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Karuseri inoratidza masiraidhi matatu panguva imwe chete. Shandisa mabhatani ekuti Yakapfuura neInotevera kuti ufambe nemasiraidhi matatu panguva imwe chete, kana kushandisa mabhatani ekuti anotsvedza ari kumagumo kuti ufambe nemasiraidhi matatu panguva imwe chete.
Kugadzira zvinhu zvinowedzera kuri kuchinja nzira iyo vaongorori nevashandi vemaindasitiri vanogadzira nekugadzira michina yemakemikari kuti ienderane nezvinodiwa zvavo. Mupepa rino, tinotaura muenzaniso wekutanga we "flow reactor" inoumbwa ne "ultrasonic additive manufacturing" (UAM) lamination yepepa resimbi rakasimba rine zvikamu zve "catalytic" zvakananga uye zvinhu zvinonzwa. Tekinoroji yeUAM haingokundi chete zvipingamupinyi zvakawanda zvine chekuita nekugadzirwa kwezvinhu zvinowedzera zvemakemikari, asiwo inowedzera zvikuru kugona kwemidziyo yakadaro. Makomichi akati wandei e1,4-disubstituted 1,2,3-triazole akakosha akagadzirwa uye akagadziriswa neCu-mediated 1,3-dipolar Huisgen cycloaddition reaction achishandisa UAM chemistry facility. Uchishandisa hunhu hwakasiyana hweUAM uye continuous flow processing, mudziyo uyu unokwanisa kukonzera maitiro anoenderera mberi pamwe nekupa 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 zvinobva pakuumbwa kwemamorekuru ari nyore eorganic1 kusvika kumakemikari emishonga2,3 uye zvigadzirwa zvechisikigo4,5,6. Kupfuura 50% yezviitiko muindasitiri yemakemikari akanaka uye yemishonga zvinogona kubatsirwa nekuyerera kunoramba kuripo7.
Mumakore achangopfuura, kwave netsika iri kukura yemapoka ari kutsvaga kutsiva zvishandiso zvemagirazi zvechinyakare kana michina yemakemikari inoyerera ne "reactors" dzemakemikari dzinochinjika8. Dhizaini idzokororwa, kugadzirwa nekukurumidza, uye kugona kwezvikamu zvitatu (3D) kwenzira idzi zvinobatsira kune avo vanoda kugadzirisa michina yavo kuti iite seti chaiyo yemaitiro, michina, kana mamiriro ezvinhu. Kusvika pari zvino, basa iri rave rakanyanya kutarisa pakushandiswa kwetekinoroji dzekudhinda dze3D dzakavakirwa papolymer dzakadai se stereolithography (SL)9,10,11, Fused Deposition Modeling (FDM)8,12,13,14 uye inkjet printing7,15. , 16. Kushaikwa kwekuvimbika 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, matekiniki ari nani anofanirwa kuongororwa anozobvumira vashandisi kugadzira midziyo yemagetsi ine makemikari akavandudzwa uye kugona kuongorora. Nzira idzi dzinofanira kubvumidza vashandisi kusarudza kubva kune dzakasiyana-siyana zvinhu zvine simba rakawanda kana zvinoshanda zvinokwanisa kushanda pasi pemamiriro akasiyana-siyana ekuita, pamwe nekubatsira mhando dzakasiyana dzekuongorora kubva mumudziyo kuti zvigone kutarisa nekudzora maitiro.
Imwe nzira yekugadzira zvinhu inogona kushandiswa kugadzira ma "custom chemical reactors" ndeye Ultrasonic Additive Manufacturing (UAM). Iyi nzira ye "solid-state sheet lamination" inoshandisa "ultrasonic vibrations" kuma "thin metal foils" kuti azvibatanidze pamwe chete "layer by layer" ne "volumetric heating" shoma uye "high plastic flow" 21, 22, 23. Kusiyana nedzimwe nzira dzakawanda dzeAM, UAM inogona kubatanidzwa zvakananga ne "subtractive production", inozivikanwa se "hybrid manufacturing process", umo "periodic in-situ numerical control (CNC) milling" kana "laser processing" inosarudza chimiro che "net shape" chezvinhu zvakasungwa 24, 25. Izvi zvinoreva kuti mushandisi haagumiri pamatambudziko ane chekuita nekubvisa zvinhu zvekuvaka zvakasara kubva mu "liquid channels" diki, izvo zvinowanzoitika mu "powder" uye "liquid systems" AM26, 27, 28. Rusununguko urwu rwekugadzira runosvikawo pakusarudza zvinhu zviripo - UAM inogona kubatanidza zvinhu zvakafanana nekupisa uye zvakasiyana muchikamu chimwe chete. Kusarudzwa kwezvinhu zvinopfuura "melting process" zvinoreva kuti zvinodiwa zvemakanika nemakemikari zvemashandisirwo chaiwo zvinogona kuzadzikiswa zviri nani. Pamusoro pekubatana kwakasimba, chimwe chiitiko chinoitika nekubatanidzwa kwe ultrasonic ndiko kuyerera kwakanyanya kwezvinhu zvepurasitiki patembiricha yakaderera 29, 30, 31, 32, 33. Hunhu uhu hwakasiyana hweUAM hunobvumira zvinhu zvemakanika/zvinodziya kuti zviiswe pakati pesimbi pasina kukuvara. Masensa eUAM akabatanidzwa anogona kubatsira kuendesa ruzivo rwenguva chaiyo kubva kumushandisi kuburikidza nekuongorora kwakabatanidzwa.
Basa rakaitwa nevanyori32 rakaratidza kugona kwemaitiro eUAM kugadzira zvivakwa zvesimbi zve3D microfluidic zvine kugona kwekunzwa kwakaiswa mukati. Mudziyo uyu ndewekutarisa chete. Chinyorwa chino chinopa muenzaniso wekutanga we microfluidic chemical reactor yakagadzirwa neUAM, mudziyo unoshanda usingangodzori chete asiwo unokurudzira kugadzirwa kwemakemikari nezvinhu zvinovaka muviri zvakabatanidzwa muchimiro. Mudziyo uyu unobatanidza mabhenefiti akati wandei ane chekuita netekinoroji yeUAM mukugadzira zvishandiso zvemakemikari zve3D, zvakaita se: kugona kushandura dhizaini yakazara ye3D zvakananga kubva kumuenzaniso wecomputer-aided design (CAD) kuita chigadzirwa; kugadzirwa kwezvinhu zvakawanda zvekubatanidza high thermal conductivity uye catalytic materials, pamwe nema thermal sensors akaiswa zvakananga pakati pe reactant streams kuti anyatso dzora uye atarisire tembiricha ye reaction. Kuratidza mashandiro e reactor, raibhurari ye1,4-disubstituted 1,2,3-triazole compounds yakakosha mumishonga yakagadzirwa ne copper-catalyzed 1,3-dipolar Huisgen cycloaddition. Basa iri rinoratidza kuti kushandiswa kwesainzi yezvinhu uye dhizaini inobatsirwa nemakombiyuta kunogona sei kuvhura mikana mitsva nemikana yekemesitiri kuburikidza nekutsvagisa kwakasiyana-siyana.
Zvese zvinonyungudutsa uye ma reagents zvakatengwa kubva kuSigma-Aldrich, Alfa Aesar, TCI, kana Fischer Scientific uye zvakashandiswa zvisina kucheneswa kare. 1H uye 13C NMR spectra dzakanyorwa pa400 ne100 MHz, zvichiteerana, dzakawanikwa paJEOL ECS-400 400 MHz spectrometer kana Bruker Avance II 400 MHz spectrometer ine CDCl3 kana (CD3)2SO se solvent. Zvese zvinoitwa zvakaitwa uchishandisa Uniqsis FlowSyn flow chemistry platform.
UAM yakashandiswa kugadzira michina yese muchidzidzo ichi. Tekinoroji iyi yakagadzirwa muna 1999 uye ruzivo rwayo rwehunyanzvi, mashandisirwo ayo uye budiriro kubva pakugadzirwa kwayo zvinogona kudzidzwa uchishandisa zvinhu zvinotevera zvakaburitswa34,35,36,37. Mudziyo uyu (Mufananidzo 1) wakagadzirwa uchishandisa sisitimu ye9 kW SonicLayer 4000® UAM ine simba guru (Fabrisonic, Ohio, USA). Zvinhu zvakasarudzwa zvekushandisa flow device zvaive Cu-110 naAl 6061. Cu-110 ine copper yakawanda (99.9% copper), zvichiita kuti ive yakanaka ye copper catalyzed reactions uye saka inoshandiswa se "active layer mukati me microreactor. Al 6061 O inoshandiswa se "bulk" material. , pamwe chete ne intercalation layer inoshandiswa pakuongorora; intercalation ye assistant alloy components uye annealed state pamwe chete ne Cu-110 layer. yakawanikwa yakagadzikana nemakemikari nema reagents anoshandiswa mubasa iri. Al 6061 O pamwe chete ne Cu-110 inoonekwawo semusanganiswa wezvinhu zvinoenderana ne UAM uye saka chinhu chakakodzera chidzidzo ichi38,42. Midziyo iyi yakanyorwa muTafura 1 pazasi.
Matanho ekugadzira reactor (1) 6061 aruminiyamu alloy substrate (2) Kugadzira nzira yepasi kubva pa copper foil (3) Kuisa thermocouples pakati pezvikamu (4) Nzira yepamusoro (5) Kupinda nekubuda (6) Monolithic reactor.
Pfungwa yekugadzira nzira yemvura ndeyekushandisa nzira inotenderera kuwedzera daro rinofambwa nemvura iri mukati mechip uku uchichengetedza saizi yechip inogoneka. Kuwedzera uku kwedaro kunodiwa kuti kuwedzere nguva yekubata catalyst-reactant uye kupa goho rakanaka rezvigadzirwa. Machips anoshandisa 90° bends pamagumo enzira yakatwasuka kuti akonzere kusanganisa kwakashata mukati memudziyo44 uye kuwedzera nguva yekubata mvura nepamusoro (catalyst). Kuti uwedzere kuwedzera kusanganisa kunogona kuitwa, dhizaini yereactor inosanganisira ma inlets maviri ereactant akabatanidzwa muY-connection asati apinda muchikamu che mixing coil. Mukova wechitatu, unoyambuka kuyerera pakati pekugara kwayo, unosanganisirwa muchirongwa che multi-stage synthesis reactions mune ramangwana.
Machaneli ese ane chimiro chesikweya (haana maangle akatetepa), izvo zvinova mugumisiro wekushandiswa kweCNC kugadzira geometry yechannel. Zviyero zvechannel zvinosarudzwa kuti zvipe goho repamusoro (re microreactor), asi zvidiki zvakakwana kuti zvive nyore kutaurirana nepamusoro (ma catalysts) kune akawanda emvura ari mairi. Saizi yakakodzera inobva pane zvakaitika kare kune vanyori nemidziyo ye metal-liquid reaction. Zviyero zvemukati zvechannel yekupedzisira zvaive 750 µm x 750 µm uye huwandu hwese hwe reactor hwaive 1 ml. Chinobatanidza chakavakirwa mukati (1/4″-28 UNF thread) chinosanganisirwa mudhizaini kuti zvibvumira nyore nyore kubatanidza mudziyo nemidziyo ye commercial flow chemistry. Saizi yechannel inoganhurirwa nehukobvu hwe foil material, hunhu hwayo hwe mechanical, uye ma bonding parameters anoshandiswa ne ultrasonics. Pahupamhi hwakati hwezvinhu zvakapihwa, zvinhu zvicha "sag" muchannel yakagadzirwa. Parizvino hapana modhi chaiyo yekuverenga uku, saka upamhi hwepamusoro hwechiteshi chezvinhu zvakapihwa nedhizaini hunoonekwa nekuyedza, umo upamhi hwe750 µm hahuzokonzere kudonha.
Chimiro (sikweya) chemugero chinoonekwa uchishandisa muchina wekucheka sikweya. Chimiro nehukuru hwemigero zvinogona kuchinjwa pamichina yeCNC uchishandisa maturusi akasiyana ekucheka kuti uwane mwero wekuyerera kwakasiyana uye hunhu hwakasiyana. Muenzaniso wekugadzira mugero wakakombama une chishandiso che125 µm unogona kuwanikwa muMonaghan45. Kana layer yefoil yaiswa yakati sandara, kushandiswa kwefoil yezvinhu kumagero kuchava nepamusoro pakatsetseka (sikweya). Mubasa iri, contour yesikweya yakashandiswa kuchengetedza symmetry yemugero.
Munguva yekumbomira kwakarongwa mukugadzirwa, masensa ekupisa ethermocouple (rudzi rweK) anovakwa zvakananga muchishandiso pakati pemapoka enzira dzepamusoro nedzepasi (Mufananidzo 1 - danho rechitatu). Mathermocouple aya anogona kudzora shanduko dzekupisa kubva -200 kusvika 1350 °C.
Maitiro ekuisa simbi anoitwa neUAM horn uchishandisa foil yesimbi ine upamhi hwe25.4 mm uye ukobvu hwe150 microns. Aya machira efoil akabatanidzwa muzvikamu zvakatevedzana zviri pedyo kuti afukidze nzvimbo yese yekuvaka; saizi yezvinhu zvakachengetwa yakakura kupfuura chigadzirwa chekupedzisira sezvo maitiro ekubvisa achigadzira chimiro chekupedzisira chakachena. CNC machining inoshandiswa kugadzira contours dzekunze nedzemukati dzemidziyo, zvichikonzera kupedzwa kwepamusoro kwemidziyo nemachannels zvinoenderana nemidziyo yakasarudzwa uye maparamendi eCNC process (mumuenzaniso uyu, angangoita 1.6 µm Ra). Kupfapfaidza uye kugadzira zvinhu zvinogadzirwa neultrasonic zvinoramba zvichienderera mberi zvinoshandiswa mukati memaitiro ekugadzira emudziyo kuti ive nechokwadi chekuti kurongeka kwehukuru kunochengetwa uye chikamu chakapedzwa chinosangana nemazinga eCNC fine milling. Upamhi hwenzira inoshandiswa pamudziyo uyu hudiki zvakakwana kuti ive nechokwadi chekuti foil material haitsvedzeri mu fluid channel, saka chiteshi chine chikamu che square cross. Mipata inogona kuitika mufoil material uye maparamendi eUAM process zvakaongororwa nekuyedza nemubatsiri wekugadzira (Fabrisonic LLC, USA).
Zvidzidzo zvakaratidza kuti panzvimbo inopindirana 46, 47 yeUAM compound hapana kupararira kushoma kwezvinhu pasina kuwedzera kupisa, saka pamidziyo iri mubasa iri, Cu-110 layer inoramba yakasiyana neAl 6061 layer uye inochinja zvakanyanya.
Isa chinodzora kumanikidzwa kwemusana (BPR) chakagadziriswa kare pa250 psi (1724 kPa) pasi pe reactor wobva wapomba mvura nepakati pe reactor nechiyero che0.1 kusvika 1 ml min-1. Kumanikidzwa kwe reactor kwakatariswa uchishandisa FlowSyn pressure transducer yakavakirwa musystem kuti ive nechokwadi chekuti system inogona kuchengetedza kumanikidzwa kwakasimba nguva dzose. Kugona kwekupisa mu flow reactor kwakaedzwa nekutsvaga mutsauko uripo pakati pe thermocouples yakavakirwa mu reactor ne thermocouples yakavakirwa mu heating plate yeFlowSyn chip. Izvi zvinoitwa nekushandura programmed hotplate tembiricha iri pakati pe100 ne150 °C mu 25 °C increments uye kutarisa mutsauko uripo pakati pe programmed ne recorded tembiricha. Izvi zvakaitwa uchishandisa tc-08 data logger (PicoTech, Cambridge, UK) uye PicoLog software.
Mamiriro ekuita kuti phenylacetylene ne iodoethane zviite cycloaddition reaction (Scheme 1-Cycloaddition yephenylacetylene ne iodoethane, Scheme 1-Cycloaddition yephenylacetylene ne iodoethane). Kugadzirisa uku kwakaitwa uchishandisa nzira yakazara yekugadzira bvunzo (DOE), uchishandisa tembiricha nenguva yekugara sezvinhu zvinoshanduka 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 sechiyero chenzvimbo yepamusoro yechigadzirwa chetriazole kune chinhu chekutanga che phenylacetylene uye yakaongororwa uchishandisa high performance liquid chromatography (HPLC). Kuti pave nekuenderana kwekuongorora, maitiro ese akatorwa pakarepo 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 x 100 mm, 5 µm particle size, yakachengetwa pa40°C. solvent yaive isocratic methanol:water 50:50 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 munzvimbo dze peak dze residual alkyne ne triazole products chete. Kuunzwa kwezvinhu zvekutanga kunoita kuti zvikwanisike kuziva peaks dzakakodzera.
Kusanganisa mhedzisiro yekuongorora reactor neMODDE DOE software (Umetrics, Malmö, Sweden) kwakabvumira ongororo yakakwana yemhedzisiro uye kuona mamiriro ekuita akanakisa ecycloaddition iyi. Kumhanyisa built-in optimizer uye kusarudza mazwi ese akakosha emuenzaniso kunogadzira seti yemamiriro ekuita akagadzirirwa kuwedzera nzvimbo yepamusoro yechigadzirwa uku uchideredza nzvimbo yepamusoro yeacetylene feedstock.
Kuoxidation kwemusoro wemhangura mukamuri re catalytic reaction kwakaitwa uchishandisa hydrogen peroxide solution (36%) inoyerera nemukamuri re reaction (flow rate = 0.4 ml min-1, nguva yekugara = 2.5 min) risati ragadzirwa reraibhurari yega yega ye triazole compound.
Kana mamiriro ezvinhu akanyatsonaka aonekwa, akaiswa kune akasiyana-siyana e-acetylene ne-haloalkane derivatives kuti zvibvumire kuunganidzwa kweraibhurari diki yekugadzira, nokudaro zvichigadzira mukana wekushandisa 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). Ma quots e3 ml emhinduro yega yega akasanganiswa ndokupombwa ne reactor ne 75 µl/min uye tembiricha ye 150°C. Vhoriyamu yese yakaunganidzwa mu vial ndokusanganiswa ne 10 ml ye ethyl acetate. Sample solution yakagezwa ne 3 x 10 ml yemvura. Aqueous layers dzakasanganiswa ndokubviswa ne 10 ml ethyl acetate, ipapo organic layers dzakasanganiswa, dzakagezwa ne 3 × 10 ml brine, dzakaomeswa pamusoro pe MgSO 4 ndokusefa, ipapo solvent yakabviswa mu vacuo. Samples dzakacheneswa ne silica gel column chromatography 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 mass spectrometer ine ESI senzvimbo yeionization. Samples dzese dzakagadzirwa uchishandisa acetonitrile se solvent.
Kuongororwa kweTLC kwakaitwa pamaplate esilica ane substrate yearuminiyamu. Maplate acho akaonekwa nechiedza cheUV (254 nm) kana kuti vanillin staining uye heating.
Mienzaniso yese yakaongororwa uchishandisa system yeVWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) ine autosampler, binary pomp ine column oven uye single wavelength detector. ACE Equivalence 5 C18 column (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland) yakashandiswa.
Majekiseni (5 µl) akagadzirwa zvakananga kubva mumusanganiswa we crude reaction wakasanganiswa (1:10 dilution) uye akaongororwa nemvura:methanol (50:50 kana 70:30), kunze kwemamwe masampuli achishandisa 70:30 solvent system (inoratidzwa senhamba yenyeredzi ) pachiyero chekuyerera kwe1.5 ml/min. Koramu yacho yakachengetwa pa40°C. Hurefu hwewavelength hwe detector i254 nm.
Nzvimbo yepamusoro yemuenzaniso yakaverengerwa kubva panzvimbo yepamusoro yealkyne yakasara, chigadzirwa chetriazole chete, uye kuiswa kwezvinhu zvekutanga kwakaita kuti zvikwanisike kuziva misoro inoenderana.
Sampuro dzese dzakaongororwa uchishandisa Thermo iCAP 6000 ICP-OES. Mitemo yese yekugadzirisa yakagadzirwa uchishandisa mhinduro yakajairika ye1000 ppm Cu mu2% nitric acid (SPEX Certi Prep). Mitemo yese yakagadzirwa mumhinduro ye5% DMF ne2% HNO3, uye sampuro dzese dzakasanganiswa ka20 nemhinduro yemuenzaniso yeDMF-HNO3.
UAM inoshandisa ultrasonic metal welding senzira yekubatanidza simbi inoshandiswa kugadzira gungano rekupedzisira. Ultrasonic metal welding inoshandisa chishandiso chesimbi chinodedera (chinonzi horn kana ultrasonic horn) kuisa kumanikidzwa kune foil/layer yakabatanidzwa kare kuti ibatane/yakabatanidzwa kare nekudedera chinhu chacho. Kuti ishande nguva dzose, sonotrode ine chimiro che cylindrical uye inotenderera pamusoro pechinhu chacho, ichinamira nzvimbo yese. Kana kumanikidzwa nekudedera zvichishandiswa, ma oxide ari pamusoro pechinhu chacho anogona kutsemuka. Kudzvinyirirwa nekudedera nguva dzose kunogona kutungamira mukuparadzwa kwekuoma kwechinhu chacho 36. Kusangana pedyo nekupisa kwenzvimbo nekudzvinyirirwa kunotungamira kune solid phase bond panzvimbo dzezvinhu; zvinogonawo kukurudzira kubatana nekuchinja simba repamusoro48. Hunhu hwe bonding mechanism inokunda matambudziko mazhinji ane chekuita nekushanduka kwekushisa uye kupisa kwakanyanya kunotaurwa mune mamwe matekinoroji ekugadzira additive. Izvi zvinobvumira kubatana zvakananga (kureva pasina kugadziriswa kwenzvimbo, fillers kana adhesives) yezvikamu zvakasiyana zvezvinhu zvakasiyana kuita chimiro chimwe chete chakabatanidzwa.
Chinhu chechipiri chakanaka cheCAM imhando yepamusoro yekuyerera kwepurasitiki inoonekwa muzvinhu zvesimbi kunyangwe patembiricha yakaderera, kureva kuti pasi penzvimbo yekunyunguduka kwezvinhu zvesimbi. Kusanganiswa kwekudengenyeka kwe ultrasonic nekumanikidzwa kunokonzera huwandu hwakanyanya hwekutama kwemiganhu yegorosi uye kudzokororwa kwecrystallization pasina kuwedzera kwakanyanya kwekupisa kwakajairika kwakabatana nezvinhu zvakawanda. Panguva yekuumbwa kwemusangano wekupedzisira, chiitiko ichi chinogona kushandiswa kuisa zvikamu zvinoshanda uye zvisingashande pakati pezvikamu zvesimbi foil, layer nelayer. Zvinhu zvakaita se optical fiber 49, reinforcement 46, electronics 50 uye thermocouples (basa iri) zvakabatanidzwa zvinobudirira muUAM structures kugadzira active uye passive composite assemblies.
Mubasa iri, zvese zvakasiyana-siyana zvinokwanisa kusunga zvinhu pamwe chete neUAM intercalation zvakashandiswa kugadzira microreactor yakakodzera yekudzora tembiricha ye catalytic.
Zvichienzaniswa nepalladium (Pd) nedzimwe simbi dzinoshandiswa zvakanyanya, Cu catalysis ine zvakanakira zvakawanda: (i) Panyaya dzehupfumi, Cu yakachipa pane dzimwe simbi dzakawanda dzinoshandiswa mu catalysis uye nokudaro isarudzo inokwezva indasitiri yemakemikari (ii) huwandu hweCu-catalyzed cross-coupling reactions huri kuwedzera uye hunoita sehunoenderana nePd51, 52, 53-based methodologies (iii) Cu-catalyzed reactions dzinoshanda zvakanaka pasina mamwe ma ligands. Aya ma ligands anowanzo kuve nyore muchimiro uye asingadhuri. kana uchida, nepo ayo anoshandiswa muPd chemistry anowanzo kuve akaomarara, anodhura, uye anonzwa mhepo (iv) Cu, inonyanya kuzivikanwa nekukwanisa kwayo kubatanidza ma alkynes mu synthesis, akadai seSonogashira's bimetallic catalyzed coupling uye cycloaddition ne azides (click chemistry) (v) Cu inogonawo kukurudzira arylation yemamwe ma nucleophiles muUllmann-type reactions.
Munguva pfupi yapfuura, mienzaniso yekuchinjana kwemaitiro ese aya pamberi peCu(0) yakaratidzwa. Izvi zvinonyanya kukonzerwa neindasitiri yemishonga uye kuwedzera kwekutarisa pakudzoreredza nekushandisazve simbi catalysts55,56.
Maitiro e1,3-dipolar cycloaddition pakati peacetylene neazide kune 1,2,3-triazole, akatanga kutaurwa naHuisgen muma196057, anoonekwa semaitiro ekuratidzirana. Zvidimbu zve1,2,3 triazole zvinobuda zvinonyanya kufarirwa semishonga inowanikwa mukutsvaga mishonga nekuda kwekushandiswa kwayo mumishonga yakasiyana-siyana.
Maitiro aya akawana kutariswa patsva apo Sharpless nevamwe vakatanga pfungwa ye "click chemistry"59. Izwi rekuti "click chemistry" rinoshandiswa kutsanangura seti yakasimba uye yakasarudzwa yemaitiro ekukurumidza kugadzira mishonga mitsva nemaraibhurari ekubatanidza achishandisa heteroatomic bonding (CXC)60. Kukwezva kwemaitiro aya kunokonzerwa negoho guru rinobatanidzwa nawo. mamiriro acho ari nyore, kuramba okisijeni nemvura, uye kupatsanurwa kwechigadzirwa kuri nyore61.
Kusanganiswa kwe 1,3-dipole Huisgen cycloaddition hakuwire muchikamu che "click chemistry". Zvisinei, Medal naSharpless vakaratidza kuti chiitiko ichi che azide-alkyne coupling chinoitwa 107-108 pamberi peCu(I) zvichienzaniswa nekukurumidzira kukuru muhuwandu hwe non-catalytic 1,3-dipolar cycloaddition 62,63. Iyi advanced reaction mechanism haidi mapoka ekudzivirira kana mamiriro ekuita akaomarara uye inopa shanduko yakakwana uye sarudzo kune 1,4-dissubstituted 1,2,3-triazoles (anti-1,2,3-triazoles) nekufamba kwenguva (Mufananidzo 3).
Mhedzisiro yeIsometric yeHuisgen cycloadditions yakajairika uye yakakamurwa nemhangura. Huisgen cycloadditions inokamurwa neCu(I) inopa 1,4-distituted 1,2,3-triazoles chete, nepo Huisgen cycloadditions inokonzerwa nekupisa inowanzo kupa 1,4- uye 1,5-triazoles musanganiswa we1:1 weazole stereoisomers.
Maitiro mazhinji anosanganisira kuderedzwa kwenzvimbo dzakagadzikana dzeCu(II), dzakadai sekuderedzwa kweCuSO4 kana Cu(II)/Cu(0) compound pamwe chete nesodium salts. Zvichienzaniswa nedzimwe nzira dzesimbi dzinoita kuti zvinhu zviite sezviri nyore kushandisa, kushandiswa kweCu(I) kune zvakanakira zvikuru zvekuti hazvidhuri uye zviri nyore kubata.
Zvidzidzo zveKinetic neIsotopic zvakaitwa naWorrell et al. 65 zvakaratidza kuti kana paine ma terminal alkynes, zvinhu zviviri zvakafanana zvemhangura zvine chekuita nekumutsa reactivity yemorekuru yega yega maererano neazide. Maitiro aya anoitwa kuburikidza nering yesimbi yemhangura ine nhengo nhanhatu inoumbwa nekubatana kweazide ne σ-bonded copper acetylede ne π-bonded copper se stable donor ligand. Copper triazolyl derivatives inoumbwa nekuda kwe ring contraction inoteverwa ne proton decomposition kuti igadzire triazole products uye kuvhara catalytic cycle.
Kunyange zvazvo mabhenefiti emidziyo yemakemikari ekuyerera kwemvura akanyorwa zvakanaka, kwave nechido chekubatanidza maturusi ekuongorora muhurongwa uhu kuti huvepo panguva chaiyo yekutarisa maitiro mu situ66,67. UAM yakaratidza kuva nzira yakakodzera yekugadzira nekugadzira ma 3D flow reactors akaomarara kubva pazvinhu zvinoshanda zvakanyanya, zvinofambisa kupisa zvine zvinhu zvinonzwa zvakananga (Mufananidzo 4).
Chinoyerera chearuminiyamu-mhangura chinogadzirwa ne ultrasonic additive manufacturing (UAM) chine chimiro chakaoma chemukati, ma thermocouples akavakirwa mukati uye catalytic reaction chamber. Kuti tifungidzire nzira dzemukati dzemvura, muenzaniso wakajeka wakagadzirwa uchishandisa stereolithography unoratidzwawo.
Kuti zvive nechokwadi chekuti ma reactor agadzirwa kuti ashandiswe mune ramangwana, zvinonyungudutsa zvinofanirwa kupiswa zvakachengeteka pamusoro pemvura yazvinofashaira; zvinoongororwa kumanikidzwa nekupisa. Kuongororwa kwekumanikidzwa kwakaratidza kuti sisitimu inochengetedza kumanikidzwa kwakasimba uye kunogara kuripo kunyangwe paine kumanikidzwa kwakakwira musisitimu (1.7 MPa). Kuongororwa kwemvura kwakaitwa patembiricha yemukamuri uchishandisa H2O semvura.
Kubatanidza thermocouple yakavakirwa mukati (Mufananidzo 1) nedata rekupisa kwakaratidza kuti tembiricha yethermocouple yaive 6 °C (± 1 °C) pasi petembiricha yakarongwa muFlowSyn system. Kazhinji, kuwedzera kwe10°C mukupisa kunowedzera kaviri reaction rate, saka mutsauko wetembiricha wemadhigirii mashoma chete unogona kuchinja reaction rate zvakanyanya. Mutsauko uyu unokonzerwa nekurasikirwa kwetembiricha mukati meRPV yese nekuda kwekupararira kwakanyanya kwekupisa kwezvinhu zvinoshandiswa mukugadzira. Kuyerera uku kwekupisa kunogara kuripo uye nekudaro kunogona kufungwa nezvako pakugadzira michina kuti ive nechokwadi chekuti tembiricha dzakarurama dzinosvikwa uye dzinoyerwa panguva yereaction. Saka, chishandiso ichi chekutarisa online chinobatsira kudzora tembiricha yereaction uye chinobatsira mukugadzirisa kwakanyatsojeka kweprocess uye kugadzira mamiriro akanaka. Aya ma sensor anogona zvakare kushandiswa kuona exothermic reactions uye kudzivirira runaway reactions mumasystem makuru.
Reactor iri mupepa rino 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 akaonekwa ane chekuita nekugadzirwa kwemhangura kana aruminiyamu (ii) kugadziriswa kwenzira yemukati kwakavandudzwa zvichienzaniswa nenzira dzekunyungudutsa muhupfu (PBF) dzakadai sekusarudza kunyungudutsa kwelaser (SLM)25,69 Kuyerera kwezvinhu zvisina kunaka uye magadzirirwo epamusoro asina kunaka26 (iii) tembiricha yakaderera yekugadzirisa, iyo inobatsira masensa ekubatanidza zvakananga, izvo zvisingagoneke mutekinoroji yehupfu, (v) kukunda hunhu husina kunaka hwemakanika uye kunzwa kwezvikamu zvepolymer kune zvakasiyana-siyana zvinosanganiswa neorganic solvents17,19.
Kushanda kwe reactor kwakaratidzwa nematanho e copper-catalyzed alkinazide cycloaddition reactions pasi pe continuous flow conditions (Mufananidzo 2). Iyo ultrasonic printed copper reactor inoratidzwa pamufananidzo 4 yakabatanidzwa ne commercial flow system uye yakashandiswa kugadzira azide library ye 1,4-disubstituted 1,2,3-triazoles uchishandisa tembiricha controlled reaction ye acetylene ne alkyl group halides pamberi pe sodium chloride (Mufananidzo 3). Kushandisa continuous flow approach kunoderedza matambudziko ekuchengetedza anogona kumuka muma batch process, 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 inoshandiswa kuisa reactor ye3DP mu flow system (kumusoro kurudyi) yakawanikwa kubva pachirongwa chakagadziridzwa (chepazasi) cheHuisgen 57 cycloaddition scheme pakati pephenylacetylene ne iodoethane kuti igadziriswe uye kuratidza ma parameter ekuchinja kwemhinduro.
Nekudzora nguva yekugara kwema reactants muchikamu che catalytic che reactor uye kunyatsotarisa tembiricha ye reaction ne thermocouple sensor yakabatana zvakananga, mamiriro e reaction anogona kugadziriswa nekukurumidza uye nemazvo nenguva shoma nezvinhu. Zvakakurumidza kuwanikwa kuti shanduko yepamusoro yakawanikwa uchishandisa nguva yekugara yemaminitsi gumi nemashanu uye tembiricha ye reaction ye150°C. Zvinogona kuonekwa kubva pa coefficient plot ye MODDE software kuti nguva yekugara uye tembiricha ye reaction zvinoonekwa semamiriro akakosha emodhi. Kumhanyisa built-in optimizer uchishandisa mamiriro aya akasarudzwa kunogadzira seti yemamiriro e reaction akagadzirirwa kuwedzera nzvimbo dzepamusoro pechigadzirwa uku uchideredza nzvimbo dzepamusoro pechigadzirwa chekutanga. Kugadzirisa uku kwakaburitsa 53% shanduko yechigadzirwa che triazole, iyo yakanyatsoenderana nekufanotaura kwemodhi ye54%.