Kuti pave nekuenderana kwekuongorora, maitiro ese akatorwa mushure mekunge musanganiswa we reaction wabva mu reactor. Ma parameter ranges akasarudzwa kuti agadziriswe anoratidzwa muTafura 2.
Samples dzese dzakaongororwa uchishandisa Chromaster HPLC system (VWR, PA, USA) ine quaternary pombi, column oven, variable wavelength UV detector uye autosampler. Column yacho yaive Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 mm muhukuru, 5 µm particle size, yakachengetedzwa pa40 °C. Iyo solvent yaive isocratic 50:50 methanol: water pa flow rate ye 1.5 mL.min-1. Vhoriyamu ye injection yaive 5 µL uye detector wavelength yaive 254 nm. Nzvimbo ye % peak ye DOE sample yakaverengerwa kubva kunzvimbo dze peak dze residual alkyne ne triazole products chete. Kubaiwa kwe starting material kunobvumira kuziva peaks dzakakodzera.
Kubatanidza zvinobuda mukuongorora reactor neMODDE DOE software (Umetrics, Malmö, Sweden) kwakabvumira kuongororwa kwakazara kwemafambiro emhedzisiro uye kusarudzwa kwemamiriro ekuita akakodzera ecycloaddition iyi. Kumhanyisa iyo yakavakirwa mukati uye kusarudza mazwi ese akakosha emuenzaniso kunopa seti yemamiriro ekuita akagadzirirwa kuwedzera nzvimbo yepamusoro yechigadzirwa uku uchideredza nzvimbo yepamusoro yezvinhu zvekutanga zveacetylene.
Kuoxidation kwemhangura yepamusoro mukati mekamuri re catalytic reaction kwakawanikwa uchishandisa mhinduro yehydrogen peroxide (36%) inoyerera nemukamuri re reaction (flow rate = 0.4 mL min-1, nguva yekugara = 2.5 min) risati ragadzirwa raibhurari yega yega ye triazole compound.
Kana mamiriro ezvinhu akanyatsonaka aonekwa, akaiswa kune akasiyana-siyana e-acetylene ne-haloalkane derivatives kuti zvibvumire kuunganidzwa kwekugadzirwa kweraibhurari diki, nokudaro zvichigadzira kugona kwekushandisa mamiriro aya kune akasiyana-siyana ezvinogona 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 ndokupombwa ne reactor pa75 µL. min-1 uye 150 °C. Huwandu hwese hwakaunganidzwa mubhodhoro ndokusanganiswa ne10 mL ye ethyl acetate. Sample solution yakagezwa ne3 × 10 mL yemvura. Aqueous layers dzakasanganiswa ndokubviswa ne10 mL ye ethyl acetate; organic layers dzakazobatanidzwa, dzakagezwa ne3 x 10 mL ye brine, dzakaomeswa pamusoro peMgSO4 ndokusefa, ipapo solvent yakabviswa mu vacuo. Samples dzakacheneswa ne column chromatography pa silica gel uchishandisa ethyl acetate vasati vaongorora ne musanganiswa we HPLC, 1H NMR, 13C NMR uye high resolution mass spectrometry (HR-MS).
Maspectra ese akawanikwa achishandisa Thermofischer precision Orbitrap resolution mass spectrometer ine ESI senzvimbo yeionization. Samples dzese dzakagadzirwa dzichishandisa acetonitrile se solvent.
Ongororo yeTLC yakaitwa pamaplate e silica ane aruminiyamu. Maplate acho akaonekwa nechiedza cheUV (254 nm) kana kuti vanillin staining uye heating.
Samples dzese dzakaongororwa pachishandiswa system yeVWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) ine autosampler, column oven binary pump uye single wavelength detector. Column yakashandiswa yaive ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland).
Majekiseni (5 µL) akagadzirwa zvakananga kubva mumusanganiswa we crude reaction diluted (1:10 dilution) uye akaongororwa nemvura:methanol (50:50 kana 70:30), kunze kwemamwe masampuli anoshandisa 70:30 solvent system (inoratidzwa senhamba yenyeredzi) pachiyero chekuyerera kwe1.5 mL/min. Chinyorwa chakachengetwa pa40 °C. Hurefu hwewavelength ye detector i254 nm.
Nzvimbo yepamusoro yemuyero yakaverengerwa kubva panzvimbo yepamusoro yealkyne yakasara, chigadzirwa chetriazole chete, uye kuiswa kwechinhu chekutanga kwakabvumira kuzivikanwa kwenzvimbo dzakakodzera.
Sampuro dzese dzakaongororwa uchishandisa Thermo iCAP 6000 ICP-OES. Mitemo yese yekugadzirisa yakagadzirwa uchishandisa mhinduro yakajairika ye1000 ppm Cu mu 2% nitric acid (SPEX Certi Prep). Mitemo yese yakagadzirwa mu 5% DMF uye 2% HNO3 solution, uye sampuro dzese dzakasanganiswa ka20 mumushonga wemuenzaniso weDMF-HNO3.
UAM inoshandisa ultrasonic metal welding senzira yekubatanidza zvinhu zvesimbi zvinoshandiswa kuvaka gungano rekupedzisira. Ultrasonic metal welding inoshandisa chishandiso chesimbi chinodedera (chinonzi horn kana ultrasonic horn) kuisa kumanikidzwa kune foil layer/yaimbova yakabatanidzwa kuti ibatane uku ichidedera zvinhu. Kuti ishande nguva dzose, sonotrode yakaita cylindrical uye inotenderera pamusoro pechinhu, ichibatanidza nzvimbo yese. Kana kumanikidzwa nekudedera zvikashandiswa, ma oxide ari pamusoro pechinhu anogona kutsemuka. Kuenderera mberi nekudzvinyirirwa nekudedera kunogona kukonzera kusasimba kwezvinhu kudonha 36. Kusangana kwepedyo nekupisa nekudzvinyirirwa kunokonzerwa nenzvimbo kunotungamira kune solid-state bonding panzvimbo dzezvinhu; zvinogonawo kubatsira kunamatira kuburikidza nekuchinja kwesimba repamusoro48. Hunhu hwe bonding mechanism inokunda matambudziko mazhinji ane chekuita nekushanduka kwekushisa uye kupisa kwakanyanya kutaurwa mune dzimwe nzira dzekugadzira zvinowedzera. Izvi zvinobvumira kubatana zvakananga (kureva, pasina kugadziriswa kwenzvimbo, fillers kana adhesives) yezvikamu zvakawanda zvezvinhu zvakasiyana kuita chimiro chimwe chete chakabatanidzwa.
Chimwe chinhu chakanaka cheUAM imhando yepamusoro yekuyerera kwepurasitiki inoonekwa muzvinhu zvesimbi, kunyangwe patembiricha yakaderera, kureva kuti pasi penzvimbo yekunyunguduka kwezvinhu zvesimbi. Kusanganiswa kwe ultrasonic oscillation nekumanikidzwa kunokonzera huwandu hwakawanda hwekufamba kwemiganhu yegorosi uye recrystallization pasina kuwedzera kukuru kwekupisa kwakajairika kwakabatana nezvinhu zvakawanda. Munguva yekuvakwa kwegungano rekupedzisira, chiitiko ichi chinogona kushandiswa kuisa zvikamu zvinoshanda uye zvisingashande pakati pezvikamu zvesimbi foil, layer nelayer. Zvinhu zvakaita se optical fibers 49, reinforcements 46, electronics 50, uye thermocouples (basa iri) zvese zvakapinzwa zvinobudirira muUAM structures kugadzira active uye passive composite assemblies.
Mubasa iri, mikana yakasiyana yekubatanidza zvinhu uye yekubatanidza UAM yakashandiswa kugadzira microreactor yepamusoro-soro yekutarisa tembiricha.
Kana tichienzanisa nepalladium (Pd) nedzimwe catalysts dzesimbi dzinowanzoshandiswa, Cu catalysis ine zvakanakira zvakawanda: (i) Panyaya dzehupfumi, Cu inodhura zvishoma pane dzimwe simbi dzakawanda dzinoshandiswa mu catalysis uye nokudaro isarudzo inokwezva indasitiri yekugadzira makemikari (ii) Mhando dzeCu-catalyzed cross-coupling reactions dziri kuwedzera uye dzinoita sedzinopindirana nenzira dzePd-based methodologies51,52,53 (iii) Cu-catalyzed reactions dzinoshanda zvakanaka pasina mamwe ma ligands. Aya ma ligands anowanzo kuve nyore muchimiro uye asingadhuri kana achida, nepo ayo anoshandiswa muPd chemistry anowanzo kuve akaomarara, anodhura, uye anonzwa mhepo (iv) Cu, inonyanya kuzivikanwa nekukwanisa kwayo kusunga ma alkynes mu synthesis, Semuenzaniso, bimetallic-catalyzed Sonogashira coupling uye cycloaddition ne azides (click chemistry) (v)Cu inokwanisawo kukurudzira arylation yema nucleophiles akati wandei muUllmann-type reactions.
Mienzaniso yekuchinjana kwemaitiro ese aya yakaratidzwa munguva pfupi yapfuura paine Cu(0). Izvi zvinonyanya kukonzerwa neindasitiri yemishonga uye kuwedzera kwekutarisa pakudzoreredza nekushandisazve simbi catalyst55,56.
Yakatangwa naHuisgen muma1960s57, 1,3-dipolar cycloaddition reaction pakati peacetylene neazide kune 1,2,3-triazole inoonekwa se synergistic demonstration reaction. Zvikamu zve 1,2,3 triazole zvinoonekwa se pharmacophore mumunda wekuwana mishonga nekuda kwekushandiswa kwayo muzvinhu zvakasiyana-siyana zvekurapa.
Maitiro aya akatanga kuonekwa zvakare apo Sharpless nevamwe vakatanga pfungwa ye "click chemistry"59. Izwi rekuti "click chemistry" rinoshandiswa kutsanangura seti yakasimba, yakavimbika uye inosarudzwa yemaitiro ekukurumidza kugadzira mishonga mitsva nemaraibhurari ekubatanidza kuburikidza ne heteroatom linkage (CXC)60 Kukwezva kwemaitiro aya kunobva mukukohwa kwawo kwakawanda, mamiriro ekuita ari nyore, kudzivirira okisijeni nemvura, uye kupatsanurwa kwechigadzirwa kuri nyore61.
Huisgen 1,3-dipole cycloaddition yekare haisi yeboka re "click chemistry". Zvisinei, Medal naSharpless vakaratidza kuti chiitiko ichi che azide-alkyne coupling chinoitwa 107 kusvika 108 pamberi peCu(I) zvichienzaniswa ne uncatalyzed 1,3-dipolar cycloaddition 62,63 significant rate acceleration. Iyi nzira yakagadziriswa ye reaction haidi mapoka ekudzivirira kana mamiriro ekuita akaomarara uye inopa kutendeuka kwakakwana uye kusarudza kune 1,4-dissubstituted 1,2,3-triazoles (anti-1,2,3-triazole) panguva yakatarwa (Mufananidzo 3).
Mhedzisiro yeIsometric yeHuisgen cycloadditions yakajairika uye yakakamurwa nemhangura. Huisgen cycloadditions inokamurwa neCu(I) inoburitsa 1,4-distituted 1,2,3-triazoles chete, nepo Huisgen cycloadditions inokonzerwa nekupisa inowanzoburitsa 1,4- uye 1,5-triazoles 1:1 musanganiswa we stereoisomers yeazoles.
Maitiro mazhinji anosanganisira kuderedza manyuko eCu(II) akagadzikana, akadai sekuderedza mhando dzeCuSO4 kana Cu(II)/Cu(0) pamwe chete nesodium salts. Zvichienzaniswa nedzimwe nzira dzinoshandiswa nesimbi, kushandiswa kweCu(I) kune mabhenefiti makuru ekusadhura zvakanyanya uye kuri nyore kubata.
Ongororo dzeKinetic neIsotopic Labeling dzakaitwa naWorrell et al. 65 dzakaratidza kuti, kana paine ma terminal alkynes, zvinhu zviviri zvakafanana zvemhangura zvinobatanidzwa mukuita kuti molekyuru yega yega iite reactivity kune azide. Nzira iyi inopfuura kuburikidza nering yesimbi yemhangura ine nhengo nhanhatu inoumbwa nekubatana kweazide kune σ-bonded copper acetylene ne π-bonded copper se stable donor ligand. Triazolyl copper derivatives inoumbwa nekupwanyika kwering, ichiteverwa nekuora kweproton kuti ipe zvigadzirwa zve triazole uye kuvhara catalytic cycle.
Kunyange hazvo mabhenefiti emidziyo yemakemikari ekuyerera kwemvura akanyorwa zvakanaka, kwave nechido chekubatanidza maturusi ekuongorora muhurongwa uhu kuti pave nekutarisa maitikiro ari mukati mehurongwa66,67. UAM yakaratidza kuva nzira yakakodzera yekugadzira nekugadzira ma 3D flow reactors akaomarara akagadzirwa nezvinhu zvinofambisa simba, zvinofambisa kupisa zvine zvinhu zvinonzwa zvakananga (Mufananidzo 4).
Chinoyerera chearuminiyamu-mhangura chakagadzirwa nekugadzira zvinhu zvinowedzerwa zve ultrasonic (UAM) chine chimiro chakaoma chemukati menzira, ma thermocouples akaiswa mukati uye catalytic reaction chamber. Kuti tione nzira dzemukati memvura, prototype yakajeka yakagadzirwa uchishandisa stereolithography inoratidzwawo.
Kuti zvive nechokwadi chekuti ma reactors agadzirwa kuti ashandiswe mune ramangwana, zvinonyungudutsa zvinofanirwa kupiswa zvakachengeteka pamusoro pekufashaira; zvinoongororwa kumanikidzwa nekupisa. Kuyedzwa kwekumanikidzwa kwakaratidza kuti sisitimu inochengetedza kumanikidzwa kwakasimba uye kunogara kuripo kunyangwe paine kumanikidzwa kwakawedzerwa kwesisitimu (1.7 MPa). Kuyedzwa kwe hydrostatic kwakaitwa patembiricha yemumba uchishandisa H2O semvura.
Kubatanidza thermocouple yakavharirwa (Mufananidzo 1) kune data rekupisa kwakaratidza kuti thermocouple yaitonhora ne 6 °C (± 1 °C) kupfuura tembiricha yakarongwa paFlowSyn system. Kazhinji, kuwedzera kwe10 °C mukupisa kunoita kuti reaction rate iwedzere kaviri, saka mutsauko wetembiricha wemadhigirii mashoma chete unogona kuchinja zvakanyanya reaction rate. Musiyano uyu unokonzerwa nekurasikirwa kwetembiricha mumuviri wese we reactor nekuda kwekupararira kwakanyanya kwekupisa kwezvinhu zvinoshandiswa mukugadzira. Kuyerera uku kwekupisa kunogara kuripo uye nekudaro kunogona kuverengerwa mugadziriro yemidziyo kuona kuti tembiricha dzakarurama dzinosvikwa uye dzinoyerwa panguva ye reaction. Saka, chishandiso ichi chekutarisa online chinobatsira kudzora tembiricha ye reaction uye chinobatsira kugadzirisa maitiro nemazvo uye kugadzira mamiriro akanaka. Aya ma sensor anogona zvakare kushandiswa kuona reaction exotherms uye kudzivirira runaway reactions mumasystem makuru.
Reactor iri kuratidzwa mubasa iri muenzaniso wekutanga wekushandiswa kwetekinoroji yeUAM mukugadzirwa kwemakemikoro emakemikari uye inotarisa zvipingamupinyi zvikuru zvakati wandei zvine chekuita nekudhinda kweAM/3D kwemidziyo iyi, zvakaita se: (i) kukunda matambudziko akataurwa ane chekuita nekugadzirwa kwemhangura kana aruminiyamu (ii) kugadziriswa kwemukati menzira zvichienzaniswa nehunyanzvi hwekubatanidza poda (PBF) senge selective laser melting (SLM)25,69 Kuyerera kwezvinhu zvisina kunaka uye magadzirirwo epamusoro asina kunaka26 (iii) Kudzikira kwekupisa kwekugadzirisa, izvo zvinoita kuti masensa akwanise kubatana zvakananga, izvo zvisingagoneke mutekinoroji yepoda, (v) kukunda hunhu husina kunaka hwemakanika uye kunzwa kwezvikamu zvepolymer-based components kune zvakasiyana-siyana zve organic solvents17,19.
Kushanda kwe reactor kwakaratidzwa nerunyorwa rwe copper-catalyzed alkyne azide cycloaddition reactions pasi pe continuous flow conditions (Mufananidzo 2). Iyo ultrasonic-printed copper reactor yakatsanangurwa muMufananidzo 4 yakabatanidzwa ne commercial flow system uye yakashandiswa kugadzira library azides ye 1,4-disubstituted 1,2,3-triazoles kuburikidza ne tembiricha-controlled reaction ye acetylene ne alkyl groups halides pamberi pe sodium chloride (Mufananidzo 3). Kushandiswa kwe continuous flow approach kunoderedza kunetseka kwekuchengetedza kunogona kuitika mu batch processes, sezvo iyi reaction ichigadzira highly reactive and hazardous azide intermediates [317], [318]. Pakutanga, reaction yakagadziriswa kuti iite cycloaddition ye phenylacetylene ne iodoethane (Scheme 1 - Cycloaddition ye phenylacetylene ne iodoethane) (ona Mufananidzo 5).
(Kumusoro kuruboshwe) Chimiro chegadziriro yakashandiswa kuisa reactor ye3DP mu flow system (kumusoro kurudyi) yakawanikwa muchirongwa chakagadziridzwa (pazasi) cheHuisgen cycloaddition 57 scheme pakati pephenylacetylene ne iodoethane kuti igadziriswe uye kuratidza chiyero chekuchinja kwemhinduro yeparameters.
Nekudzora nguva yekugara kwema reagents muchikamu che catalytic che reactor uye kunyatsotarisa tembiricha ye reaction ne thermocouple probe yakabatanidzwa zvakananga, mamiriro e reaction anogona kugadziriswa nekukurumidza uye nemazvo nenguva shoma uye kushandiswa kwezvinhu. Zvakakurumidza kuonekwa kuti shanduko dzepamusoro dzakawanikwa kana nguva yekugara yemaminitsi gumi nemashanu uye tembiricha ye reaction ye150 °C yashandiswa. Kubva pa coefficient plot ye MODDE software, zvinogona kuonekwa kuti tembiricha yenguva yekugara uye reaction inoonekwa semashoko akakosha emuenzaniso. Kumhanyisa built-in optimizer uchishandisa aya mazwi akasarudzwa kunogadzira seti yemamiriro e reaction akagadzirirwa kuwedzera nzvimbo dzepamusoro pechigadzirwa uku uchideredza nzvimbo dzepamusoro pechigadzirwa chekutanga. Kugadzirisa uku kwakaburitsa 53% yekushandurwa kwechigadzirwa che triazole, icho chakanyatsoenderana nekufanotaura kwemuenzaniso kwe54%.
Zvichibva pane zvakanyorwa zvinoratidza kuti copper(I) oxide (Cu2O) inogona kushanda semhando inoshanda ye catalytic pamusoro pe zero-valent copper surfaces mukuita uku, kugona kwe pre-oxidize pamusoro pe reactor usati waita reaction mukuyerera kwakaongororwa70,71. Kuita pakati pe phenylacetylene ne iodoethane kwakazoitwa zvakare mumamiriro ezvinhu akanaka uye goho rakaenzaniswa. Zvakaonekwa kuti kugadzirira uku kwakaguma nekuwedzera kukuru mukushandurwa kwezvinhu zvekutanga, izvo zvakaverengerwa kuva >99%. Zvisinei, kutarisa kwakaitwa neHPLC kwakaratidza kuti kushandurwa uku kwakaderedza zvakanyanya nguva ye reaction yakareba zvakanyanya kusvika pamaminitsi angangoita makumi mapfumbamwe, ipapo chiitiko chacho chakaita sechakaenzana uye chasvika "mumamiriro akatsiga". Izvi zvinoratidza kuti sosi ye catalytic activity inowanikwa kubva pamusoro pe copper oxide pane zero-valent copper substrate. Cu metal inooxidized nyore nyore patembiricha yemukamuri kuti igadzire CuO neCu2O zvisiri zvikamu zvinozvidzivirira. Izvi zvinobvisa kudiwa kwekuwedzera sosi ye assistant copper(II) ye co-composition71.