Zikomo chifukwa chochezera Nature.com.Msakatuli wa msakatuli omwe mukugwiritsa ntchito ali ndi chithandizo chochepa cha CSS.Kuti mukhale ndi chidziwitso chabwino kwambiri, tikukulimbikitsani kuti mugwiritse ntchito msakatuli wosinthidwa (kapena muzimitsa mawonekedwe ogwirizana mu Internet Explorer).Pakalipano, kuti titsimikizire kuti kupitirizabe kuthandizidwa, tidzawonetsa malo opanda masitayelo ndi JavaScript.
Kupanga kowonjezera kukusintha momwe ofufuza ndi akatswiri opanga mafakitale amapangira ndi kupanga zida zamankhwala kuti zikwaniritse zosowa zawo zenizeni. Mu ntchitoyi, timapereka chitsanzo choyamba cha makina othamanga opangidwa ndi njira yolimba yachitsulo yopangira zitsulo zamagetsi Ultrasonic Additive Manufacturing (UAM) yokhala ndi zida zophatikizika zophatikizika komanso zozindikira. mndandanda wa mankhwala ofunika kwambiri a biologically 1,4-disubstituted 1,2,3-triazole anapangidwa bwino ndi kukonzedwa bwino ndi Cu-mediated Huisgen 1,3-dipolar cycloaddition reaction pogwiritsa ntchito UAM chemistry set-up.
Chifukwa cha ubwino wake wochuluka kuposa mnzake wochuluka, chemistry yothamanga ndi gawo lofunika komanso lomwe likukula m'maphunziro onse a maphunziro ndi mafakitale chifukwa cha mphamvu zake zowonjezera kusankha ndi kugwiritsira ntchito mankhwala opangidwa ndi mankhwala. Zoposa 50% za zomwe zimachitikira m'mafakitale abwino amankhwala ndi mankhwala zitha kupindula ndikugwiritsa ntchito mosalekeza otaya processing7.
M'zaka zaposachedwa, pakhala pali chizoloŵezi chokulirapo cha magulu omwe akufuna kusintha zida zamagalasi kapena zida zamakina othamanga ndi zida zopangira zowonjezera (AM) chemistry "reaction vessels"8.Mapangidwe obwerezabwereza, kupanga mofulumira, ndi luso la 3-dimensional (3D) la njirazi ndizopindulitsa kwa iwo omwe akufuna kusintha zipangizo zawo kuti zikhale ndi ndondomeko yeniyeni ya machitidwe, tsiku, zipangizo, kapena ntchito zomwe zimagwiritsidwa ntchito pokhapokha. njira zosindikizira za 3D polima monga sterolithography (SL)9,10,11, fused deposition modeling (FDM)8,12,13,14 ndi inkjet kusindikiza 7, 15,16. za AM m'munda uno17, 18, 19, 20 .
Chifukwa cha kuchulukirachulukira kwa ma flow chemistry komanso zinthu zabwino zomwe zimagwirizanitsidwa ndi AM, pakufunika kufufuza njira zapamwamba kwambiri zomwe zimathandiza ogwiritsa ntchito kupanga zotengera zomwe zikuyenda bwino ndi mankhwala owonjezera komanso luso lowunikira. Njirazi zikuyenera kupangitsa ogwiritsa ntchito kusankha kuchokera kuzinthu zolimba kwambiri kapena zogwira ntchito zomwe zimatha kuthana ndi zochitika zosiyanasiyana, komanso kuwongolera njira zosiyanasiyana zowunikira kuti ziwongolere zomwe zimachokera ku chipangizocho.
Njira imodzi yowonjezera yopanga yomwe imatha kupanga makina opangira mankhwala ndi Akupanga Additive Manufacturing (UAM) .Iyi yolimba-state sheet lamination njira imagwiritsa ntchito ultrasonic oscillations ku zitsulo zopyapyala zachitsulo kuti zigwirizane nazo pamodzi wosanjikiza ndi wosanjikiza ndi kutentha kochepa kwambiri komanso kutsika kwa pulasitiki 21 , 22 , 23 .Mosiyana kwambiri ndi AM tech integrated, Mosiyana ndi AM tech integrated, 23 . monga hybrid kupanga ndondomeko, mmene mu-situ periodic kompyuta manambala kulamulira (CNC) mphero kapena laser Machining amatanthauza ukonde mawonekedwe a wosanjikiza zinthu zomangika 24, 25. Izi zikutanthauza kuti wosuta si malire ndi mavuto okhudzana ndi kuchotsa zotsalira yaiwisi kumanga zinthu ku ngalande yaing'ono madzimadzi, amene nthawi zambiri ndi ufa ndi madzi zamadzimadzi kusankha AM2 28, 27 Ufulu wa zinthu zopezeka ku U. Kusankha kwa zinthu zophatikizika kupitilira njira yosungunuka kumatanthauza kuti makina ndi mankhwala omwe amafunidwa pazantchito zinazake amatha kukhala bwino. Kuphatikiza pa kulumikizana kolimba kwa boma, chodabwitsa china chomwe timakumana nacho panthawi yolumikizana ndi akupanga ndichokwera kwambiri kwa zida zapulasitiki pamtunda wochepa kwambiri29,30,31,31,32,33AM. zigawo popanda kuwonongeka.Masensa ophatikizidwa a UAM amatha kuthandizira kutumiza chidziwitso cha nthawi yeniyeni kuchokera ku chipangizo kupita kwa wogwiritsa ntchito pogwiritsa ntchito ma analytics ophatikizika.
Ntchito yapitayi ya olemba32 inasonyeza kuthekera kwa ndondomeko ya UAM kupanga zitsulo zazitsulo za 3D microfluidic zomwe zimakhala ndi mphamvu zowonongeka.Iyi ndi chipangizo chokha choyang'anira.Pepalali likupereka chitsanzo choyamba cha microfluidic chemical reactor yopangidwa ndi UAM; chipangizo chogwira ntchito chomwe sichimangoyang'anitsitsa komanso chimapangitsa kuti pakhale kuphatikizika kwa mankhwala pogwiritsa ntchito zipangizo zopangira zopangira.Chidacho chimaphatikizapo ubwino wambiri wokhudzana ndi teknoloji ya UAM mu 3D kupanga zipangizo zamakina, monga: kuthekera kosintha mapangidwe athunthu a 3D mwachindunji kuchokera ku zitsanzo zothandizidwa ndi makompyuta (CAD) kukhala mankhwala; zopangira zinthu zambiri kuphatikiza ma conductivity apamwamba amafuta ndi zida zothandizira; Kuwonetsa magwiridwe antchito a riyakitala, laibulale yamankhwala ofunikira 1,4-disubstituted 1,2,3-triazole mankhwala adapangidwa ndi Huisgen-catalyzed Huisgen 1,3-dipolar sayansi. kupanga kungatsegule mwayi watsopano ndi mwayi wa chemistry kudzera mu kafukufuku wosiyanasiyana.
Zosungunulira zonse ndi ma reagents anagulidwa ku Sigma-Aldrich, Alfa Aesar, TCI kapena Fischer Scientific ndipo amagwiritsidwa ntchito popanda kuyeretsedwa kale.1H ndi 13C NMR mawonekedwe ojambulidwa pa 400 MHz ndi 100 MHz, motero, adapezedwa pogwiritsa ntchito JEOL ECS-400 400 400 MHz 400 MHz 400 MHz kapena Brush 400 MHz spectrometer ndi CDCl3 kapena (CD3)2SO monga zosungunulira.Zochita zonse zinachitidwa pogwiritsa ntchito Uniqsis FlowSyn flow chemistry platform.
UAM inagwiritsidwa ntchito kupanga zipangizo zonse mu phunziroli.Tekinolojeyi inakhazikitsidwa mu 1999, ndipo zambiri zaukadaulo, magawo ogwiritsira ntchito ndi zomwe zikuchitika kuyambira pomwe zidapangidwa zimatha kuphunziridwa kudzera m'zinthu zosindikizidwa zotsatirazi34,35,36,37. kupanga otaya chipangizo anali Cu-110 ndi Al 6061.Cu-110 ali mkulu okhutira zamkuwa (osachepera 99.9% zamkuwa), kupanga phungu wabwino kwa zochita mkuwa-catalyzed, choncho ntchito ngati "yosanjikiza yogwira mkati mwa microreactor. Al 6061 O amagwiritsidwa ntchito ngati "zochuluka" zakuthupi zomwe zimagwiritsidwa ntchito polemba ndi kusindikiza; chikhalidwe cha annealed pamodzi ndi Cu-110 wosanjikiza Al 6061 O ndi zinthu zomwe zasonyezedwa kuti zimagwirizana kwambiri ndi njira za UAM38, 39, 40, 41 ndipo zayesedwa ndipo zapezeka kuti zimakhala zokhazikika ndi ma reagents omwe amagwiritsidwa ntchito pa ntchitoyi. 38,42 Zida izi zalembedwa mu Table 1 pansipa.
Magawo opangira makina opangira nyukiliya (1) Al 6061 gawo lapansi (2) Kupanga njira yapansi yokhazikitsidwa ku zojambula zamkuwa (3) Kuyika ma thermocouples pakati pa zigawo (4) Chapamwamba (5) Kulowetsa ndi kutulutsa (6) Monolithic reactor.
Kapangidwe ka nzeru zamadzimadzi njira ndi kugwiritsa ntchito njira convoluted kuonjezera mtunda wa madzimadzi akuyenda mkati chip, pamene kusunga Chip pa kukula manageable.Kuwonjezeka kwa mtunda ndi zofunika kuonjezera chothandizira/reagent mogwirizana nthawi ndi kupereka kwambiri product yields.The tchipisi ntchito 90 ° mapindikira pa malekezero a njira yowongoka kulimbikitsa mkati kukhudzana ndi chipwirikiti madzimadzi4 kusanganikirana pamwamba pa chipangizo ndi chipwirikiti kusakaniza madzi4 ndi reagent kusanganikirana nthawi. (chothandizira) .Kuti muwonjezere kusanganikirana komwe kungapezeke, mapangidwe a riyakitala amaphatikizapo zolowetsa ziwiri za reagent zomwe zimagwirizanitsidwa pa Y-mphambano musanalowe mu gawo losakanikirana la serpentine. Njira yachitatu, yomwe imadutsa mtsinjewo pakati pa malo ake okhala, imaphatikizidwa mu mapangidwe a tsogolo la multistep reaction syntheses.
Makanema onse ali ndi mawonekedwe a sikweya (palibe ngodya zolembera), zotsatira za mphero yanthawi zonse ya CNC yomwe imagwiritsidwa ntchito popanga njira ya geometry. Miyeso ya tchanelo imasankhidwa kuti iwonetsetse kuchuluka kwa voliyumu (kwa microreactor), kukhala yaying'ono mokwanira kuti ithandizire kuyanjana kwamadzi (zothandizira) pamadzi ambiri omwe ali. µm x 750 µm ndipo voliyumu yonse ya riyakitala inali 1 ml. Cholumikizira chophatikizika (1/4″—28 UNF ulusi) chikuphatikizidwa m'mapangidwe kuti alole kulumikizana kosavuta kwa chipangizocho ndi zida zamalonda zama chemistry. Kukula kwa njira kumachepa ndi makulidwe a zojambulazo, mawonekedwe ake amakina, ndi magawo olumikizana omwe amagwiritsidwa ntchito ndi ultrasonics. Pam'lifupi mwachinthu choperekedwa, zinthuzo "zidzalowa" munjira yopangidwa. Pakalipano palibe chitsanzo chenicheni cha kuwerengera uku, kotero kuti m'lifupi mwake m'lifupi mwazinthu zomwe zapatsidwa ndi mapangidwe ake amatsimikiziridwa moyesera; Pankhaniyi, m'lifupi mwake 750 μm sikudzayambitsa sag.
Mawonekedwe (mzere) wa njirayo amatsimikiziridwa pogwiritsa ntchito square cutter.Mawonekedwe ndi kukula kwa mayendedwe amatha kusinthidwa ndi makina a CNC pogwiritsa ntchito zida zosiyanasiyana zodula kuti apeze maulendo osiyanasiyana othamanga ndi makhalidwe.Chitsanzo chopanga njira yokhotakhota yokhotakhota pogwiritsa ntchito chida cha 125 μm chingapezeke mu ntchito ya Monaghan45.Pamene wosanjikiza zojambulazo zimayikidwa pamwamba pa ndondomeko ya foil yokhala ndi ndondomeko yowonongeka, idzakhala ndi zinthu pamwamba pa ndondomeko ya foil. (square) finish.Mu ntchito iyi, pofuna kusunga symmetry ya tchanelo, ndondomeko ya square idagwiritsidwa ntchito.
Panthawi yopuma yokonzedweratu popanga, makina a kutentha kwa thermocouple (Mtundu wa K) amalowetsedwa mwachindunji mkati mwa chipangizo pakati pa magulu apamwamba ndi otsika (Chithunzi 1 - Gawo 3) .Ma thermocouples awa amatha kuyang'anitsitsa kusintha kwa kutentha kuchokera -200 mpaka 1350 ° C.
Njira yoyika zitsulo imachitidwa ndi nyanga ya UAM pogwiritsa ntchito 25.4 mm m'lifupi, 150 micron wandiweyani zitsulo zojambulazo.Zigawo zazitsulozi zimamangirizidwa muzitsulo zotsatizana zoyandikana kuti zitseke malo onse omanga; kukula kwa zinthu waikamo ndi wamkulu kuposa chomaliza mankhwala monga subtractive ndondomeko umabala chomaliza ukonde shape.CNC Machining ntchito makina kunja ndi mkati contours wa zipangizo, chifukwa pamwamba mapeto a zipangizo ndi njira ofanana ndi anasankha chida ndi CNC ndondomeko magawo (pafupifupi 1.6 μm Ra mu chitsanzo ichi) . kuonetsetsa kuti kulondola kwa dimensional kumasungidwa ndipo gawo lomalizidwa lidzakumana ndi CNC kumaliza mphero yolondola milingo.M'lifupi mwa njira yomwe imagwiritsidwa ntchito pa chipangizochi ndi yaying'ono kuti zitsimikizire kuti zojambulazo sizikhala "kugwedezeka" mumtsinje wamadzimadzi, kotero kuti njirayo imakhala ndi gawo lalikulu.Mipata yotheka muzojambula zojambulazo ndi magawo a ndondomeko ya UAM adatsimikiziridwa moyesera ndi bwenzi lopanga, USA Fabrisonic.
Kafukufuku wasonyeza kuti kufalikira kwapang'ono kwapang'onopang'ono kumachitika pa mawonekedwe a UAM ogwirizana 46, 47 popanda chithandizo chowonjezera chamafuta, kotero pazida zomwe zili mu ntchitoyi, wosanjikiza wa Cu-110 umakhala wosiyana ndi wosanjikiza wa Al 6061 ndipo umasintha mwadzidzidzi.
Ikani pre-calibrated 250 psi (1724 kPa) back pressure regulator (BPR) kuti mutuluke pa riyakitala ndi kupopera madzi kudzera mu riyakitala pamlingo wa 0.1 mpaka 1 mL min-1. Kuthamanga kwa riyakitala kumayang'aniridwa pogwiritsa ntchito FlowSyn yomangidwa mu system pressure sensor kuti atsimikizire kuti makinawo amatha kukhalabe ndi mphamvu yokhazikika yoyezera kutentha kwanthawi zonse. kusiyana pakati pa ma thermocouples ophatikizidwa mkati mwa riyakitala ndi omwe amaikidwa mkati mwa FlowSyn chip heat plate.Izi zimatheka ndi kusinthasintha kutentha kwa hotplate pakati pa 100 ndi 150 °C mu 25 °C increments ndikuwona kusiyana kulikonse pakati pa kutentha kwadongosolo ndi kujambulidwa.Izi zinatheka pogwiritsa ntchito logger, UK datach, Cambridge kutsagana ndi pulogalamu ya PicoLog.
The cycloaddition reaction conditions of phenylacetylene and iodoethane were optimized (Scheme 1- Cycloaddition of phenylacetylene and iodoethane Scheme 1- Cycloaddition of phenylacetylene and iodoethane) alkyne:azide chiŵerengero pa 1:2.
Osiyana njira za sodium azide (0.25 M, 4: 1 DMF: H2O), iodoethane (0.25 M, DMF), ndi phenylacetylene (0.125 M, DMF) anali okonzeka. phenylacetylene poyambira zinthu ndipo anatsimikiza ndi mkulu ntchito madzi chromatography (HPLC) .Kuti kugwirizana kwa kusanthula, zochita zonse anali sampuli atangochoka anachita osakaniza anasiya riyakitala.The magawo osiyanasiyana osankhidwa kukhathamiritsa zikuwonetsedwa Table 2.
Zitsanzo zonse zidawunikidwa pogwiritsa ntchito Chromaster HPLC system (VWR, PA, USA) yomwe ili ndi mpope wa quaternary, ovuni yazazambiri, chojambulira cha UV cha UV ndi autosampler. isocratic 50: 50 methanol: madzi pa mlingo wothamanga wa 1.5 mL.min-1. Voliyumu ya jekeseni inali 5 µL ndipo detector wavelength inali 254 nm. Gawo lapamwamba la% la chitsanzo cha DOE linawerengedwa kuchokera kumadera apamwamba a alkyne otsalira ndi triazole ya mankhwala oyambira oyambira.
Kuphatikizira kusanthula kwa riyakitala ku pulogalamu ya MODDE DOE (Umetrics, Malmö, Sweden) kunalola kusanthula mozama za zotsatira ndi kutsimikiza kwa momwe zinthu zikuyendera pa cycloaddition iyi.Kuthamangitsa chowonjezera chomangirira ndikusankha mawu onse ofunikira kumabweretsa zinthu zingapo zomwe zimapangidwira kuti ziwonjezeke pamalo okwera kwambiri ndikuchepetsa kuchuluka kwa zinthu zomwe zimayambira.
The makutidwe ndi okosijeni pamwamba mkuwa mkati chothandizira anachita chipinda chinatheka ntchito njira ya hydrogen peroxide (36%) ikuyenda mu anachita chipinda (otaya mlingo = 0,4 mL mphindi-1, okhala nthawi = 2.5 min) isanafike synthesis aliyense triazole pawiri laibulale.
Kamodzi kachitidwe koyenera kamene kakadziwika, adagwiritsidwa ntchito pamitundu yambiri ya acetylene ndi haloalkane kuti alole kuphatikizika kwa kaphatikizidwe kakang'ono ka laibulale, potero kukhazikitsa mphamvu yogwiritsira ntchito mikhalidwe imeneyi kuzinthu zambiri zomwe zingatheke (Chithunzi 1) .2).
Konzani njira zosiyana za sodium azide (0.25 M, 4: 1 DMF:H2O), haloalkanes (0.25 M, DMF) ndi alkynes (0.125 M, DMF) 3 mL aliquots pa njira iliyonse anali osakaniza ndi kupopera kudzera riyakitala pa 75 µL.min-1 ndi 150 °C ndi kuchepetsedwa ndi 100 ° C. ethyl acetate.Chitsanzochitsanzo chinatsukidwa ndi 3 × 10 mL ya madzi.Zigawo zamadzimadzi zinaphatikizidwa ndi kuchotsedwa ndi 10 mL ya ethyl acetate; zigawo za organic zinaphatikizidwa, kutsukidwa ndi 3 x 10 mL ya brine, zouma pamwamba pa MgSO4 ndi zosefedwa, ndiye zosungunulirazo zinachotsedwa mu vacuo.Zitsanzozo zinayeretsedwa ndi chromatography ya silika pa gel osakaniza pogwiritsa ntchito ethyl acetate isanayambe kusanthula ndi kuphatikiza kwa HPLC, 1H NMR, 13C misa ya NMR (13C HR-NMR).
Zowonera zonse zidapezedwa pogwiritsa ntchito Thermofischer precision Orbitrap resolution mass spectrometer ndi ESI monga ionization source.Zitsanzo zonse zidakonzedwa pogwiritsa ntchito acetonitrile monga zosungunulira.
Kusanthula kwa TLC kunkachitika pazitsulo za silika zothandizidwa ndi aluminiyamu. Mapulani adawonetsedwa ndi kuwala kwa UV (254 nm) kapena madontho a vanillin ndi kutentha.
Zitsanzo zonse zidawunikidwa pogwiritsa ntchito makina a VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) okhala ndi autosampler, pampu ya oven oven binary ndi single wavelength detector.Chigawo chomwe chinagwiritsidwa ntchito chinali ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Ltd.,Scotland Aberlogies Technologies).
jakisoni (5 µL) anapangidwa mwachindunji kuchepetsedwa zosakayikitsa anachita osakaniza (1:10 dilution) ndi kusanthula ndi madzi: methanol (50:50 kapena 70:30), kupatulapo zitsanzo zina ntchito 70:30 zosungunulira dongosolo (amatanthauza ngati nyenyezi nambala) pa otaya mlingo wa 1.5 mL / C ndime anali kusungidwa pa 4 ° ndime kapena detect. 254 nm.
The % pachimake dera chitsanzo anawerengedwa kuchokera pachimake dera alkyne otsalira, mankhwala triazole yekha, ndi jekeseni wa zinthu poyambira analola chizindikiritso cha nsonga zogwirizana.
Zitsanzo zonse zinafufuzidwa pogwiritsa ntchito Thermo iCAP 6000 ICP-OES. Miyezo yonse yoyezetsa inakonzedwa pogwiritsa ntchito njira yothetsera 1000 ppm Cu mu 2% nitric acid (SPEX Certi Prep) . Miyezo yonse inakonzedwa mu 5% DMF ndi 2% HNO3 yankho, ndipo zitsanzo zonse zinachepetsedwa muyeso wa DMF 20-HNO3.
UAM imagwiritsa ntchito kuwotcherera kwachitsulo kopangidwa ndi akupanga ngati njira yolumikizira zitsulo zopangidwa ndi zitsulo zomwe zimagwiritsidwa ntchito pomanga msonkhano womaliza. Ultrasonic zitsulo kuwotcherera imagwiritsa ntchito chida chogwedeza chachitsulo (chotchedwa nyanga kapena nyanga ya akupanga) kuti igwiritse ntchito kukakamiza kwa zojambulazo / zomwe zidaphatikizidwa kale kuti zimangidwe pamene zikugwedeza zinthuzo. kumangiriza dera lonse.Pamene kupanikizika ndi kugwedezeka kumagwiritsidwa ntchito, ma oxides pamwamba pa zinthuzo amatha kusweka.Kupanikizika kosalekeza ndi kugwedezeka kungayambitse asperities ya zinthu kugwa 36 .Kukhudzana kwapamtima ndi kutentha komwe kumapangitsa kuti pakhale kutentha ndi kupanikizika kumatsogolera ku mgwirizano wolimba-boma pazitsulo zakuthupi; zingathandizenso kumamatira kupyolera mu kusintha kwa pamwamba pa mphamvu48.Chikhalidwe cha njira yolumikizirana imagonjetsa mavuto ambiri okhudzana ndi kutentha kwa kutentha kwa kutentha ndi kutentha kwapamwamba pambuyo pa zotsatira zomwe zimatchulidwa mu njira zina zopangira zowonjezera zowonjezera.
Chinthu chachiwiri chabwino kwa UAM ndi kuchuluka kwa pulasitiki yotuluka muzitsulo zazitsulo, ngakhale kutentha pang'ono, mwachitsanzo, pansi pa malo osungunuka a zitsulo.Kuphatikiza kwa akupanga oscillation ndi kupanikizika kumapangitsa kuti m'madera ambiri azitha kusamuka ndi kukonzanso popanda kutentha kwakukulu komwe kumagwirizanitsidwa ndi zinthu zambiri. zitsulo zopangidwa ndi zitsulo, zosanjikiza ndi layer.Elements monga optical fibers 49, reinforcements 46, electronics 50, ndi thermocouples (ntchito iyi) zonse zakhala zikuphatikizidwa bwino muzomangamanga za UAM kuti apange misonkhano yogwira ntchito komanso yopanda pake.
Pantchitoyi, kulumikizana kwazinthu zosiyanasiyana komanso kuphatikizika kwa UAM kwagwiritsidwa ntchito popanga chothandizira kwambiri chowunikira kutentha kwa microreactor.
Poyerekeza ndi palladium (Pd) ndi zina zomwe zimagwiritsidwa ntchito zitsulo, Cu catalysis ili ndi ubwino wambiri: (i) Pazachuma, Cu ndi yotsika mtengo kusiyana ndi zitsulo zina zambiri zomwe zimagwiritsidwa ntchito pothandizira, choncho ndi njira yokongola yamakampani opangira mankhwala (ii) Zosiyanasiyana za Cu-catalyzed cross-coupling reactions zikuchulukirachulukira ndipo zikuwoneka kuti ndizowonjezera Pd51o (3) Cu-catalyzed zochita bwino pakalibe ligands ena, Ligands Izi nthawi zambiri structurally zosavuta ndi zotsika mtengo ngati n'koyenera, pamene anthu ntchito Pd umagwirira nthawi zambiri zovuta, zodula, ndi mpweya tcheru (iv) Cu, makamaka odziwika chifukwa cha luso lake kumanga alkynes mu kaphatikizidwe, Mwachitsanzo, bimetallic-catalyzedcling-cocatalyzedcling-cocatalyzedclip chemistry) (v) Cu imathanso kulimbikitsa ma nucleophiles angapo mu machitidwe amtundu wa Ullmann.
Zitsanzo za heterogenization ya machitidwe onsewa posachedwapa zasonyezedwa pamaso pa Cu (0) .Izi makamaka chifukwa cha makampani opanga mankhwala ndi kukula kwa chidwi pa zitsulo chothandizira kubwezeretsa ndi reuse55,56.
Anachita upainiya ndi Huisgen mu 1960s57, 1,3-dipolar cycloaddition reaction pakati pa acetylene ndi azide mpaka 1,2,3-triazole imatengedwa ngati synergistic demonstration reaction. othandizira achire 58 .
Izi zinayambikanso pamene Sharpless ndi ena adayambitsa lingaliro la "click chemistry" 59.Mawu oti "click chemistry" amagwiritsidwa ntchito kufotokoza machitidwe olimba, odalirika komanso osankhidwa a kaphatikizidwe katsopano ka mankhwala atsopano ndi malaibulale ophatikizika kudzera pa heteroatom linkage (CXC)60 The synthetic chemistry of these reactions is used to explain a robust, odalirika and selective seti of reactions for the rapid synthesis of new compounds and combinatorial library through heteroatom linkage (CXC)60 The synthetic chemistry of these reactions is used to explain a robust, odalirika ndi kusankha seti ya zochita za kaphatikizidwe mofulumira wa mankhwala atsopano ndi malaibulale combinatorial via heteroatom linkage (CXC)60 The synthetic chemistry of these reactions are , kulekana ndi kophweka61.
The classical Huisgen 1,3-dipole cycloaddition sali m'gulu la "click chemistry". sikutanthauza magulu oteteza kapena zovuta kuchita zinthu ndi zokolola pafupi kutembenuka wathunthu ndi selectivity kwa 1,4-disubstituted 1,2,3-triazoles (anti- 1,2,3-triazole) pa nthawi sikelo (Chithunzi 3).
Zotsatira za Isometric za Huisgen cycloadditions wamba komanso zamkuwa.Cu(I)-catalyzed Huisgen cycloadditions zimangotulutsa 1,4-disubstituted 1,2,3-triazoles, pomwe ma cycloadditions opangidwa ndi thermally amatulutsa 1,51-triazoles yosakanikirana ndi 1,51-triazoles. stereoisomers a azole.
Mapulogalamu ambiri amaphatikizapo kuchepetsa magwero okhazikika a Cu (II), monga kuchepetsa CuSO4 kapena Cu (II) / Cu (0) kugwirizanitsa mitundu ndi mchere wa sodium. Poyerekeza ndi machitidwe ena opangidwa ndi zitsulo, kugwiritsa ntchito Cu (I) kuli ndi ubwino waukulu wokhala wotchipa komanso wosavuta kugwira.
Maphunziro a Kinetic ndi isotopic olembedwa ndi Worrell et al. 65 inasonyeza kuti, pa nkhani ya ma alkynes otsiriza, awiri ofanana ndi mkuwa akukhudzidwa ndi kuyambitsa reactivity ya molekyulu iliyonse kwa azide.Makina omwe akufuna kuti apitirire kupyolera mu mphete yazitsulo yamkuwa yokhala ndi mamembala asanu ndi limodzi yopangidwa ndi mgwirizano wa azide ku σ-bond copper acetylide yokhala ndi π-bonded copper ngati stable deorzondor. Kuchepa kwa mphete, kutsatiridwa ndi kuwonongeka kwa protoni kuti apereke mankhwala a triazole ndikutseka kuzungulira kothandizira.
Ngakhale kuti ubwino wa zipangizo zamakina othamanga zimalembedwa bwino, pakhala pali chikhumbo chophatikiza zida zowunikira m'makinawa a in-line, in-situ, process monitoring66,67.UAM yakhala njira yabwino yopangira ndi kupanga zovuta kwambiri za 3D flow reactors zopangidwa ndi catalytically active, thermally conductive materials with direct embegusted sensing elements 4 (Fid 4).
Aluminiyamu-mkuwa otaya riyakitala yopangidwa ndi akupanga zowonjezera kupanga (UAM) ndi zovuta mkati kanjira kamangidwe, ophatikizidwa thermocouples ndi chothandizira anachita chamber.Kuti muone m'maganizo madzimadzi njira, mandala prototype anapeka ntchito sterolithography amasonyezedwa.
Kuonetsetsa kuti ma reactors apangidwa kuti agwirizane ndi mtsogolo, zosungunulira ziyenera kutenthedwa bwino pamwamba pa kuwira; iwo ali kupanikizika ndi kutentha kuyesedwa.Kuyesedwa kwapakati kunasonyeza kuti dongosololi limakhalabe lokhazikika komanso lokhazikika ngakhale ndi kuwonjezereka kwa dongosolo (1.7 MPa) .Kuyesa kwa hydrostatic kunkachitika kutentha kutentha pogwiritsa ntchito H2O monga madzi.
Kulumikiza ophatikizidwa (Chithunzi 1) thermocouple ndi kutentha deta logger anasonyeza kuti thermocouple anali 6 °C (± 1 °C) ozizira kuposa kutentha pulogalamu pa FlowSyn system. mkulu matenthedwe diffusivity wa zipangizo ntchito kupanga process.This matenthedwe kutengeka n'kogwirizana choncho akhoza mlandu mu khwekhwe zida kuonetsetsa kutentha olondola anafika ndi kuyeza pa reaction.Therefore, izi Intaneti polojekiti chida facilitates kulamulira zolimba anachita kutentha ndi facilitates zolondola ndondomeko kukhathamiritsa ndi chitukuko cha mulingo woyenera kwambiri conditions.These masensa kuzindikiritsa kachitidwe reaction.
The riyakitala yomwe yaperekedwa mu ntchitoyi ndi chitsanzo choyamba cha kugwiritsa ntchito ukadaulo wa UAM popanga zida zamagetsi ndikuthana ndi zolephera zingapo zazikulu zomwe zikugwirizana ndi AM / 3D kusindikiza kwa zida izi, monga: (i) kuthana ndi mavuto omwe adanenedwa okhudzana ndi mkuwa kapena aluminium alloy processing (ii) kuwongolera njira yamkati poyerekeza ndi kuphatikizika kwa bedi la ufa (PBF) kapena kusankha njira zaposachedwa za SL6, kapena njira zotulutsira 9 zotulutsa laser, SL6. rough surface texture26 (iii) Kuchepetsa kutentha kwa processing, komwe kumathandizira kulumikizana kwachindunji kwa masensa, zomwe sizingatheke muukadaulo wa bedi la ufa, (v) zimagonjetsa zinthu zosauka zamakina ndi kukhudzidwa kwa zigawo zozikidwa polima kumitundu yosiyanasiyana yamafuta osungunulira organic17,19.
The magwiridwe a riyakitala anasonyeza ndi angapo mkuwa-catalyzed alkyne azide cycloaddition zimachitikira pansi mosalekeza otaya zinthu (mkuyu. 2) . The akupanga-kusindikizidwa mkuwa riyakitala mwatsatanetsatane mu Chithunzi 4 anali Integrated ndi malonda otaya dongosolo ndi ntchito lithe laibulale azides zosiyanasiyana 1,4-disubstituted via3tricealed-azoled-acontrol reaction, 1,4-disubstituted 1,4-disubstituted ndi-tricealed-control 1,2-azoled-acontrol reaction. ndi magulu a alkyl halides pamaso pa sodium chloride (Chithunzi 3) .Kugwiritsira ntchito njira yopitira mosalekeza kumachepetsa nkhawa za chitetezo zomwe zingayambike mumagulu a batch, monga momwe izi zimapangidwira kwambiri komanso zowopsa za azide intermediates [317], [318] . Cycloaddition ya phenylacetylene ndi iodoethane) (onani Chithunzi 5).
(Pamwamba kumanzere) Schematic ya khwekhwe ntchito kuphatikizira 3DP riyakitala mu otaya dongosolo (pamwamba kumanja) zopezedwa wokometsedwa (pansi) chiwembu cha Huisgen cycloaddition 57 chiwembu pakati phenylacetylene ndi iodoethane kukhathamiritsa ndi kusonyeza wokometsedwa magawo anachita kutembenuka mlingo.
Poyang'anira nthawi yogona ya reagents mu gawo lothandizira la riyakitala ndikuyang'anitsitsa kutentha komwe kukuchitika ndi kafukufuku wophatikizika wa thermocouple, zinthu zomwe zingachitike zitha kukonzedwa mwachangu komanso molondola ndi nthawi yochepa komanso kugwiritsa ntchito zinthu zakuthupi. zonse zogona nthawi ndi kutentha anachita amaonedwa zofunika chitsanzo terms.Kuthamanga anamanga-mu optimizer ntchito mawu osankhidwa amapanga seti ya zinthu zimene anakonza kuti azikulitsa mankhwala nsonga madera pamene kuchepetsa kuyambira zinthu pachimake areas.This kukhathamiritsa anabala 53% kutembenuka kwa triazole mankhwala, amene kwambiri chikufanana kulosera chitsanzo cha 54%.
Kutengera zolemba zomwe zikuwonetsa kuti mkuwa (I) okusayidi (Cu2O) utha kukhala ngati njira yothandiza kwambiri pazigawo zamkuwa za zero-valent pazochita izi, kuthekera kopangira maoxidize pamwamba pa riyakitala isanagwire ntchito yotaya idafufuzidwa70,71. Zomwe zimachitika pakati pa phenylacetylene ndi iodoethane zidachitikanso poyerekezera ndi zokolola zabwino zomwe zidachitikanso pokonzekera bwino. mu kutembenuka kwa zinthu zoyambira, zomwe zinawerengedwa kuti ndi> 99%. kutentha kupanga CuO ndi Cu2O zomwe sizidziteteza zokha.Izi zimathetsa kufunika kowonjezera mkuwa wothandiza (II) gwero la co-composition71.