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Mosebetsing ona, re tlaleha mohlala oa pele oa mochine o phallang o entsoeng ke mokhoa o tiileng oa ho hlahisa letlapa la tšepe Ultrasonic Additive Manufacturing (UAM) e nang le likarolo tsa catalytic tse kopantsoeng ka ho toba le likarolo tsa ho lemoha. Letoto la metsoako ea bohlokoa ea biologically 1,4-disubstituted 1,2,3-triazole e ile ea etsoa ka katleho le ho ntlafatsoa ke Cu-mediated Huisgen 1,3-dipolar cycloaddition reaction ka ho sebelisa UAM chemistry set-up.
Ka lebaka la melemo ea eona e kholo ho feta molekane oa eona oa bongata, k'hemistri ea phallo ke tšimo ea bohlokoa le e ntseng e hōla maemong a thuto le a indasteri ka lebaka la bokhoni ba eona ba ho eketsa khetho le katleho ea lik'hemik'hale tsa metsoako.Sena se fetela ho tloha ho sebopeho se bonolo sa molek'hule1 ho ea ho metsoako ea meriana2,3 le lihlahisoa tsa tlhaho4,5,6. Ho feta 50% ea karabelo indastering e ntle ea lik'hemik'hale le ea meriana e ka rua molemo ts'ebelisong ea ts'ebetso e tsoelang pele ea phallo7.
Lilemong tsa morao tjena, ho 'nile ha e-ba le mokhoa o ntseng o hōla oa lihlopha tse batlang ho nkela lisebelisoa tsa khale tsa khalase kapa lisebelisoa tsa k'hemistri ka mokhoa oa customizable additive production (AM) chemistry "reaction vessels"8. Moralo o pheta-phetoang, tlhahiso e potlakileng, le bokhoni ba 3-dimensional (3D) ea mekhoa ena e molemo ho ba lakatsang ho fetola lisebelisoa tsa bona ho ea ka sete e itseng ea liketso, letsatsi, lisebelisoa, kapa maemo a khethehileng. mekhoa ea khatiso ea 3D e thehiloeng ho polymer e kang stereolithography (SL)9,10,11, fused deposition modeling (FDM)8,12,13,14 le khatiso ea inkjet 7, 15, 16. Ho haella ha matla le bokhoni ba lisebelisoa tse joalo ho etsa mefuta e mengata ea lik'hemik'hale tsa lik'hemik'hale / tlhahlobo e kholo ea 18201 ke 9 ea AM tšimong ena17, 18, 19, 20 .
Ka lebaka la ts'ebeliso e ntseng e eketseha ea k'hemistri ea phallo le thepa e ntle e amanang le AM, ho hlokahala hore ho hlahlojoe mekhoa e tsoetseng pele e lumellang basebelisi ho etsa likepe tse nang le lik'hemik'hale tse matlafalitsoeng le bokhoni ba ho hlahloba.
Mokhoa o mong oa ho etsa li-additive o nang le bokhoni ba ho hlahisa li-reactors tse tloaelehileng tsa lik'hemik'hale ke Ultrasonic Additive Manufacturing (UAM) .Tsela ena e tiileng-state sheet lamination e sebetsa ka ultrasonic oscillations ho li-foil tse tšesaane tsa tšepe e le ho li kopanya hammoho lera ka ho futhumatsa ho fokolang haholo le tekanyo e phahameng ea phallo ea polasetiki 21 e le mokhoa oa tlhahiso ea lebasetere, moo in-situ periodic computer numberal control (CNC) milling kapa laser machining e hlalosang sebopeho sa letlooa la lesela la lintho tse tlamiloeng 24, 25.Sena se bolela hore mosebelisi ha a felle ka mathata a amanang le ho tlosa masala a mahlahahlaha a kaho ho tloha likanaleng tse nyane tsa mokelikeli, tseo hangata li leng joalo ka phofo le mokelikeli oa lisebelisoa tse fumanehang ho AM26.27. tlamahano ea thepa e ts'oanang ka mocheso le e fapaneng ka mohato o le mong oa ts'ebetso.Khetho ea metsoako ea lintho tse bonahalang ka nģ'ane ho ts'ebetso ea ho qhibiliha e bolela hore litlhoko tsa mechine le tsa lik'hemik'hale tsa lik'hemik'hale tse khethehileng li ka finyelloa hamolemo.Ho phaella ho solid state bonding, ntho e' ngoe e ileng ea etsahala nakong ea bonding ea ultrasonic ke phallo e phahameng ea thepa ea polasetiki ka mocheso o batlang o le tlase29,30,31,31,32,33AM e ka khonang ho kopanya lisebelisoa tsa tšepe tse ikhethang. likarolo ntle le tšenyo.Li-sensor tse kentsoeng tsa UAM li ka thusa ho fana ka tlhahisoleseding ea nako ea sebele ho tloha mochine ho ea ho mosebedisi ka li-analytics tse kopantsoeng.
Mosebetsi oa nakong e fetileng oa bangoli32 o bontšitse bokhoni ba mokhoa oa UAM oa ho etsa lisebelisoa tsa tšepe tsa 3D microfluidic tse nang le bokhoni bo kopanetsoeng ba ho lemoha.Sena ke sesebelisoa sa ho beha leihlo feela.Pampiri ena e fana ka mohlala oa pele oa mochine oa lik'hemik'hale oa microfluidic o entsoeng ke UAM; sesebelisoa se sebetsang se sa hlokomeleng feela empa se boetse se kenyelletsa lik'hemik'hale tsa lik'hemik'hale ka lisebelisoa tse entsoeng ka mokhoa o hlophisitsoeng. ho etsa lintho tse ngata ho kopanya mocheso o phahameng oa mocheso le lisebelisoa tsa catalytic; le ho kenya lisebelisoa tsa mocheso ka ho toba pakeng tsa melapo ea reagent bakeng sa tlhokomelo e nepahetseng ea mocheso oa karabelo le taolo.Ho bonts'a ts'ebetso ea reactor, laebrari ea metsoako ea bohlokoa ea meriana ea 1,4-disubstituted 1,2,3-triazole e entsoe ka koporo-catalyzed Huisgen 1,3-dipolar science. moralo o ka bula menyetla e mecha le menyetla ea k'hemistri ka lipatlisiso tse ngata.
Lihlahisoa tsohle le li-reagents li ile tsa rekoa ho Sigma-Aldrich, Alfa Aesar, TCI kapa Fischer Scientific 'me tsa sebelisoa ntle le ho hloekisoa pele.1H le 13C NMR spectra e rekotiloeng ho 400 MHz le 100 MHz, ka ho latellana, li ile tsa fumanoa ho sebelisoa JEOL ECS-400 400 spectro ea 400 MHz 400 MHz II spectrometer le CDCl3 kapa (CD3)2SO e le solvent. Likarabo tsohle li ile tsa etsoa ho sebelisoa Uniqsis FlowSyn chemistry platform.
UAM e ne e sebelisetsoa ho etsa lisebelisoa tsohle thutong ena.Theknoloji e qapiloe ka 1999, 'me lintlha tsa eona tsa theknoloji, litekanyetso tsa ts'ebetso le tsoelo-pele ho tloha ha e qaptjoa e ka ithutoa ka lisebelisoa tse hatisitsoeng tse latelang34,35,36,37.Sesebelisoa (setšoantšo sa 1) se ile sa kenngoa ts'ebetsong ka ho sebelisa matla a holimo-limo, 9kW SonicLayer UAM 4000 tsamaiso ea lisebelisoa tsa OHbri, USA. ho etsoa ha sesebelisoa sa phallo e ne e le Cu-110 le Al 6061.Cu-110 e na le koporo e ngata (bonyane 99.9% ea koporo), e etsa hore e be mokhethoa ea molemo bakeng sa likarabo tsa koporo-catalyzed, 'me ka hona e sebelisoa e le "lesela le sebetsang ka hare ho microreactor. boemo ba annealed bo kopantsoeng le lera la Cu-110 Al 6061 O ke boitsebiso bo bontšitsoeng hore bo lumellana haholo le mekhoa ea UAM38, 39, 40, 41 'me e lekoa le ho fumanoa e tsitsitse ka lik'hemik'hale le li-reagents tse sebelisoang mosebetsing ona. 38,42 Lisebelisoa tsena li thathamisitsoe ho Lethathamo la 1 ka tlase.
Mekhahlelo ea ho etsa li-reactor (1) Al 6061 substrate (2) Ho etsoa ha mocha o ka tlaase o behiloeng ho foil ea koporo (3) Ho kenngoa ha thermocouples pakeng tsa lihlopha (4) Top channel (5) Inlet le outlet (6) Monolithic reactor.
Filosofi ea moralo oa tsela ea mokelikeli ke ho sebelisa tsela ea convoluted ho eketsa sebaka sa mokelikeli o tsamaeang ka har'a chip, ha o ntse o boloka chip ka boholo bo laolehang. Keketseho ena ea sebaka se hole ke ntho e lakatsehang ho eketsa nako ea ho sebelisana le li-catalyst / reagent le ho fana ka lihlahisoa tse ntle haholo tsa lihlahisoa. (catalyst).Ho eketsa ho kopanya ho ka finyelloang, moqapi oa mochine o na le lisebelisoa tse peli tsa reagent tse kopantsoeng le Y-junction pele li kena karolong ea ho kopanya ea noha. Seketsoana sa boraro, se phunyeletsang molapo bohareng ba ho lula ha sona, se kenyelelitsoe moralong oa li-syntheses tsa nakong e tlang tsa multistep reaction.
Liteishene tsohle li na le profil ea lisekoere (ha ho na li-angles), sephetho sa "CNC milling" ea nako le nako e sebelisetsoang ho theha geometry ea kanale. Litekanyo tsa kanane li khethoa ho netefatsa phallo ea molumo o phahameng (bakeng sa microreactor), ha e ntse e le nyane ka ho lekana ho thusa ho sebelisana ka holim'a metsi (li-catalysts) bakeng sa metsi a mangata. µm x 750 µm le kakaretso ea molumo oa reactor e ne e le 1 ml. Sehokelo se kopantsoeng (1/4″—28 UNF thread) se kenyelelitsoe moahong ho lumella ho hokahana ha bonolo ha sesebelisoa ka thepa ea k'hemistri ea phallo ea khoebo. Boholo ba mocha bo lekanyelitsoe ke botenya ba thepa ea foil, thepa ea eona ea mochine, le mekhoa ea ho kopanya e sebelisoang le ultrasonics. Ka bophara bo khethehileng bakeng sa boitsebiso bo fanoeng, boitsebiso bo tla "sag" ka har'a mocha o entsoeng. Hajoale ha ho na mohlala o ikhethileng oa palo ena, ka hona bophara bo boholo ba mocha bakeng sa thepa e fanoeng le moralo bo khethoa ka liteko; tabeng ena, bophara ba 750 μm bo ke ke ba baka sag.
Sebopeho (sekoere) sa mocha se khethoa ka ho sebelisa square cutter.Sebopeho le boholo ba likanale li ka fetoloa ke mechine ea CNC e sebelisang lisebelisoa tse fapaneng tsa ho itšeha ho fumana litekanyetso tse fapaneng tsa phallo le litšoaneleho.Mohlala oa ho theha mocha oa sebopeho se kobehileng o sebelisa sesebelisoa sa 125 μm se ka fumanoa mosebetsing oa Monaghan45. (square) finish
Nakong ea khefu e entsoeng esale pele ha ho etsoa, ​​​​mofuta oa mocheso oa mocheso oa mocheso (Mofuta oa K) o kenngoa ka ho toba ka har'a sesebelisoa pakeng tsa lihlopha tse ka holimo le tse ka tlaase (Setšoantšo sa 1 - Mothati oa 3). Li-thermocouples tsena li ka shebella liphetoho tsa mocheso ho tloha -200 ho ea ho 1350 ° C.
Ts'ebetso ea ho kenya tšepe e etsoa ke lenaka la UAM le sebelisang bophara ba 25.4 mm, 150 micron e teteaneng ea tšepe. boholo ba thepa e behiloeng e kholo ho feta sehlahisoa sa ho qetela ha ts'ebetso ea ho tlosa e hlahisa sebopeho sa ho qetela sa letlooa.CNC machining e sebelisoa ho mochine ka ntle le ka hare ho lisebelisoa tsa thepa, ho fella ka ho qeta holim'a lisebelisoa le likanale tse lekanang le sesebelisoa se khethiloeng le mekhoa ea ts'ebetso ea CNC (hoo e ka bang 1.6 μm Ra ka mohlala ona). etsa bonnete ba hore ho nepahala ha dimensional ho bolokoa 'me karolo e phethiloeng e tla kopana le CNC finish milling accuracy levels.Bophara ba kanale bo sebelisitsoeng bakeng sa sesebelisoa sena bo nyane ho lekana ho etsa bonnete ba hore thepa ea foil ha e "sag" ka har'a kanale ea mokelikeli, kahoo mocha o boloka sebaka sa lisekoere tse fapaneng.Likheo tse ka bang teng ka thepa ea foil le mekhahlelo ea ts'ebetso ea UAM e ne e khethiloe ka liteko ke molekane oa tlhahiso, USA Fabrisonic.
Liphuputso li bontšitse hore phallo e nyenyane ea motheo e etsahala ho UAM bonding interface 46, 47 ntle le phekolo e eketsehileng ea mocheso, kahoo bakeng sa lisebelisoa tse sebetsang mosebetsing ona, lesela la Cu-110 le lula le fapane le lera la Al 6061 'me le fetoha ka tšohanyetso.
Kenya pre-calibrated 250 psi (1724 kPa) back pressure regulator (BPR) ho ea ho outlet of the reactor and pump water through the reactor at the rate of 0.1 to 1 mL min-1. Khatello ea reactor e ne e shejoa ka ho sebelisa FlowSyn e hahiloeng ka har'a mochine oa khatello ea tsamaiso ho netefatsa hore tsamaiso e ne e ka boloka mocheso o tsitsitseng oa ho phalla ka nako leha e le efe ea mocheso o tsitsitseng. phapang pakeng tsa li-thermocouples tse kentsoeng ka har'a reactor le tse kentsoeng ka har'a poleiti ea ho futhumatsa ea FlowSyn chip. Sena se finyelloa ka ho fetola mocheso oa hotplate o hlophisitsoeng pakeng tsa 100 le 150 °C ho 25 °C increments le ho hlokomela phapang leha e le efe pakeng tsa mocheso o hlophisitsoeng le o rekotiloeng.Sena se fihletsoe ka ho sebelisa UK datach, Cambridge-08 datach, Cambridge e tsamaeang le PicoLog software.
The cycloaddition reaction conditions of phenylacetylene and iodoethane were optimized (Scheme 1- Cycloaddition of phenylacetylene and iodoethane Scheme 1- Cycloaddition of phenylacetylene and iodoethane) . Ntlafatso ena e entsoe ka moralo o felletseng oa factorial oa liteko, ho sebelisoa mokhoa oa ho feto-fetoha oa mocheso le nako ea ho phomola, ho sebelisoa mokhoa oa ho lokisa mocheso le nako ea ho phomola (DOE). karo-karolelano ea alkyne:azide ka 1:2.
Litharollo tse arohaneng tsa sodium azide (0.25 M, 4: 1 DMF: H2O), iodoethane (0.25 M, DMF), le phenylacetylene (0.125 M, DMF) li ile tsa lokisoa.A 1.5 mL aliquot ea tharollo e 'ngoe le e' ngoe e ne e tsoakane 'me ea phunyeletsoa ka terekere ka tekanyo e lakatsehang ea phallo le mocheso e le sebaka sa triak ea karabo ea sehlahisoa sa sehlahisoa sa pezole. phenylacetylene ho qala lintho tse bonahalang le ho khethoa ke phahameng tshebetso mokelikeli chromatography (HPLC).
Mehlala eohle e ile ea hlahlojoa ho sebelisoa tsamaiso ea Chromaster HPLC (VWR, PA, USA) e nang le pompo ea quaternary, oven oven, variable wavelength UV detector le autosampler. The column was an Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 100 mm ka boholo, 5 µm ka boholo, 5 µm. isocratic 50:50 methanol:metsi ka tekanyo ea phallo ea 1.5 mL.min-1. Molumo oa ente e ne e le 5 µL le detector wavelength e ne e le 254 nm. Sebaka sa tlhōrō sa % sa sampuli ea DOE se ne se baloa ho tloha libakeng tse phahameng tsa alkyne e setseng le triazole ea lihlahisoa tse loketseng ho qala feela.
Ho kopanya tlhahiso ea tlhahlobo ea reactor ho software ea MODDE DOE (Umetrics, Malmö, Sweden) e lumelletse tlhahlobo e phethahetseng ea mekhoa ea sephetho le boikemisetso ba maemo a nepahetseng a karabelo bakeng sa cycloaddition ena.Ho tsamaisa sebatli se hahelletsoeng le ho khetha mantsoe ohle a bohlokoa a mohlala ho fana ka maemo a karabelo a etselitsoeng ho holisa sebaka sa tlhoro sa sehlahisoa ha ho ntse ho fokotsa sebaka sa tlhoro ea thepa.
The oxidation ea holim'a koporo ka hare ho catalytic reaction chamber e ile ea finyelloa ho sebelisa tharollo ea hydrogen peroxide (36%) e phallang ka kamoreng ea karabelo (sekhahla sa phallo = 0.4 mL min-1, nako ea bolulo = 2.5 min) pele ho qaptjoa ha laebrari e 'ngoe le e' ngoe ea motsoako oa triazole.
Hang ha maemo a nepahetseng a khetholloa, a ne a sebelisoa ho mefuta e mengata ea acetylene le haloalkane derivatives ho lumella ho bokelloa ha pokello e nyenyane ea laebrari, ka hona ho theha bokhoni ba ho sebelisa maemo ana ho mefuta e mengata ea li-reagents tse ka 'nang tsa e-ba teng (Setšoantšo sa 1) .2).
Lokisetsa litharollo tse arohaneng tsa sodium azide (0.25 M, 4: 1 DMF: H2O), haloalkanes (0.25 M, DMF) le alkynes (0.125 M, DMF) 3 mL aliquots tsa tharollo ka 'ngoe li ne li tsoakoa 'me tsa pompeloa ka mochine oa 75 µL.min-1 le 150 ° C. ethyl acetate.Tharollo ea mohlala e ne e hlatsuoa ka 3 × 10 mL ea metsi. Likarolo tse nang le metsi li kopantsoe le ho ntšoa ka 10 mL ea ethyl acetate; li-organic layers li ne li kopanngoa, li hlatsuoa ka 3 x 10 mL ea brine, li omisitsoe holim'a MgSO4 le ho hloekisoa, joale mokelikeli o ne o tlosoa ka vacuo.Mehlala e ne e hloekisoa ka kholomo ea chromatography holim'a silica gel e sebelisang ethyl acetate pele ho tlhahlobo ka motsoako oa HPLC, 1H NMR, 13C HRM-spectrum (high resolution mass-NMR).
Lipono tsohle li ile tsa fumanoa ho sebelisoa Thermofischer precision Orbitrap mass spectrometer le ESI e le mohloli oa ionization.Mehlala eohle e ne e lokiselitsoe ho sebelisa acetonitrile e le solvent.
Tlhahlobo ea TLC e ne e etsoa ka lipoleiti tsa silica tse tšehelitsoeng ka aluminium.
Mehlala eohle e ile ea hlahlojoa ho sebelisoa tsamaiso ea VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) e nang le autosampler, column oven binary pump and single wavelength detector.Molomo o sebelisitsoeng e ne e le ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Ltd.,Scotland Aberlogides).
Liente (5 µL) li entsoe ka kotloloho ho tsoa ho motsoako o hlapollotsoeng oa crude reaction (1:10 dilution) 'me tsa hlahlobisisoa ka metsi:methanol (50:50 kapa 70:30), ntle le lisampole tse ling tse sebelisang sesebelisoa sa solvent sa 70:30 (e hlalosoang e le nomoro ea naleli) ka sekhahla sa phallo ea 1.5 mL/min. 254 nm.
Sebaka sa tlhoro sa% sa sampole se ne se baloa ho tloha sebakeng se phahameng sa alkyne e setseng, sehlahisoa sa triazole feela, mme ente ea thepa ea ho qala e lumelletse ho tsebahatsa litlhoro tse amehang.
Mehlala eohle e ile ea hlahlojoa ho sebelisoa Thermo iCAP 6000 ICP-OES. Litekanyetso tsohle tsa calibration li ne li lokiselitsoe ho sebelisoa tharollo e tloaelehileng ea 1000 ppm Cu ka 2% nitric acid (SPEX Certi Prep) . Litekanyetso tsohle li ne li lokiselitsoe ka 5% DMF le 2% HNO3 tharollo, 'me mehlala eohle e ne e hlapolotsoe ka sampuli ea DMF3 ka 20-H NO3.
UAM e sebelisa ultrasonic metal welding e le mokhoa oa ho kopanya bakeng sa thepa ea tšepe ea tšepe e sebelisetsoang ho haha ​​kopano ea ho qetela.Ultrasonic metal welding utilizes a vibrating metal tool (e bitsoang lenaka kapa lenaka la ultrasonic) ho kenya khatello ho lera la foil / pele le kopantsoe lera hore le tlamahane ha le ntse le thothomela. ho kopanya sebaka sohle.Ha khatello le ho sisinyeha ho sebelisoa, li-oxide tse holim'a lintho tse bonahalang li ka phunyeha.Khatello e tsoelang pele le ho sisinyeha ho ka etsa hore asperities ea thepa e oe 36 .Ho kopana haufi-ufi le mocheso o bakoang ke sebaka sa heno le khatello e ntan'o lebisa ho tlamahano e tiileng-'muso libakeng tse bonahalang; e ka boela ea thusa ho khomarela ka liphetoho holim'a matla a holim'a matla48. Sebopeho sa mochine oa ho kopanya o hlōla mathata a mangata a amanang le mocheso o fapaneng oa ho qhibiliha le mocheso o phahameng ka mor'a liphello tse boletsoeng mekhoeng e meng ea ho etsa li-additive.Sena se lumella ho kopanya ka ho toba (ke hore, ntle le phetoho ea holim'a metsi, li-fillers kapa li-adhesives) tsa lihlopha tse ngata tsa lisebelisoa tse sa tšoaneng ho ba sebopeho se le seng se kopantsoeng.
Ntho ea bobeli e ntle bakeng sa UAM ke tekanyo e phahameng ea phallo ea polasetiki e hlokometsoeng ka thepa ea tšepe, esita le ka mocheso o tlaase, ke hore ka tlase ho ntlha ea ho qhibiliha ea lisebelisoa tsa tšepe. Motsoako oa oscillation ea ultrasonic le khatello e etsa hore ho be le maemo a phahameng a ho falla ha moeli oa lijo-thollo le recrystallization ntle le keketseho e kholo ea mocheso ka tloaelo e amanang le lisebelisoa tse ngata. metal foil, layer by layer.Elements tse kang optical fibers 49, reinforcement 46, electronics 50, le thermocouples (mosebetsi ona) kaofela li kentsoe ka katleho meahong ea UAM ho theha likopano tse sebetsang le tse sa sebetseng.
Mosebetsing ona, menyetla e fapaneng ea maqhama le menyetla ea ho hokahana ea UAM e se e sebelisitsoe ho theha microreactor ea ho qetela ea ho lekola mocheso.
Ha ho bapisoa le palladium (Pd) le lisebelisoa tse ling tsa tšepe tse sebelisoang ka tloaelo, Cu catalysis e na le melemo e 'maloa: (i) Ka moruo, Cu e theko e tlaase ho feta litšepe tse ling tse ngata tse sebelisoang ka catalysis 'me ka hona ke khetho e ntle bakeng sa indasteri ea ho sebetsana le lik'hemik'hale (ii) Mefuta e mengata ea liketso tsa Cu-catalyzed cross-coupling reactions e ntse e eketseha' me e bonahala e le mokhoa o itseng o tlatsetsang, 251) Cu-catalyzed reactions sebetsa hantle ka ho ba sieo ha ligand tse ling, Ligands tsena hangata structural bonolo le theko e tlaase haeba ho lakatseha, athe tse sebelisoang ka Pd k'hemistri hangata rarahaneng, theko e boima, 'me moea-sensitive (iv) Cu, haholo-holo tsejoa ka bokhoni ba eona ba ho tlama alkynes ka synthesis, Ka mohlala, bimetallic-catalyzedcling-cocatalyzedcling le Solo-catalyzedcling chemistry) (v) Cu e boetse e khona ho khothaletsa arylation ea li-nucleophiles tse 'maloa liketsong tsa mofuta oa Ullmann.
Mehlala ea heterogenization ea liketso tsena kaofela e sa tsoa bontšoa ka pel'a Cu (0) .Sena haholo-holo ka lebaka la indasteri ea meriana le ho tsepamisa maikutlo ho ntseng ho hola ho tsosolosoa ha tšepe ea tšepe le ho sebelisa hape55,56.
E qaliloe ke Huisgen lilemong tsa bo-196057, 1,3-dipolar cycloaddition reaction pakeng tsa acetylene le azide ho 1,2,3-triazole e nkoa e le synergistic show reaction. meriana ea phekolo 58 .
Boitšoaro bona bo ile ba boela ba tsepamisa maikutlo ha Sharpless le ba bang ba hlahisa khopolo ea "tobetsa k'hemistri" 59. Poleloana "click chemistry" e sebelisoa ho hlalosa mekhoa e matla, e ka tšeptjoang le e khethiloeng bakeng sa motsoako o potlakileng oa metsoako e mecha le lilaebrari tse kopanyang ka heteroatom linkage (CXC)60 The synthetic chemistry of these reactions is associated with their reactions is high-processeds from their oksijene ho hanyetsa, lihlahisoa tse phahameng tsa metsi le lihlahisoa tsa bona tse amanang le oksijene. karohano e bonolo61.
The classical Huisgen 1,3-dipole cycloaddition ha se karolo ea "click chemistry".Leha ho le joalo, Medal le Sharpless li bontšitse hore ketsahalo ena ea coupling azide-alkyne e feta 107 ho 108 ka boteng ba Cu(I) bapisoa le uncatalyzed 1,3-dipolar rate 6cceledi3 reaction ea bohlokoa ea cycload 626. ha e hloke lihlopha tse sireletsang kapa maemo a thata a karabelo le lihlahisoa tse haufi le phetoho e feletseng le khetho ho 1,4-disubstituted 1,2,3-triazoles (anti- 1,2,3-triazole) ka nako ea nako (Setšoantšo sa 3).
Liphetho tsa Isometric tsa Huisgen cycloadditions tse tloaelehileng le tsa koporo.Cu(I)-catalyzed Huisgen cycloadditions e fana ka 1,4-disubstituted 1,2,3-triazoles feela, athe Huisgen cycloadditions e entsoeng ka thermally hangata e hlahisa 1,51-triazole li-stereoisomers tsa azole.
Li-protocol tse ngata li kenyelletsa ho fokotseha ha mehloli e tsitsitseng ea Cu (II), e kang ho fokotseha ha mefuta ea CuSO4 kapa Cu (II) / Cu (0) e kopantsoeng le letsoai la sodium.Ha ho bapisoa le liketso tse ling tse entsoeng ka tšepe, tšebeliso ea Cu (I) e na le melemo e meholo ea ho ba theko e tlaase le e bonolo ho sebetsana le eona.
Lithuto tsa Kinetic le isotopic labeling ka Worrell et al. 65 e bontšitse hore, tabeng ea li-alkyne tsa terminal, tse peli tse lekanang le koporo li kenyelelitsoe ho kenya ts'ebetsong ts'ebetso ea molek'hule ka 'ngoe ho ea ho azide.Mochine o reriloeng o tsoela pele ka lesale la tšepe la koporo le nang le litho tse tšeletseng tse entsoeng ka ho hokahanya ha azide ho σ-bonded copper acetylide e nang le π-bonded copper e le copper e tsitsitseng e entsoeng ke copper e tsitsitseng. ringage shrinkage, e lateloang ke proton decomposition ho fana ka lihlahisoa tsa triazole le ho koala potoloho ea catalytic.
Le hoja melemo ea lisebelisoa tsa lik'hemik'hale tsa phallo e ngotsoe hantle, ho bile le takatso ea ho kenyelletsa lisebelisoa tsa ho hlahloba lits'ebetsong tsena bakeng sa in-line, in-situ, ts'ebetso ea ts'ebetso66,67.UAM e ipakile e le mokhoa o loketseng oa ho qapa le ho hlahisa li-reactors tse rarahaneng haholo tsa 3D tse entsoeng ka lisebelisoa tsa catalytically active, thermally conductive tse nang le likarolo tsa 4 tse kenngoeng ka ho toba (fifinseng 4).
Aluminium-copper flow reactor e entsoeng ke tlhahiso ea li-ultrasonic additive (UAM) e nang le mohaho o rarahaneng oa mochine oa ka hare, li-thermocouples tse kentsoeng le catalytic reaction chamber.Ho bona litsela tsa metsi a ka hare, prototype e hlakileng e entsoeng ka ho sebelisa stereolithography e boetse e bontšoa.
Ho etsa bonnete ba hore li-reactors li entsoe bakeng sa ho sebetsa ka moso, lihlapolli li hloka ho futhumatsoa ka mokhoa o sireletsehileng ka holim'a ntlha e belang; ke khatello le mocheso o lekiloeng.Teko ea khatello e bontšitse hore tsamaiso e boloka khatello e tsitsitseng le e sa khaotseng esita le ka khatello e eketsehileng ea tsamaiso (1.7 MPa) .Teko ea hydrostatic e ne e etsoa ka mocheso oa kamore ho sebelisa H2O e le mokelikeli.
Ho kopanya thermocouple e kentsoeng (setšoantšo sa 1) ho mochine oa data oa mocheso ho bontšitse hore thermocouple e ne e le 6 °C (± 1 °C) e pholileng ho feta mocheso o hlophisitsoeng tsamaisong ea FlowSyn. high thermal diffusivity of the materials used in the industrial process.This thermal drift is consistent and therefore can be accounted in the equipment setup ho etsa bonnete ba hore mocheso o nepahetseng o fihlellwa le ho lekanyetswa nakong ya reaction.Therefore, this online monitoring tool facilitates tight control of reaction temperature and facilitates more correct process optimization and development of optimal conditions.These sensors ho hlwaya escale reaction-systems e ka boela ea sebelisoa.
Reactor e hlahisitsoeng mosebetsing ona ke mohlala oa pele oa tšebeliso ea theknoloji ea UAM ho etsoa ha lik'hemik'hale tsa lik'hemik'hale 'me e sebetsana le mefokolo e mengata e meholo eo hona joale e amanang le khatiso ea AM / 3D ea lisebelisoa tsena, tse kang: (i) ho hlōla mathata a tlalehiloeng a amanang le ts'ebetso ea koporo kapa ea aluminium alloy (ii) e ntlafetseng ea tharollo ea ka hare ho bapisoa le phofshoana ea bethe ea phofo (PBF) mekhoa ea ho phalla ha bethe ea phofshoana (PBF) tse kang khetha6 laser kapa lisebelisoa tsa Pomel5, SLM 9, mohlala, SLM 2. rough surface texture26 (iii) Mocheso o fokotsehileng oa ho sebetsa, o nolofalletsang ho tlamahanngoa ka ho toba ha li-sensor, tse ke keng tsa khoneha ho thekenoloji ea bethe ea phofo, (v) ho hlōla thepa e fokolang ea mochine le kutloisiso ea likarolo tse thehiloeng ho polymer ho mefuta e sa tšoaneng e tloaelehileng ea li-solvent17,19.
Ts'ebetso ea sekontiri se ile sa bontšoa ke letoto la li-alkyne azide cycloaddition reactions tsa koporo-catalyzed tlas'a maemo a phallang a tsoelang pele (Setšoantšo sa 2) . The ultrasonic-printed koporo reactor e qaqileng ho Figure 4 e ne e kopantsoe le tsamaiso ea khoebo ea phallo 'me e sebelisetsoa ho kopanya li-azides tsa laebrari tsa mefuta e sa tšoaneng ea 1,4-disubstituted 1,4-disubstituted 1,4-disubstituted 1,4-disubstituted 1,4-disubstituted 1,4-disubstituted the-control 1,4-disubstituted 1,4-disubstituted 1,4-disubstituted the-control-azoled-control reaction, le lihlopha tsa alkyl halides boteng ba sodium chloride (Setšoantšo sa 3) .Tšebeliso ea mokhoa o tsoelang pele oa ho phalla o fokotsa mathata a tšireletso a ka hlahang ka mekhoa ea batch, kaha karabelo ena e hlahisa li-intermediate tsa azide tse sebetsang haholo le tse kotsi [317], [318] . Cycloaddition ea phenylacetylene le iodoethane) (sheba setšoantšo sa 5).
(Holimo ka ho le letšehali) Schematic ea setup e sebelisetsoang ho kenyelletsa mochine oa 3DP tsamaisong ea phallo (ka holimo ka ho le letona) e fumanoang ka mokhoa o ntlafalitsoeng (ka tlaase) oa morero oa Huisgen cycloaddition 57 pakeng tsa phenylacetylene le iodoethane bakeng sa ho ntlafatsa le ho bontša litekanyo tse ntlafalitsoeng tsa phetoho ea tekanyo ea phetoho.
Ka ho laola nako ea bolulo ea li-reagents karolong ea catalytic ea reactor le ho shebella mocheso oa karabelo ka mochine o kopantsoeng ka ho toba oa thermocouple, maemo a karabelo a ka ntlafatsoa ka potlako le ka mokhoa o nepahetseng ka nako e fokolang le tšebeliso ea lintho tse bonahalang. nako ea bolulo ka bobeli le mocheso oa karabelo li nkoa e le mantsoe a bohlokoa a mohlala.Ho matha sesebediswa se hahelletsoeng ka har'a optimizer ho sebelisa mantsoe ana a khethiloeng ho hlahisa maemo a karabelo a etselitsoeng ho eketsa libaka tsa tlhoro ea sehlahisoa ha a ntse a fokotsa libaka tse qalang tsa tlhōrō ea lintho tse bonahalang.Tlhahiso ena e ile ea fana ka phetoho ea 53% ea sehlahisoa sa triazole, se neng se tšoana hantle le polelo ea mohlala ea 54%.
Ho ipapisitsoe le lingoliloeng tse bonts'ang hore koporo(I) oxide (Cu2O) e ka sebetsa e le mofuta o sebetsang oa ho thusa holim'a koporo ea zero-valent maemong ana, bokhoni ba ho etsa oxidize holim'a metsi pele ho ts'ebetso ea phallo e ile ea batlisisoa70,71. Karabelo lipakeng tsa phenylacetylene le iodoethane e ile ea boela ea etsoa ka lebaka la keketseho e kholo maemong a eona. phetohong ea thepa ea ho qala, e neng e baloa ho > 99% . Leha ho le joalo, tlhokomelo ea HPLC e bontšitse hore phetoho ena e fokolitse haholo nako e telele ea ho itšoara ka nako e telele ho fihlela hoo e ka bang metsotso ea 90, moo mosebetsi o neng o bonahala o le boemong bo botle 'me o fihla "boemong bo tsitsitseng". mocheso ho theha CuO le Cu2O tseo e seng lihlopha tsa ho itšireletsa.Sena se felisa tlhokahalo ea ho eketsa mohloli oa koporo (II) o thusang bakeng sa ho kopanya71.