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Carousel e bonts'ang li-slide tse tharo ka nako e le 'ngoe.Sebelisa likonopo tse Fetileng le Tse Latelang ho feta har'a li-slide tse tharo ka nako, kapa sebelisa likonopo tsa selaete qetellong ho tsamaea har'a li-slide tse tharo ka nako.
Tlhahiso e eketsehileng e fetola tsela eo bafuputsi le bo-raliindasetsi ba qapang le ho etsa lisebelisoa tsa lik'hemik'hale ho finyella litlhoko tsa bona tse khethehileng.Ka pampiri ena, re tlaleha mohlala oa pele oa mochine o phallang o entsoeng ke ultrasonic additive industrial (UAM) lamination ea letlapa le tiileng le nang le likarolo tsa catalytic tse kopantsoeng ka ho toba le likarolo tsa kutlo.Theknoloji ea UAM ha e hlōle feela meeli e mengata e amanang le tlhahiso ea lik'hemik'hale tsa lik'hemik'hale, empa e boetse e eketsa bokhoni ba lisebelisoa tse joalo.Lik'hemik'hale tse 'maloa tsa bohlokoa tsa biologically 1,4-disubstituted 1,2,3-triazole li entsoe ka katleho le ho ntlafatsoa ke Cu-mediated 1,3-dipolar Huisgen cycloaddition reaction ho sebelisa setsi sa lik'hemik'hale sa UAM.E sebelisa thepa e ikhethang ea UAM le ts'ebetso e tsoelang pele ea phallo, sesebelisoa se khona ho ts'oara karabelo e tsoelang pele le ho fana ka maikutlo a nako ea nnete ho lekola le ho ntlafatsa karabelo.
Ka lebaka la melemo ea eona e kholo ho feta molekane oa eona ka bongata, k'hemistri ea phallo ke tšimo ea bohlokoa le e ntseng e hola maemong a thuto le a indasteri ka lebaka la bokhoni ba eona ba ho eketsa khetho le katleho ea motsoako oa lik'hemik'hale.Sena se fetela ho thehoa ha limolek'hule tse bonolo tsa organic1 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 ho phallo e tsoelang pele7.
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 thepa ea k'hemistri ea phallo ka lik'hemik'hale tse feto-fetohang "li-reactor"8.Moralo o ipheta-phetang, oa ho etsa ka potlako, le bokhoni ba likarolo tse tharo (3D) tsa mekhoa ena li bohlokoa ho ba batlang ho etsa lisebelisoa tsa bona ka mokhoa o ikhethileng bakeng sa karabelo e itseng, lisebelisoa kapa maemo.Ho fihlela joale, mosebetsi ona o tsepamisitse maikutlo hoo e batlang e le ho sebelisoa ha 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 inkjet7,15., 16. Ho hloka botšepehi le bokhoni ba lisebelisoa tse joalo ho etsa mefuta e mengata ea lik'hemik'hale / litlhahlobo17, 18, 19, 20 ke ntho e ka sehloohong e thibelang tšebeliso e pharaletseng 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 metle e tla lumella basebelisi ho etsa likepe tse sebetsanang le phallo tse nang le bokhoni bo ntlafalitsoeng ba k'hemistri le tlhahlobo.Mekhoa ena e lokela ho lumella basebelisi ho khetha ho tsoa mefuteng e mengata ea matla a phahameng kapa lisebelisoa tse sebetsang tse khonang ho sebetsa tlas'a maemo a mangata a karabelo, hammoho le ho nolofatsa mefuta e fapaneng ea tlhahiso ea tlhahlobo ho tsoa sesebelisoa ho thusa ho beha leihlo le ho laola karabelo.
Ts'ebetso e 'ngoe ea tlatsetso e ka sebelisoang ho nts'etsapele li-reactor tsa lik'hemik'hale tse tloaelehileng ke Ultrasonic Additive Manufacturing (UAM).Mokhoa ona o tiileng oa letlapa la lamination o sebetsa ka li-vibrations tsa ultrasonic ho li-foil tse tšesaane tsa tšepe ho li kopanya hammoho lera ka lera le nang le mocheso o fokolang oa volumetric le tekanyo e phahameng ea phallo ea polasetiki 21, 22, 23. Ho fapana le mahlale a mang a mangata a AM, UAM e ka kopanngoa ka ho toba le tlhahiso ea subtractive, e tsejoang e le mokhoa oa ho etsa lihlahisoa tse nyalisitsoeng, moo nako le nako in-situ-situ e lekanyetsang taolo ea linomoro tsa 4 kapa CNC (CNC) 25. Sena se bolela hore mosebedisi ha a felle feela mathateng a amanang le ho tlosoa ha thepa ea ho haha ​​​​ea pele e setseng ho tloha liteisheneng tse nyenyane tsa metsi, tseo hangata li leng teng ka phofo le mekhoa ea metsi AM26,27,28.Tokoloho ena ea moralo e boetse e fetela ho khetho ea lisebelisoa tse fumanehang - UAM e ka kopanya metsoako ea thepa e tšoanang le ea mocheso ka mokhoa o le mong oa ts'ebetso.Khetho ea metsoako ea thepa e fetang mokhoa oa ho qhibiliha e bolela hore litlhoko tsa mochine le tsa lik'hemik'hale tsa lisebelisoa tse khethehileng li ka fihlelleha hamolemo.Ho phaella ho tlamahano e tiileng, ntho e 'ngoe e etsahalang ka bonding ea ultrasonic ke metsi a mangata a thepa ea polasetiki ka mocheso o batlang o le tlaase29,30,31,32,33.Tšobotsi ena e ikhethang ea UAM e lumella lisebelisoa tsa mochini / mocheso hore li behoe pakeng tsa likarolo tsa tšepe ntle le tšenyo.Li-sensor tsa UAM tse kentsoeng li ka thusa ho fana ka tlhaiso-leseling ea nako ea nnete ho tloha sesebelisoa ho ea ho mosebelisi ka li-analytics tse kopaneng.
Mosebetsi o fetileng oa bangoli32 o bonts'itse bokhoni ba ts'ebetso ea UAM ho theha meaho ea tšepe ea 3D ea microfluidic e nang le matla a ho lemoha a kenelletseng.Sesebelisoa sena ke sa merero ea ho beha leihlo feela.Sengoliloeng sena se fana ka mohlala oa pele oa "microfluidic chemical reactor" e entsoeng ke UAM, sesebelisoa se sebetsang se sa laoleng feela empa se boetse se etsa hore lik'hemik'hale li kopane ka lisebelisoa tse entsoeng ka mokhoa o hlophisitsoeng.Sesebelisoa sena se kopanya melemo e 'maloa e amanang le theknoloji ea UAM ha ho etsoa lisebelisoa tsa lik'hemik'hale tsa 3D, tse kang: bokhoni ba ho fetola moralo o feletseng oa 3D ka ho toba ho tloha moetsong oa lisebelisoa tsa k'homphieutha (CAD) ho sehlahisoa;tlhahiso ea lisebelisoa tse ngata bakeng sa motsoako oa mocheso o phahameng oa mocheso le lisebelisoa tsa catalytic, hammoho le li-sensor tsa mocheso tse kenngoeng ka ho toba pakeng tsa melapo ea reactant bakeng sa taolo e nepahetseng le tsamaiso ea mocheso o arabelang.E le ho bonts'a ts'ebetso ea mochine, laebrari ea metsoako ea bohlokoa ea meriana ea 1,4-disubstituted 1,2,3-triazole e entsoe ka koporo-catalyzed 1,3-dipolar Huisgen cycloaddition.Mosebetsi ona o totobatsa kamoo tšebeliso ea mahlale a thepa le moralo o thusoang ke khomphutha li ka bulang menyetla le menyetla e mecha bakeng sa k'hemistri ka lipatlisiso tse fapaneng.
Lisebelisoa 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 le 100 MHz, ka ho latellana, e fumanoe ho JEOL ECS-400 400 MHz spectrometer kapa Bruker Avance II 400 MHz spectrometer e nang le CDCl3 kapa (CD3)2SO e le solvent.Likarabo tsohle li entsoe ho sebelisoa sethala sa chemistry sa Uniqsis FlowSyn.
UAM e sebelisitsoe ho etsa lisebelisoa tsohle thutong ena.Theknoloji e qapiloe ka 1999 mme lintlha tsa eona tsa tekheniki, mekhahlelo ea ts'ebetso le nts'etsopele ho tloha ha e qaptjoa e ka ithutoa ka lisebelisoa tse latelang tse hatisitsoeng34,35,36,37.Sesebelisoa (setšoantšo sa 1) se ile sa sebelisoa ho sebelisa mosebetsi o boima oa 9 kW SonicLayer 4000® UAM system (Fabrisonic, Ohio, USA).Lisebelisoa tse khethiloeng bakeng sa sesebelisoa sa phallo 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 ea molemo bakeng sa liketso tse entsoeng ka koporo 'me ka hona e sebelisoa e le "lesela le sebetsang ka hare ho microreactor.Al 6061 O e sebelisoa e le thepa ea "bongata"., hammoho le lera la intercalation le sebelisetsoang tlhahlobo;ho hokahanngoa ha likarolo tsa alloy tse thusang le boemo ba annealed hammoho le lera la Cu-110.e fumanoe e tsitsitse lik'hemik'hale le li-reagents tse sebelisoang mosebetsing ona.Al 6061 O hammoho le Cu-110 e boetse e nkoa e le motsoako oa thepa o lumellanang bakeng sa UAM 'me ka hona ke boitsebiso bo loketseng thutong ena38,42.Lisebelisoa tsena li thathamisitsoe ho Lethathamo la 1 ka tlase.
Mehato ea ho etsa li-reactor (1) 6061 aluminium alloy substrate (2) Ho etsoa ha mocha o tlaase ho tloha foil ea koporo (3) Ho kenngoa ha li-thermocouples pakeng tsa lihlopha (4) mocha o ka holimo (5) Inlet le outlet (6) Monolithic reactor.
Filosofi ea moralo oa mocha oa mokelikeli ke ho sebelisa tsela e boima ho eketsa sebaka se tsamaeang ke mokelikeli o ka hare ho chip ha o ntse o boloka boholo bo laolehang ba chip.Keketseho ena ea bohole e lakatseha ho eketsa nako ea ho ikopanya le catalyst-reactant le ho fana ka lihlahisoa tse ntle haholo tsa lihlahisoa.Li-chips li sebelisa 90 ° ho khumama lipheletsong tsa tsela e otlolohileng ho etsa hore ho be le motsoako o moferefere ka har'a sesebelisoa44 le ho eketsa nako ea ho kopana le metsi ka holim'a metsi (catalyst).Ho tsoela pele ho ntlafatsa ho kopanya ho ka finyelloang, moqapi oa mochine o kenyelletsa li-inlets tse peli tsa reactant tse kopantsoeng le Y-connection pele li kena karolong ea coil e kopanyang.Monyako oa boraro, o tšelang phallo bohareng ba sebaka sa eona sa bolulo, o kenyelelitsoe morerong oa kamoso oa methati e mengata ea methati.
Liteishene tsohle li na le profil ea lisekoere (ha ho na li-angles tsa taper), e leng phello ea nako le nako CNC milling e sebelisitsoeng ho theha geometry ea mocha.Litekanyo tsa kanane li khethiloe ho fana ka chai e phahameng (bakeng sa microreactor) ea volumetric, leha ho le joalo e nyane ho lekana ho nolofatsa tšebelisano le bokaholimo (li-catalyst) bakeng sa bongata ba maro a teng.Boholo bo loketseng bo ipapisitse le boiphihlelo ba bangoli ba nakong e fetileng ka lisebelisoa tsa tšepe tsa metsi.Litekanyo tse ka hare tsa mocha oa ho qetela e ne e le 750 µm x 750 µm 'me kakaretso ea molumo oa reactor e ne e le 1 ml.Sehokelo se hahelletsoeng (1/4″-28 UNF thread) se kenyellelitsoe moqapong oa ho lumella ho hokahana habonolo ha sesebelisoa ka lisebelisoa tsa k'hemistri ea phallo ea khoebo.Boholo ba mocha bo lekanyelitsoe ke botenya ba thepa ea foil, thepa ea eona ea mechine, le mekhoa ea ho kopanya e sebelisoang le ultrasonics.Ka bophara bo itseng bakeng sa boitsebiso bo fanoeng, boitsebiso bo tla "sag" mocha o entsoeng.Hajoale ha ho na mohlala o ikhethileng oa lipalo tsena, kahoo boholo ba bophara ba kanale bakeng sa thepa e fanoeng le moralo bo khethoa ka liteko, moo bophara ba 750 µm bo ke keng ba baka tsitsipano.
Sebopeho (sekoere) sa mocha se ikemiselitsoe ho sebelisa "square cutter".Sebopeho le boholo ba likanale li ka fetoloa mochining oa CNC ho sebelisa lisebelisoa tse fapaneng tsa ho itšeha ho fumana litefiso le litšobotsi tse fapaneng tsa phallo.Mohlala oa ho theha mocha o kobehileng ka sesebelisoa sa 125 µm o ka fumanoa Monaghan45.Ha lesela la foil le sebelisoa ka sephara, ho sebelisoa ha thepa ea foil ho likanale ho tla ba le sebaka se bataletseng (sekwere).Mosebetsing ona, ho ile ha sebelisoa square contour ho boloka symmetry ea kanale.
Nakong ea khefu e hlophisitsoeng ea tlhahiso, li-sensorer tsa mocheso oa thermocouple (mofuta oa K) li hahiloe ka ho toba ka har'a sesebelisoa pakeng tsa lihlopha tse ka holimo le tse tlaase (setšoantšo sa 1 - sethaleng sa 3).Li-thermocouples tsena li ka laola ho fetoha ha mocheso ho tloha ho -200 ho ea ho 1350 °C.
Ts'ebetso ea ho beha tšepe e etsoa ke lenaka la UAM le sebelisa foil ea tšepe e bophara ba limilimithara tse 25.4 le botenya ba li-micron tse 150.Mekhahlelo ena ea foil e hokahane ka letoto la likhoele tse haufi ho koahela sebaka sohle sa kaho;boholo ba thepa e kentsoeng e kholo ho feta sehlahisoa sa ho qetela kaha mokhoa oa ho tlosa o etsa hore ho be le sebopeho se hloekileng sa ho qetela.Mechine ea CNC e sebelisetsoa ho kenya lisebelisoa tsa ka ntle le tse ka hare tsa lisebelisoa, ho fella ka ho fela ha lisebelisoa le likanale tse tsamaellanang le sesebelisoa se khethiloeng le mekhoa ea ts'ebetso ea CNC (mohlala ona, hoo e ka bang 1.6 µm Ra).E tsoelang pele, e tsoelang pele ea ultrasonic thepa ea ho fafatsa le mechine ea mechine e sebelisoa ho pholletsa le ts'ebetso ea tlhahiso ea lisebelisoa ho etsa bonnete ba hore ho nepahala hoa bolokoa 'me karolo e phethiloeng e kopana le maemo a nepahetseng a CNC.Bophara ba mocha o sebelisoang bakeng sa sesebelisoa sena bo nyane ka ho lekaneng ho etsa bonnete ba hore thepa ea foil ha e "sag" ka mocha oa mokelikeli, kahoo mocha o na le karolo ea sefapano sa lisekoere.Likheo tse ka bang teng ka har'a thepa ea foil le litekanyetso tsa ts'ebetso ea UAM li ile tsa khethoa ka liteko ke molekane oa tlhahiso (Fabrisonic LLC, USA).
Liphuputso li bontšitse hore ho sebopeho sa 46, 47 sa motsoako oa UAM ho na le phapang e fokolang ea likarolo ntle le phekolo e eketsehileng ea mocheso, kahoo bakeng sa lisebelisoa tse sebetsang mosebetsing ona lera la Cu-110 le lula le fapane le Al 6061 le ho fetoha haholo.
Kenya "pre-calibrated back pressure regulator" (BPR) ho 250 psi (1724 kPa) ho ea tlaase ho setsi sa motlakase 'me u pompe metsi ka mochine ka tekanyo ea 0.1 ho 1 ml min-1.Khatello ea li-reactor e ne e behiloe leihlo ho sebelisa FlowSyn khatello ea transducer e hahiloeng tsamaisong ho netefatsa hore tsamaiso e ka boloka khatello e tsitsitseng kamehla.Li-gradients tse ka bang teng tsa mocheso mochining oa phallo li ile tsa lekoa ka ho batla phapang lipakeng tsa li-thermocouples tse hahelletsoeng ka har'a reactor le li-thermocouples tse hahiloeng ka har'a poleiti ea ho futhumatsa ea chip ea FlowSyn.Sena se finyelloa ka ho fetola mocheso o hlophisitsoeng oa hotplate pakeng tsa 100 le 150 °C ka 25 °C increments le ho hlokomela phapang leha e le efe pakeng tsa mocheso o hlophisitsoeng le o rekotiloeng.Sena se ile sa finyelloa ho sebelisoa tc-08 data logger (PicoTech, Cambridge, UK) le software e tsamaeang le PicoLog.
Maemo a cycloaddition reaction ea phenylacetylene le iodoethane a ntlafalitsoe (Scheme 1-Cycloaddition ea phenylacetylene le iodoethane, Scheme 1-Cycloaddition ea phenylacetylene le iodoethane).Ntlafatso ena e entsoe ka mokhoa o felletseng oa moralo oa liteko (DOE), ho sebelisoa mocheso le nako ea bolulo e le lintho tse fapaneng ha ho ntse ho lokisoa karolelano ea alkyne:azide ho 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.Aliquot ea 1.5 ml ea tharollo e 'ngoe le e' ngoe e ne e tsoakoa 'me ea pompeloa ka mochine oa motlakase ka tekanyo e lakatsehang ea ho phalla le mocheso.Karabelo ea mohlala e ile ea nkuoa e le karo-karolelano ea sebaka se phahameng sa sehlahisoa sa triazole ho thepa e qalang ea phenylacetylene mme e ile ea khethoa ho sebelisoa chromatography ea metsi a phahameng (HPLC).Bakeng sa ts'ebetso ea tlhahlobo, liketso tsohle li nkuoe hang ka mor'a hore motsoako oa karabelo o tlohe ho reactor.Mekhahlelo e khethiloeng bakeng sa ntlafatso e bonts'itsoe ho Lethathamo la 2.
Mehlala eohle e ile ea hlahlobjoa ho sebelisoa mochini oa Chromaster HPLC (VWR, PA, USA) o nang le pompo ea quaternary, ovine ea litšiea, mochine oa UV oa wave wave le autosampler.Kholomo e ne e le Equivalence 5 C18 (VWR, PA, USA), 4.6 x 100 mm, 5 µm ea boholo ba likaroloana, e bolokiloe ho 40°C.The solvent e ne e le isocratic methanol:metsi 50:50 ka tekanyo ea phallo ea 1.5 ml · min-1.Bophahamo ba ente e ne e le 5 μl mme bolelele ba maqhubu a detector e ne e le 254 nm.Sebaka sa tlhōrō sa % sa sampole ea DOE se baloa ho tloha libakeng tse phahameng tsa masala a alkyne le lihlahisoa tsa triazole feela.Kenyelletso ea boitsebiso bo qalang e etsa hore ho khonehe ho khetholla litlhōrō tse tsamaellanang.
Ho kopanya liphetho tsa tlhahlobo ea reactor le software ea MODDE DOE (Umetrics, Malmö, Sweden) ho lumelletse tlhahlobo e felletseng ea liphetho le boikemisetso ba maemo a nepahetseng a karabelo bakeng sa cycloaddition ena.Ho tsamaisa sebatli se hahelletsoeng kahare le ho khetha mantsoe ohle a bohlokoa a mohlala ho theha maemo a karabelo a etselitsoeng ho holisa sebaka se phahameng sa sehlahisoa ha o ntse o fokotsa sebaka sa tlhoro sa acetylene feedstock.
Oxidation ea bokaholimo ba koporo ka kamoreng e susumetsang maikutlo e ile ea finyelloa ho sebelisoa tharollo ea hydrogen peroxide (36%) e phallang ka kamoreng ea ho arabela (sekhahla sa phallo = 0.4 ml min-1, nako ea bolulo = 2.5 min) pele ho motsoako oa motsoako o mong le o mong oa triazole.laeborari.
Hang ha maemo a nepahetseng a se a khethiloe, a ile a sebelisoa ho mefuta e mengata ea acetylene le haloalkane derivatives ho lumella ho bokelloa ha laebrari e nyenyane ea synthesis, ka hona ho theha monyetla oa 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).Li-aliquots tsa 3 ml tsa tharollo e 'ngoe le e 'ngoe li ile tsa tsoakoa 'me tsa pompeloa ka har'a reactor ka sekhahla sa 75 µl/min le mocheso oa 150°C.Molumo oohle o ne o bokelloa ka vial mme o hlapolotsoe ka 10 ml ea ethyl acetate.Tharollo ea mohlala e hlatsuoa ka 3 x 10 ml ea metsi.Likarolo tsa metsi li ne li kopantsoe 'me li ntšoa ka 10 ml ethyl acetate, joale lihlopha tsa manyolo li kopantsoe, li hlatsuoa ka 3 × 10 ml brine, li omisitsoe holim'a MgSO 4 le ho tlhotluoa, ebe solvent e tlosoa ka vacuo.Mehlala e ile ea hloekisoa ka silica gel column chromatography e sebelisa ethyl acetate pele ho tlhahlobo ka motsoako oa HPLC, 1H NMR, 13C NMR le high resolution mass spectrometry (HR-MS).
Lipontšo tsohle li ile tsa fumanoa ho sebelisoa Thermofischer Precision Orbitrap mass spectrometer e nang le ESI e le mohloli oa ionization.Mehlala eohle e lokisitsoe ho sebelisoa acetonitrile joalo ka mokelikeli.
Tlhahlobo ea TLC e entsoe ka lipoleiti tsa silica tse nang le substrate ea aluminium.Lipoleiti li ne li bonoa ka leseli la UV (254 nm) kapa litlolo tsa vanillin le ho futhumatsa.
Mehlala eohle e ile ea hlahlojoa ho sebelisoa VWR Chromaster system (VWR International Ltd., Leighton Buzzard, UK) e nang le autosampler, pompo ea binary e nang le onto ea litšiea le mochine o le mong oa maqhubu.Kholomo ea ACE Equivalence 5 C18 (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland) e sebelisitsoe.
Liente (5 µl) li entsoe ka kotloloho ho tsoa motsoakong o hlapollotsoeng oa crude reaction (1:10 dilution) 'me tsa hlahlojoa ka metsi:methanol (50:50 kapa 70:30), ntle le lisampole tse ling tse sebelisang sesebelisoa sa solvent sa 70:30 (se hlalosoang e le nomoro ea naleli) ka sekhahla sa phallo ea 1.5 ml/min.Mokokotlo o ne o bolokoa ka mocheso oa 40°C.Bolelele ba maqhubu a detector ke 254 nm.
Sebaka sa tlhoro sa% sa sampole se baloa ho tloha sebakeng se phahameng sa alkyne e setseng, sehlahisoa sa triazole feela, mme kenyelletso ea thepa ea ho qala e entse hore ho khonehe ho khetholla litlhoro tse tsamaellanang.
Mehlala eohle e ile ea hlahlojoa ho sebelisoa Thermo iCAP 6000 ICP-OES.Litekanyetso tsohle tsa ho lekanya li ile tsa lokisoa ho sebelisoa tharollo e tloaelehileng ea 1000 ppm Cu ho 2% nitric acid (SPEX Certi Prep).Litekanyetso tsohle li ne li lokiselitsoe ka tharollo ea 5% DMF le 2% HNO3, 'me lisampole tsohle li ile tsa hlapolloa ka makhetlo a 20 ka tharollo ea sampole ea DMF-HNO3.
UAM e sebelisa ultrasonic metal welding e le mokhoa oa ho kopanya lesela la tšepe le sebelisoang ho theha kopano ea ho qetela.Ultrasonic metal welding e sebelisa sesebelisoa sa tšepe se thothomelang (se bitsoang lenaka kapa lenaka la ultrasonic) ho kenya khatello ho foil / lera le kopantsoeng pele le tlamahanngoa / le kopantsoe pele ka ho sisinyeha thepa.Bakeng sa ts'ebetso e tsoelang pele, sonotrode e na le sebōpeho sa cylindrical 'me e phalla holim'a thepa, e kopanya sebaka sohle.Ha khatello le vibration li sebelisoa, li-oxide tse holim'a thepa li ka phunyeha.Khatello e sa khaotseng le ho sisinyeha ho ka lebisa ho timetsong ea ho ba thata ha thepa 36 .Ho kopana haufi-ufi le mocheso le khatello ea sebaka seo ho lebisang ho tlamahano e tiileng ea mohato ho li-interfaces tsa thepa;e ka boela ea khothalletsa momahano ka ho fetola matla a holim'a metsi48.Sebopeho sa mochine o kopanyang o hlōla mathata a mangata a amanang le mocheso o fapaneng oa ho qhibiliha le liphello tse phahameng tsa mocheso tse boletsoeng ho mekhoa e meng ea theknoloji ea tlhahiso ea tlatsetso.Sena se lumella khokahanyo e tobileng (ke hore ntle le phetoho ea holim'a metsi, li-fillers kapa li-adhesives) tsa lihlopha tse 'maloa tsa lisebelisoa tse fapaneng ho ba mohaho o le mong o kopantsoeng.
Ntho ea bobeli e ntle bakeng sa CAM ke tekanyo e phahameng ea phallo ea polasetiki e bonoang ka thepa ea tšepe esita le ka mocheso o tlase, ke hore, ka tlase ho ntlha ea ho qhibiliha ea thepa ea tšepe.Motsoako oa li-vibrations tsa ultrasonic le khatello li baka boemo bo phahameng ba moeli oa lijo-thollo oa sebaka sa ho falla le ho tsosolosa ntle le mocheso o moholo oa mocheso ka tloaelo o amanang le thepa e ngata.Nakong ea ho thehoa ha kopano ea ho qetela, ketsahalo ena e ka sebelisoa ho kenya likarolo tse sebetsang le tse sa sebetseng pakeng tsa lihlopha tsa tšepe ea tšepe, lera ka lera.Lintho tse kang optical fiber 49, reinforcement 46, electronics 50 le thermocouples (mosebetsi ona) li kenyelelitsoe ka katleho meahong ea UAM ho theha likopano tse sebetsang le tse sa sebetseng.
Mosebetsing ona, bokhoni bo fapaneng ba tlamahano ea thepa le bokhoni ba ho hokahana ba UAM bo ile ba sebelisoa ho theha microreactor e loketseng bakeng sa taolo ea mocheso oa catalytic.
Ha ho bapisoa le palladium (Pd) le tse ling tse atisang ho sebelisoa tšepe catalysts, Cu catalysis na le menyetla e 'maloa: (i) Moruo, Cu e theko e tlaase ho feta tšepe tse ling tse ngata tse sebelisoang ho catalysis 'me ka hona ke khetho e khahlehang bakeng sa indasteri ea lik'hemik'hale (ii) mefuta e fapaneng ea liketso tsa Cu-catalyzed cross-coupling reactions e ntse e atoloha' me e bonahala e le mokhoa o itseng oa Pd,5caary,5caary 5,51,51,51,51,51,51,51,51,51,51-3. karabelo ea talyzed e sebetsa hantle ha ho se na li-ligands tse ling.Hangata li-ligand tsena li na le sebopeho se bonolo le se theko e tlaase.haeba ho lakatseha, athe tse sebelisoang k'hemistri ea Pd hangata li rarahane, li theko e boima, 'me li na le moea (iv) Cu, haholo-holo e tsejoang ka bokhoni ba eona ba ho kopanya li-alkynes ka synthesis, tse kang Sonogashira's bimetallic catalyzed coupling le cycloaddition with azides (tobetsa k'hemistri) (v) Cu e ka boela ea khothalletsa arylation ea Usmann-phile karabelo ea nullmann-type e itseng.
Haufinyane tjena, mehlala ea heterogenization ea karabelo ena kaofela boteng ba Cu(0) e bontšitsoe.Sena se bakoa haholo ke indasteri ea meriana le tsepamiso e ntseng e hola ea ho hlaphoheloa le ho sebelisa li-catalyst tsa tšepe hape55,56.
Karabelo ea 1,3-dipolar cycloaddition pakeng tsa acetylene le azide ho 1,2,3-triazole, e hlahisitsoeng pele ke Huisgen ka 1960s57, e nkoa e le karabelo ea pontšo ea synergistic.Likaroloana tse hlahisoang ke 1,2,3 triazole li thahasella ka ho khetheha e le pharmacophore ho sibolloa ha lithethefatsi ka lebaka la ts'ebeliso ea bona ea likokoana-hloko le ho sebelisoa ho li-agent tse fapaneng tsa phekolo 58.
Karabelo ena e ile ea fumana tlhokomelo e nchafalitsoeng ha Sharpless le ba bang ba hlahisa mohopolo oa "tobetsa chemistry"59.Poleloana "click chemistry" e sebelisoa ho hlalosa sete e matla le e khethang ea karabelo e potlakileng ea metsoako e mecha le lilaebrari tse kopanyang tse sebelisang heteroatomic bonding (CXC)60.Boipiletso ba maiketsetso ba liketso tsena bo bakoa ke lihlahisoa tse phahameng tse amanang le tsona.maemo a bonolo, ho hanyetsa oksijene le metsi, 'me karohano ea lihlahisoa e bonolo61.
The classical 1,3-dipole Huisgen cycloaddition ha e oele sehlopheng sa "click chemistry".Leha ho le joalo, Medal le Sharpless li bontšitse hore ketsahalo ena ea coupling ea azide-alkyne e feta 107-108 ka pel'a Cu (I) ha e bapisoa le ho potlakisa ho hoholo ha sekhahla sa "non-catalytic 1,3-dipolar cycloaddition" 62,63.Mokhoa ona o tsoetseng pele oa ho itšoara ha o hloke lihlopha tse sireletsang kapa maemo a thata a itšoarang 'me o fana ka phetoho e batlang e feletseng le khetho ho 1,4-disubstituted 1,2,3-triazoles (anti-1,2,3-triazoles) ka nako (setšoantšo sa 3).
Liphetho tsa Isometric tsa li-cycloadditions tse tloaelehileng le tsa koporo-catalyzed Huisgen.Cu(I) -catalyzed Huisgen cycloadditions e fana ka 1,4-disubstituted 1,2,3-triazoles feela, ha Huisgen cycloadditions e susumetsoang ka mocheso ka tloaelo e fana ka 1,4- le 1,5-triazoles motsoako oa 1:1 oa azole stereoisomers.
Li-protocol tse ngata li kenyelletsa ho fokotseha ha mehloli e tsitsitseng ea Cu (II), e kang ho fokotseha ha CuSO4 kapa motsoako oa Cu (II) / Cu (0) hammoho le letsoai la sodium.Ha ho bapisoa le lintho 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 ka Worrell et al.65 li bontšitse hore tabeng ea li-alkyne tsa terminal, tse peli tse lekanang le koporo li kenyelelitsoe ho kenya ts'ebetsong ts'ebetsong ea molek'hule ka 'ngoe mabapi le azide.Mokhoa o reriloeng o tsoela pele ka lesale la tšepe la koporo la litho tse tšeletseng le entsoeng ka ho hokahanya ha azide ho σ-bonded acetylide ea koporo e nang le π-bond copper e le ligand e tsitsitseng ea mofani.Li-derivatives tsa koporo tsa triazolyl li thehoa ka lebaka la ho fokotseha ha selikalikoe se lateloa ke ho senyeha ha proton ho etsa lihlahisoa tsa triazole le ho koala potoloho ea catalytic.
Le hoja melemo ea lisebelisoa tsa k'hemistri ea phallo e ngotsoe hantle, ho bile le takatso ea ho kenyelletsa lisebelisoa tsa ho hlahloba lits'ebetsong tsena bakeng sa ho hlahloba ts'ebetso ea nako ea sebele ho situ66,67.UAM e ipakile e le mokhoa o loketseng oa ho rala le ho etsa li-reactors tse rarahaneng haholo tsa 3D tse tsoang ho li-catalytically active, thermally conductive materials tse nang le likarolo tsa kutlo tse kentsoeng ka kotloloho (setšoantšo sa 4).
Aluminium-copper flow reactor e entsoeng ke tlhahiso ea li-ultrasonic additive (UAM) e nang le mohaho o rarahaneng oa ka hare oa mochine, li-thermocouples tse hahiloeng ka hare le kamore ea catalytic reaction.Ho bona ka mahlo a kelello litsela tsa mokelikeli o ka hare, ho boetse ho bontšoa setšoantšo se hlakileng se entsoeng ka stereolithography.
Ho etsa bonnete ba hore li-reactors li etselitsoe ho sebetsa ka moso, lihlapolli li tlameha ho futhumatsoa ka mokhoa o sireletsehileng ka holim'a ntlha e belang;li lekoa ka khatello le mocheso.Tlhahlobo ea khatello e bontšitse hore tsamaiso e boloka khatello e tsitsitseng le e tsitsitseng esita le khatello e phahameng ea tsamaiso (1.7 MPa).Liteko tsa Hydrostatic li ne li etsoa ka mocheso oa kamore ho sebelisoa H2O joalo ka mokelikeli.
Ho kopanya thermocouple e hahiloeng (setšoantšo sa 1) ho mochine oa data oa mocheso o bontšitse hore mocheso oa thermocouple o ne o le 6 ° C (± 1 ° C) ka tlas'a mocheso o hlophisitsoeng tsamaisong ea FlowSyn.Ka tloaelo, ho eketseha ha mocheso ka 10 ° C ho imena habeli sekhahla sa karabelo, kahoo phapang ea mocheso ea likhato tse 'maloa feela e ka fetola sekhahla sa karabelo haholo.Phapang ena e bakoa ke tahlehelo ea mocheso ho pholletsa le RPV ka lebaka la phapang e phahameng ea mocheso oa thepa e sebelisoang ha ho etsoa tlhahiso.Mocheso ona o lula o le teng, kahoo o ka eloa hloko ha ho etsoa thepa ho netefatsa hore mocheso o nepahetseng oa fihla le ho lekanyetsoa nakong ea karabelo.Ka hona, sesebelisoa sena sa ho beha leihlo inthaneteng se thusa ho laola ka thata mocheso oa karabelo mme se kenya letsoho ntlafatsong e nepahetseng ea ts'ebetso le nts'etsopele ea maemo a nepahetseng.Li-sensor tsena li ka boela tsa sebelisoa ho bona karabelo e makatsang le ho thibela ts'ebetso ea ho baleha lits'ebetsong tse kholo.
Reactor e hlahisitsoeng pampiring ena ke mohlala oa pele oa ts'ebeliso 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 hlokomelehang a amanang le ho sebetsana le koporo kapa alloy aluminium (ii) ho ntlafala ha mocha oa ka hare ho bapisoa le phofshoana ea bethe e qhibilihisang (PBive9) kapa mekhoa ea ho qhibiliha ha bethe ea phofshoana (PBive9M)2 mokhoa oa ho qhibiliha ha bethe (PBive6) kapa mekhoa ea ho qhibiliha ha laser (PBF9)2. 26 (iii) mocheso o tlaase oa ho sebetsa, o nolofalletsang li-sensor tse hokahanyang ka ho toba, tse ke keng tsa khoneha ho thekenoloji ea bethe ea phofo, (v) ho hlōla mekhoa e futsanehileng ea mechine 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 lik'hemik'hale tsa koporo-catalyzed alkinazide cycloaddition tlas'a maemo a phallang a tsoelang pele (setšoantšo sa 2).The ultrasonic hatisitsoeng koporo reactor e bontšitsoeng ka feiga.4 e ne e kopantsoe le tsamaiso ea khoebo ea phallo 'me e sebelisetsoa ho etsa laebrari ea azide ea mefuta e sa tšoaneng ea 1,4-disubstituted 1,2,3-triazoles e sebelisang mocheso o laoloang ke mocheso oa acetylene le alkyl sehlopha sa halides ka pel'a sodium chloride (Setšoantšo sa 3).Tšebeliso ea mokhoa oa ho phalla o tsoelang pele o fokotsa litaba tsa ts'ireletso tse ka hlahang lits'ebetsong tsa batch, kaha karabelo ena e hlahisa li-intermediate tsa azide tse sebetsang haholo le tse kotsi [317], [318].Qalong, karabelo e ile ea ntlafatsoa bakeng sa cycloaddition ea phenylacetylene le iodoethane (Scheme 1 - Cycloaddition ea phenylacetylene le iodoethane) (bona setšoantšo sa 5).
(Ka holimo ka ho le letšehali) Schematic ea setupo se sebelisetsoang ho kenyelletsa mochine oa 3DP tsamaisong ea phallo (ka holimo ka ho le letona) e fumanoang ho tsoa ho morero o ntlafalitsoeng (ka tlaase) oa Huisgen 57 cycloaddition scheme pakeng tsa phenylacetylene le iodoethane bakeng sa ho ntlafatsa le ho bontša litekanyetso tse ntlafalitsoeng tsa phetoho ea karabelo.
Ka ho laola nako ea bolulo ea li-reactants karolong ea catalytic ea reactor le ho shebella ka hloko mocheso oa karabelo ka sensor e kopantsoeng ka ho toba ea thermocouple, maemo a karabelo a ka etsoa kapele le ka nepo ka bonyane ba nako le lisebelisoa.Ho ile ha fumanoa ka potlako hore phetoho e phahameng ka ho fetisisa e finyeletsoe ho sebelisoa nako ea bolulo ea metsotso e 15 le mocheso oa karabelo oa 150 ° C.E ka bonoa ho tsoa ho coefficient plot ea MODDE software hore nako ea bolulo le mocheso oa karabelo li nkuoa e le maemo a bohlokoa a mohlala.Ho tsamaisa sebatli se hahelletsoeng ka ho sebelisa maemo ana a khethiloeng ho theha maemo a karabelo a etselitsoeng ho holisa libaka tsa tlhoro ea sehlahisoa ha a ntse a fokotsa libaka tsa tlhoro ea thepa.Ntlafatso ena e hlahisitse phetoho ea 53% ea sehlahisoa sa triazole, e ts'oanang hantle le polelo ea mohlala ea 54%.