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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. Lik'hemik'hale tsa bohlokoa tsa 1,4-disubstituted 1,2,3-triazole li ile tsa etsoa ka katleho 'me tsa 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 k'hemik'hale sebaka sa khale kapa lisebelisoa tsa k'hemistri ka 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, kapa maemo a sebelisoang ke poly-based feela. mekhoa ea khatiso e kang stereolithography (SL)9,10,11, fused deposition modeling (FDM)8,12,13,14 le inkjet printing 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 / litlhahlobo17, 18, limiting 2018 sebakeng sena se seholo, 20 AM 19 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) .This solid-state sheet lamination techniques e sebetsa ka ultrasonic oscillations to thin metal foils in order to join them together layer by layer with minimal bulk heat and high degree of plastic flow 21 ts'ebetso, eo ho eona in-situ periodic computer numberal control (CNC) milling kapa laser machining e hlalosang sebopeho sa letlooa la lera la lintho tse tlamiloeng 24, 25.Sena se bolela hore mosebelisi ha a lekanyetsoe ke mathata a amanang le ho tlosa thepa ea ho aha e tala ho tloha liteisheneng tse nyane tsa mokelikeli, tseo hangata ho leng joalo ka phofo le litsamaiso tsa mokelikeli tsa AM26,27,28. metsoako ea lintho tse bonahalang mohatong o le mong oa ts'ebetso.Khetho ea metsoako ea thepa e fetang mokhoa oa 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 tlamahano ea boemo bo tiileng, ntho e' ngoe e etsahalang nakong ea bonding ea ultrasonic ke phallo e phahameng ea thepa ea polasetiki ka mocheso o batlang o le tlase29,30,31,32,33.Tlhaloso ena e ikhethang ea UAM ea ho etsa hore ho be bonolo ho senya lisebelisoa tsa tšepe tsa UAM ntle le ho etsa hore ho be bonolo ho senya / ho tsamaisa lisebelisoa tsa tšepe. 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 li-sensor tsa mocheso ka ho toba pakeng tsa melapo ea reagent bakeng sa tlhahlobo e nepahetseng ea mocheso oa karabelo le taolo.Ho bontša 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 e ka bulang moralo o mocha oa lisebelisoa menyetla le menyetla ea k'hemistri ka lipatlisiso tse ngata.
Li-solvents le li-reagents kaofela 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, e ile ea fumanoa ho sebelisoa JEOL ECS-400 400 spectrometer 400 MHz spectra ea 400 MHz le CMHz II MHz l3 kapa (CD3)2SO e le solvent.Likarabo tsohle li entsoe ho sebelisoa Uniqsis FlowSyn chemistry platform.
UAM e ne e sebelisetsoa ho etsa lisebelisoa tsohle thutong ena.Theknoloji e ile ea qaptjoa ka 1999, 'me lintlha tsa eona tsa tekheniki, mekhahlelo ea 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 ho sebelisoa matla a phahameng haholo, 9kW SonicLayer UAM 4000 tsamaiso ea thepa ea OFabri ea OFabri ea OHbri ea USA 4000. sesebelisoa e ne e le Cu-110 le Al 6061.Cu-110 e na le lintho tse ngata tsa koporo (bonyane 99.9% ea koporo), e leng se etsang hore e be mokhethoa o motle bakeng sa liketso tsa koporo-catalyzed, 'me ka hona e sebelisoa e le "lesela le sebetsang ka hare ho microreactor.Al 6061 O e sebelisoa e le "bongata" thepa, hape Embedding layer e sebelisetsoang tlhahlobo;Karolo e thusang ea motsoako oa motsoako le 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 Lik'hemik'hale li tsitsitse le li-reagents tse sebelisoang mosebetsing ona.Motsoako oa Al 6061 O le Cu-110 o boetse o nkoa e le motsoako oa thepa o lumellanang bakeng sa UAM 'me ka hona ke boitsebiso bo loketseng thutong ena.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. ho kopanya ho ka finyelloang, moqapi oa li-reactor o na le li-inlets tse peli tsa reagent tse kopantsoeng le Y-junction pele li kena karolong e kopanyang ea noha. Sekoti sa boraro, se phunyeletsang molapo bohareng ba sebaka sa bolulo ba sona, se kenyelelitsoe moqapong oa li-syntheses tsa li-multistep reaction tsa nakong e tlang.
Liteishene tsohle li na le profil ea lisekoere (ha ho na li-angles), sephetho sa nako le nako CNC milling e sebelisetsoang ho etsa geometry ea kanale 750 µm le kakaretso ea molumo oa reactor e ne e le 1 ml. Sehokelo se kopantsoeng (1/4″—28 UNF thread) se kenyelelitsoe moqapong oa ho lumella ho hokahanya 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. sebetsa, e le ho boloka symmetry ea mocha, ho ne ho sebelisoa kemiso ea lisekoere.
Nakong ea khefu e reriloeng esale pele ha ho etsoa, ​​​​li-thermocouple tsa mocheso (Mofuta oa K) li 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). ho nepahala ho bolokoa 'me karolo e phethiloeng e tla kopana le maemo a ho nepahala ha CNC finish milling.Bophara ba kanale bo sebelisitsoeng bakeng sa sesebelisoa sena bo nyane ka ho lekaneng ho etsa bonnete ba hore thepa ea foil ha e "sag" ka har'a mocha oa mokelikeli, kahoo mocha o boloka sekoahelo sa lisekoere.Likheo tse ka khonehang tsa thepa ea foil le mekhoa ea ts'ebetso ea UAM e ile ea khethoa ka liteko ke molekane oa tlhahiso (Fabrisonic LLC, USA).
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 tsoa ho reactor le ho pompa metsi ka mochine ka sekhahla sa 0.1 ho 1 mL min-1. Khatello ea motlakase e ne e hlahlojoa ka ho sebelisa FlowSyn e hahiloeng ka har'a mochine oa khatello ea tsamaiso ho netefatsa hore tsamaiso e ka boloka phapang e tsitsitseng ea mocheso pakeng tsa mocheso o sa khaotseng oa mocheso. li-rmocouples tse kentsoeng ka har'a reactor le tse kentsoeng ka har'a FlowSyn chip heat plate
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 (DOE le reside reside ratio) 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 ne li lokiselitsoe.A 1.5 mL aliquot ea tharollo e 'ngoe le e' ngoe e ne e tsoakane 'me ea phunyeletsoa ka mochine ka tekanyo e lakatsehang ea phallo le mocheso e le sebaka sa triaea phezole sehlahiswa se neng se nkiloe ho ea karabelo ea thepa ea triace le phezole. ka high performance liquid chromatography (HPLC) .Bakeng sa ho tsitsana ha tlhahlobo, litloaelo tsohle li ile tsa etsoa sampuli feela ka mor'a hore motsoako oa karabelo o tlohe ho reactor.Mekhahlelo ea paramethara e khethiloeng bakeng sa ho ntlafatsa e bontšoa ho Lethathamo la 2.
Mehlala eohle e ile ea hlahlojoa ho sebelisoa tsamaiso ea Chromaster HPLC (VWR, PA, USA) e nang le pompo ea quaternary, oven ea column, variable wavelength UV detector le autosampler. The column e ne e le Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 100 mm ka boholo, particletic 500 mm, particletic 500 mm. 50 methanol:metsi ka sekhahla sa phallo ea 1.5 mL.min-1. Bophahamo ba ente e ne e le 5 µL le bolelele ba maqhubu a detector e ne e le 254 nm. Sebaka sa tlhoro sa% sa sampole ea DOE se ne se baloa ho tloha libakeng tse phahameng tsa masala a alkyne le lihlahisoa tsa triazole feela.Ente ea thepa e loketseng e lumellang tlhōrō ea lisebelisoa tse qalang.
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 ea dilutate ka kakaretso ea 150 ° C. .Mohlala oa tharollo o ile oa hlatsuoa ka 3 × 10 mL ea metsi. Likarolo tse nang le metsi li kopantsoe 'me li 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 'me li tlhotliloeng, ebe solvent e 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-spection mass (13C HRM-spectrum).
Lisebelisoa tsohle li ile tsa fumanoa ka ho sebelisa 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 motsoakong o hlapolotsoeng oa crude reaction (1:10 dilution) mme tsa hlahlobjoa ka metsi:methanol (50:50 kapa 70:30), ntle le disampole 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/C5m2 e bolokiloe ka kholumo ea 4 ° th 4. .
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 e qalang 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 sisinya thepa. 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-'mmuso ho li-interfaces tsa thepa;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 tlase, ke hore, ka tlas'a ntlha ea ho qhibiliha ea lisebelisoa tsa tšepe. Motsoako oa ultrasonic oscillation 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. ka lera.Lintho 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 tse atisang ho sebelisoa tšepe, Cu catalysis e na le melemo e 'maloa: (i) 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 fapaneng ea liketso tsa Cu-catalyzed cross-coupling reactions e ntse e eketseha' me e bonahala e le mokhoa o itseng oa ho tlatsana le Pd5caly Zed reactions sebetsa hantle ka ho ba sieo ha ligand tse ling, Li-ligands tsena hangata structurally 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-catalyzed chemistry le Sonogashides cycload ke promothaling Sonogashides couple 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 demonstration reaction. .
Boitšoaro bona bo ile ba boela ba tsepamisa maikutlo ha Sharpless le ba bang ba hlahisa khopolo ea "tobetsa k'hemistri" 59. Lentsoe "tobetsa k'hemistri" le sebelisetsoa ho hlalosa mekhoa e matla, e ka tšeptjoang le e khethiloeng bakeng sa motsoako o potlakileng oa metsoako e mecha le lilaebrari tsa combinatorial ka heteroatom linkage (CXC)60 The synthetic chemistry of these reactions is 60 the synthetic reaction of these reactions high reactions is 6 1.
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 ea azide-alkyne e feta 107 ho 108 ka ho ba teng ha Cu(I) bapisoa le uncatalyzed 1,3-dipolar rate ha e hloke 6cceledi 62. lihlopha 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 Boistame tsa Manahatso le Copper Huadzed huiscload ea li-huplyzing.cu (i)-trifited huissecles 1,4 le 1,2-Tears ea li-shrereoos tsa Azoles.
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 kenya letsoho ho kenya ts'ebetsong ts'ebetso ea molek'hule e 'ngoe le e' ngoe ho ea ho azide.Mochine o reriloeng o tsoela pele ka lesale la tšepe le nang le litho tse tšeletseng tse entsoeng ka ho hokahanya ha azide ho σ-bonded koporo acetylide e nang le π-bonded copper e le copper e tsitsitseng ea copper. , e lateloa 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 (setšoantšo sa 1) thermocouple ho data data logger e bontšitse hore thermocouple e ne e le 6 °C (± 1 °C) e pholileng ho feta mocheso o hlophisitsoeng tsamaisong ea FlowSyn. Ka tloaelo, ho eketseha ha 10 ° C mocheso ho fella ka ho imena habeli ha sekhahla sa karabelo, kahoo phapang ea mocheso ea likhato tse seng kae feela ka lebaka la ho lahleheloa ke 'mele oa reactor e ka fetoha haholo. ffusivity of the materials used in the industrial process.This thermal drift is consistent and therefore can be accounted in the equipment setup to sure to right the temperatures access and measureed during the reaction.Therefore, this online monitoring tool facilitates tight control of reaction temperature and be facilitates more correct process optimization and development of optimal conditions.These sensors can also be used to detect the huge reactions.These sensors can also be used to detect the huge reaction-e-processing.
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 koporo kapa aluminium alloy processing (ii) e ntlafetseng ea tharollo ea ka hare ho bapisoa le phofo ea bethe fusion (PBF) mekhoa e mengata ea ho phalla ha laser 6 (PBF) mekhoa e mengata ea ho phalla ha laser6, le ho khetha mekhoa ea 6 laser ea ho phalla holimo. (iii) Mocheso o fokotsehileng oa ho sebetsa, o nolofalletsang ho kopana ka ho toba ha li-sensor, tse ke keng tsa khoneha ho thekenoloji ea bethe ea phofo, (v) ho hlōla mekhoa e mebe ea mechine le kutloisiso ea likaroloana tsa 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 (Fig. 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 the-tricealed reaction, 1. halides ka boteng ba sodium chloride (Setšoantšo sa 3) .Tšebeliso ea mokhoa o tsoelang pele oa ho phalla o fokotsa mathata a ts'ireletso a ka hlahang mekhoeng ea li-batch, kaha karabelo ena e hlahisa li-intermediate tsa azide tse sebetsang haholo le tse kotsi [317], [318]. 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 ho lula ha li-reagents karolong ea catalytic ea reactor le ho shebella mocheso oa karabelo ka probe e kopantsoeng ka ho toba ea thermocouple, maemo a karabelo a ka ntlafatsoa ka potlako le ka mokhoa o nepahetseng ka nako e fokolang le tšebeliso ea thepa. le mocheso karabelo li nkoa e le tsa bohlokoa mohlala mantsoe a.Matha a haha-ka optimizer sebelisa mantsoe ana a khethiloeng hlahisa sete ya maemo a itšoara joang etselitsoe ho maximize libaka tlhōrō ea lihlahisoa ha ho fokotsa ho qala thepa tlhōrō libaka.This optimization ile a hlahisa 53% phetoho ea sehlahisoa triazole, e leng haufi-ufi tšoanang le mohlala ho bolela esale pele ea 54%.
Ho ipapisitsoe le lingoliloeng tse bonts'ang hore koporo(I) oxide (Cu2O) e ka sebetsa e le mofuta o matla 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 bo ile ba fuputsoa70,71. Karabelo lipakeng tsa phenylacetylene le iodoethane e ile ea etsoa hape tlasa maemo a bohlokoa a ho lokisoa. ea thepa ea ho qala, e neng e baloa ho > 99%.Leha ho le joalo, tlhahlobo 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". ha se mekhahlelo e itšireletsang.Sena se felisa tlhokahalo ea ho eketsa mohloli o thusang oa koporo(II) bakeng sa ho kopanya71.