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Kupanga kowonjezera kukusintha momwe ofufuza ndi akatswiri opanga mafakitale amapangira ndi kupanga zida zamagetsi kuti zikwaniritse zosowa zawo zenizeni.Mu pepalali, ife lipoti chitsanzo choyamba cha otaya riyakitala wopangidwa ndi akupanga zowonjezera kupanga (UAM) lamination wa olimba zitsulo pepala ndi mwachindunji Integrated mbali chothandizira ndi kuzindikira zinthu.Ukadaulo wa UAM sikuti umangogonjetsa zolepheretsa zambiri zomwe zikukhudzana ndi kupanga zowonjezera zamakina amagetsi, komanso zimakulitsa luso la zida zotere.Zambiri za biologically 1,4-disubstituted 1,2,3-triazole mankhwala apangidwa bwino ndi kukonzedwa ndi Cu-mediated 1,3-dipolar Huisgen cycloaddition reaction pogwiritsa ntchito UAM chemistry center.Pogwiritsa ntchito mawonekedwe apadera a UAM ndi kusuntha kosalekeza, chipangizochi chimatha kulimbikitsa zochitika zomwe zikuchitika komanso kupereka ndemanga zenizeni zenizeni kuti ziwonetsetse ndi kukhathamiritsa zomwe zikuchitika.
Chifukwa chaubwino wake wokulirapo kuposa mnzake wochulukirapo, chemistry yoyenda ndi gawo lofunikira komanso lomwe likukula m'maphunziro onse ndi mafakitale chifukwa chakutha kukulitsa kusankhira komanso kuchita bwino kwa kaphatikizidwe kamankhwala.Izi zimayambira pakupanga mamolekyu osavuta a organic1 kupita ku mankhwala a mankhwala2,3 ndi zinthu zachilengedwe4,5,6.Zoposa 50% zamachitidwe m'mafakitale abwino amankhwala ndi mankhwala zitha kupindula ndikuyenda kosalekeza7.
M'zaka zaposachedwa, pakhala pali chizoloŵezi chokulirapo chamagulu omwe akufuna kusintha zida zamagalasi kapena zida zama chemistry zosinthika ndi "reactors"8.Mapangidwe obwerezabwereza, kupanga mwachangu, ndi kuthekera kwa magawo atatu (3D) a njirazi ndizothandiza kwa iwo omwe akufuna kusintha zida zawo kuti zigwirizane ndi machitidwe, zida, kapena mikhalidwe.Mpaka pano, ntchitoyi yangoyang'ana kwambiri pakugwiritsa ntchito njira zosindikizira za 3D polima polima monga stereolithography (SL)9,10,11, Fused Deposition Modeling (FDM)8,12,13,14 ndi inkjet printing7,15., 16. Kusadalirika komanso kuthekera kwa zida zotere kuti zigwiritse ntchito mitundu yosiyanasiyana yamankhwala / kusanthula17, 18, 19, 20 ndizomwe zimalepheretsa kugwiritsa ntchito kwakukulu kwa AM m'munda uno17, 18, 19, 20.
Chifukwa chakuchulukirachulukira kwa chemistry yoyenda komanso zinthu zabwino zomwe zimagwirizanitsidwa ndi AM, njira zabwinoko ziyenera kufufuzidwa zomwe zingathandize ogwiritsa ntchito kupanga zotengera zomwe zikuyenda bwino ndi chemistry komanso luso lowunikira.Njirazi ziyenera kulola ogwiritsa ntchito kusankha kuchokera ku mphamvu zambiri kapena zipangizo zogwirira ntchito zomwe zingathe kugwira ntchito pazochitika zosiyanasiyana, komanso kuwongolera njira zosiyanasiyana zowunikira kuchokera ku chipangizocho kuti athe kuyang'anira ndi kuwongolera zomwe zikuchitika.
Chimodzi mwazinthu zopangira zopangira zomwe zingagwiritsidwe ntchito popanga makina opangira mankhwala ndi Akupanga Additive Manufacturing (UAM).Izi olimba-boma pepala lamination njira ntchito akupanga kugwedera kwa woonda zitsulo zojambulazo kuwamanga pamodzi wosanjikiza ndi wosanjikiza ndi osachepera volumetric Kutentha ndi mkulu digiri ya pulasitiki otaya 21, 22, 23. Mosiyana ndi ena ambiri AM matekinoloje, UAM akhoza mwachindunji Integrated ndi subtractive kupanga, otchedwa wosakanizidwa kupanga ndondomeko, imene periodic mu-situ mu-situ ndi manambala kulamulira kwa mphero, CNC kutsimikizira manambala ang'onoang'ono kuwongolera kapena kugwirizana zitsulo zopangira laser (CNC) 25. Izi zikutanthawuza kuti wogwiritsa ntchitoyo sakhala ndi mavuto okhudzana ndi kuchotsedwa kwa zotsalira zoyambirira zomangira kuchokera kumayendedwe ang'onoang'ono amadzimadzi, omwe nthawi zambiri amakhala mu ufa ndi machitidwe amadzimadzi AM26,27,28.Ufulu wapangidwe uwu umaphatikizaponso kusankha kwa zipangizo zomwe zilipo - UAM ikhoza kumangiriza kuphatikizika kwa zipangizo zofananira ndi zowonongeka mu sitepe imodzi yokha.Kusankhidwa kwa zinthu zophatikizika kupitilira kusungunuka kumatanthauza kuti zofunikira zamakina ndi zamankhwala pazogwiritsa ntchito zina zitha kukwaniritsidwa bwino.Kuwonjezera olimba kugwirizana, chodabwitsa china chimene chimapezeka ndi akupanga kugwirizana ndi mkulu fluidity wa pulasitiki zipangizo pa ndi otsika kutentha29,30,31,32,33.Mbali yapaderayi ya UAM imalola zinthu zamakina / zotentha kuti ziziyikidwa pakati pa zigawo zachitsulo popanda kuwonongeka.Masensa ophatikizidwa a UAM amatha kuthandizira kutumizidwa kwa zidziwitso zenizeni zenizeni kuchokera ku chipangizocho kupita kwa wogwiritsa ntchito pogwiritsa ntchito ma analytics ophatikizika.
Ntchito yam'mbuyomu ya olemba32 idawonetsa kuthekera kwa njira ya UAM kupanga zitsulo zazitsulo za 3D za microfluidic zokhala ndi luso lozindikira.Chipangizochi ndi chowunika kokha.Nkhaniyi ikupereka chitsanzo choyamba cha microfluidic chemical reactor yopangidwa ndi UAM, chipangizo chogwira ntchito chomwe sichimangoyang'anira komanso chimapangitsa kuti mankhwala azitha kuphatikizika ndi zipangizo zothandizira.Chipangizochi chimaphatikizapo ubwino wambiri wokhudzana ndi teknoloji ya UAM popanga zipangizo zamakono za 3D, monga: kukwanitsa kutembenuza mapangidwe athunthu a 3D mwachindunji kuchokera ku makina opangidwa ndi makompyuta (CAD) kukhala mankhwala;Kupanga kwazinthu zambiri zophatikizira matenthedwe apamwamba kwambiri komanso zida zothandizira, komanso masensa otenthetsera ophatikizidwa mwachindunji pakati pa mitsinje ya reactant kuti athe kuwongolera bwino ndikuwongolera kutentha komwe kumachitika.Kuwonetsa magwiridwe antchito a riyakitala, laibulale yamankhwala ofunikira 1,4-disubstituted 1,2,3-triazole mankhwala adapangidwa ndi mkuwa-catalyzed 1,3-dipolar Huisgen cycloaddition.Ntchitoyi ikuwonetsa momwe kugwiritsa ntchito sayansi yazinthu ndi kapangidwe kothandizidwa ndi makompyuta kungatsegulire mwayi watsopano ndi mwayi wa chemistry kudzera mu kafukufuku wamitundu yosiyanasiyana.
Zosungunulira zonse ndi ma reagents adagulidwa ku Sigma-Aldrich, Alfa Aesar, TCI, kapena Fischer Scientific ndipo amagwiritsidwa ntchito popanda kuyeretsedwa kale.1H ndi 13C NMR mawonekedwe ojambulidwa pa 400 ndi 100 MHz, motero, anapezedwa pa JEOL ECS-400 400 MHz spectrometer kapena Bruker Avance II 400 MHz spectrometer ndi CDCl3 kapena (CD3)2SO monga zosungunulira.Zochita zonse zidachitika pogwiritsa ntchito nsanja ya Uniqsis FlowSyn flow chemistry.
UAM idagwiritsidwa ntchito kupanga zida zonse mu kafukufukuyu.Tekinolojeyi idapangidwa mu 1999 ndipo zambiri zake zaukadaulo, magawo ogwiritsira ntchito ndi zomwe zikuchitika kuyambira pomwe zidapangidwa zitha kuphunziridwa pogwiritsa ntchito zida zosindikizidwa zotsatirazi34,35,36,37.Chipangizocho (mkuyu 1) chinagwiritsidwa ntchito pogwiritsa ntchito ntchito yolemetsa ya 9 kW SonicLayer 4000® UAM system (Fabrisonic, Ohio, USA).The zipangizo osankhidwa otaya chipangizo anali Cu-110 ndi Al 6061. Cu-110 ali okhutira mkulu mkuwa (osachepera 99.9% mkuwa), kupanga phungu wabwino mkuwa catalyzed zimachitikira choncho ntchito ngati "wosanjikiza yogwira mkati microreactor.Al 6061 O amagwiritsidwa ntchito ngati "zambiri" zakuthupi., komanso wosanjikizana wogwiritsidwa ntchito posanthula;kuphatikizika kwa zigawo za aloyi wothandiza ndi gawo la annealed kuphatikiza ndi wosanjikiza wa Cu-110.adapezeka kuti ali okhazikika pamakina ndi ma reagents omwe amagwiritsidwa ntchito pantchitoyi.Al 6061 O kuphatikiza ndi Cu-110 imawonedwanso ngati chophatikizira cha UAM ndipo ndichofunika pa kafukufukuyu38,42.Zida izi zalembedwa mu Table 1 pansipa.
Masitepe opangira makina opangira zida (1) 6061 aluminium alloy substrate (2) Kupanga njira yotsika kuchokera ku zojambula zamkuwa (3) Kuyika ma thermocouples pakati pa zigawo (4) Chapamwamba (5) Cholowera ndi chotulukira (6) Monolithic reactor.
Filosofi yopangira njira yamadzimadzi ndikugwiritsa ntchito njira yowawa kuti muwonjezere mtunda woyenda ndi madzimadzi mkati mwa chip ndikusunga kukula kwa chip.Kuwonjezeka kwa mtunda kumeneku ndikofunikira kuti muwonjezere nthawi yolumikizirana ndi chothandizira komanso kupereka zokolola zabwino kwambiri.Tchipisi zimagwiritsa ntchito kupindika kwa 90 ° kumapeto kwa njira yowongoka kuti apangitse kusakanikirana kosokoneza mkati mwa chipangizochi44 ndikuwonjezera nthawi yolumikizana ndi madzi ndi pamwamba (chothandizira).Kupititsa patsogolo kusakaniza komwe kungapezeke, mapangidwe a riyakitala amaphatikizapo zolowetsa ziwiri zowonongeka zomwe zimagwirizanitsidwa ndi Y-kugwirizana musanalowe mu gawo losakaniza coil.Khomo lachitatu, lomwe limadutsa pakati pa malo okhalamo, likuphatikizidwa mu dongosolo la zochitika zamtsogolo zamagulu ambiri.
Makanema onse ali ndi masikweya (palibe ma taper angles), zomwe ndi zotsatira za mphero yanthawi zonse ya CNC yomwe imagwiritsidwa ntchito popanga geometry ya tchanelo.Makulidwe a tchanelo amasankhidwa kuti apereke zokolola zambiri (za microreactor) za volumetric, koma zazing'ono kuti zithandizire kulumikizana ndi pamwamba (zothandizira) pazakumwa zambiri zomwe zilimo.Kukula koyenera kumatengera zomwe olemba adakumana nazo m'mbuyomu ndi zida zazitsulo zamadzimadzi.Miyezo yamkati ya njira yomaliza inali 750 µm x 750 µm ndipo voliyumu yonse ya reactor inali 1 ml.Cholumikizira chomangidwira (1/4″-28 UNF ulusi) chimaphatikizidwa ndi mapangidwe kuti alole kulumikizana kosavuta kwa chipangizocho ndi zida zamalonda zama chemistry.Kukula kwa Channel kumachepa ndi makulidwe a zojambulazo, makina ake, ndi magawo ogwirizana omwe amagwiritsidwa ntchito ndi ultrasonics.Pakukula kwina kwa zinthu zomwe zaperekedwa, zinthuzo "zidzalowa" munjira yopangidwa.Pakali pano palibe chitsanzo chenicheni cha kuwerengetseraku, kotero kuti kukula kwa tchanelo kwa chinthu choperekedwa ndi kapangidwe kake kumatsimikiziridwa moyesera, pomwe m'lifupi mwake 750 µm sikungayambitse kugwa.
Mawonekedwe (mzere) wa njirayo amatsimikiziridwa pogwiritsa ntchito chodula chapakati.Maonekedwe ndi kukula kwa mayendedwe angasinthidwe pa makina CNC ntchito zida kudula osiyana kupeza mitengo otaya osiyana ndi makhalidwe.Chitsanzo chopanga njira yokhotakhota yokhala ndi chida cha 125 µm chingapezeke ku Monaghan45.Pamene chojambulacho chikugwiritsidwa ntchito mopanda phokoso, kugwiritsa ntchito zojambulazo kuzitsulo kudzakhala ndi malo ophwanyika (mabwalo).Pantchito iyi, mizere yozungulira idagwiritsidwa ntchito kusunga ma symmetry.
Panthawi yopuma yopangidwa, zowunikira kutentha kwa thermocouple (mtundu wa K) zimamangidwa mwachindunji mu chipangizo pakati pa magulu apamwamba ndi otsika (mkuyu 1 - siteji 3).Ma thermocouples awa amatha kuwongolera kusintha kwa kutentha kuchokera pa -200 mpaka 1350 °C.
Njira yoyika zitsulo imachitika ndi nyanga ya UAM pogwiritsa ntchito zojambula zachitsulo 25.4 mm m'lifupi ndi 150 microns wandiweyani.Zigawo za zojambulazo zimagwirizanitsidwa mndandanda wa mizere yoyandikana kuti iphimbe malo onse omanga;kukula kwa zinthu zoyikidwa ndi zazikulu kuposa zomaliza monga njira yochotsera imapanga mawonekedwe oyera omaliza.Makina a CNC amagwiritsidwa ntchito popanga makina akunja ndi mkati mwa zida, zomwe zimapangitsa kuti pakhale kutha kwa zida ndi njira zomwe zimagwirizana ndi chida chosankhidwa ndi magawo a ndondomeko ya CNC (mu chitsanzo ichi, pafupifupi 1.6 µm Ra).Kusalekeza, mosalekeza akupanga zinthu kupopera mbewu mankhwalawa ndi Machining m'zinthu ntchito mu chipangizo kupanga ndondomeko kuonetsetsa dimensional olondola anakhalabe ndi yomalizidwa gawo akukumana CNC zabwino mphero mwatsatanetsatane milingo.M'lifupi mwa njira yomwe imagwiritsidwa ntchito pa chipangizochi ndi yaying'ono mokwanira kuti zitsimikizire kuti zojambulazo "zisagwere" mumsewu wamadzimadzi, kotero kuti njirayo imakhala ndi gawo lalikulu.Mipata yotheka muzojambulazo ndi magawo a njira ya UAM idatsimikiziridwa moyesera ndi wopanga mnzake (Fabrisonic LLC, USA).
Kafukufuku wasonyeza kuti pa mawonekedwe a 46, 47 a UAM pawiri pali kufalikira pang'ono kwa zinthu popanda mankhwala owonjezera kutentha, kotero kwa zipangizo mu ntchitoyi Cu-110 wosanjikiza amakhalabe wosiyana ndi Al 6061 wosanjikiza ndi kusintha kwambiri.
Ikani pre-calibrated back pressure regulator (BPR) pa 250 psi (1724 kPa) kunsi kwa riyakitala ndikupopa madzi kudzera mu riyakitala pamlingo wa 0.1 mpaka 1 ml min-1.Kuthamanga kwa riyakitala kumayang'aniridwa pogwiritsa ntchito FlowSyn pressure transducer yomwe idamangidwa mu dongosolo kuti zitsimikizire kuti dongosololi limatha kukhalabe ndi mphamvu yokhazikika.Kutentha komwe kungatheke mu choyatsira choyatsira adayesedwa poyang'ana kusiyana kulikonse pakati pa ma thermocouples omwe amamangidwa mu reactor ndi ma thermocouples omangidwa mu mbale yotenthetsera ya FlowSyn chip.Izi zimatheka mwa kusintha kutentha kwa hotplate yokonzedwa pakati pa 100 ndi 150 ° C mu 25 ° C increments ndi kuyang'anira kusiyana kulikonse pakati pa kutentha kokonzedwa ndi kujambulidwa.Izi zinatheka pogwiritsa ntchito tc-08 data logger (PicoTech, Cambridge, UK) ndi pulogalamu yotsatizana nayo ya PicoLog.
Mikhalidwe ya cycloaddition reaction ya phenylacetylene ndi iodoethane imakonzedwa (Scheme 1-Cycloaddition of phenylacetylene ndi iodoethane, Scheme 1-Cycloaddition of phenylacetylene ndi iodoethane).Kukhathamiritsa kumeneku kunachitika pogwiritsa ntchito njira yoyeserera yoyeserera (DOE), pogwiritsa ntchito kutentha ndi nthawi yokhalamo monga zosinthika pomwe mukukonza chiŵerengero cha alkyne:azide pa 1:2.
Njira zosiyana za sodium azide (0.25 M, 4: 1 DMF: H2O), iodoethane (0.25 M, DMF), ndi phenylacetylene (0.125 M, DMF) zinakonzedwa.A 1.5 ml aliquot ya njira iliyonse anali osakaniza ndi kupopera riyakitala pa kufunika otaya mlingo ndi kutentha.Yankho lachitsanzo linatengedwa ngati chiŵerengero cha pachimake cha mankhwala triazole kwa zinthu zoyambira phenylacetylene ndipo anatsimikiza ntchito mkulu ntchito madzi chromatography (HPLC).Pakuti kusanthula kugwirizana, zonse anachita anatengedwa mwamsanga zimene osakaniza anasiya riyakitala.Magawo osankhidwa kuti akwaniritse bwino akuwonetsedwa mu Gulu 2.
Zitsanzo zonse zidawunikidwa pogwiritsa ntchito Chromaster HPLC system (VWR, PA, USA) yomwe ili ndi pampu ya quaternary, uvuni wa column, variable wavelength UV detector ndi autosampler.Mzerewu unali Equivalence 5 C18 (VWR, PA, USA), 4.6 x 100 mm, 5 µm particle size, yosungidwa pa 40°C.The zosungunulira anali isocratic methanol: madzi 50:50 pa otaya mlingo wa 1.5 ml · min-1.Voliyumu ya jakisoni inali 5 μl ndipo kutalika kwa detector kunali 254 nm.Dera lapamwamba la % la chitsanzo cha DOE linawerengedwa kuchokera kumadera apamwamba a zotsalira za alkyne ndi triazole zokha.Kuyamba kwa zinthu zoyambira kumathandizira kuzindikira nsonga zofananira.
Kuphatikiza zotsatira za kusanthula kwa riyakitala ndi pulogalamu ya MODDE DOE (Umetrics, Malmö, Sweden) idalola kusanthula kwatsatanetsatane kwazotsatira ndi kutsimikiza kwa momwe angachitire pa cycloaddition iyi.Kuthamangitsa chowonjezera chokhazikika ndikusankha mawu onse ofunikira kumapangitsa kuti pakhale zochitika zomwe zimapangidwira kukulitsa gawo lazogulitsazo ndikuchepetsa malo okwera kwambiri a acetylene feedstock.
Makutidwe ndi okosijeni wa pamwamba mkuwa mu chothandizira anachita chipinda chinatheka ntchito hydrogen peroxide njira (36%) ikuyenda mu anachita chipinda (otaya mlingo = 0,4 ml min-1, zogona nthawi = 2.5 min) isanafike synthesis aliyense pawiri triazole.laibulale.
Pamene mikhalidwe yabwino kwambiri idatsimikiziridwa, idagwiritsidwa ntchito pamitundu yambiri ya acetylene ndi haloalkane kuti alole kuphatikizika kwa laibulale yaing'ono yophatikizira, potero kukhazikitsa mwayi wogwiritsa ntchito mikhalidwe imeneyi kuzinthu zambiri zomwe zingayambitse (mkuyu 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).Ma Aliquots a 3 ml ya yankho lililonse adasakanizidwa ndikupopedwa kudzera mu riyakitala pamlingo wa 75 µl/min ndi kutentha kwa 150°C.Voliyumu yonseyo idasonkhanitsidwa mu vial ndikuchepetsedwa ndi 10 ml ya ethyl acetate.Njira yothetsera vutoli idatsukidwa ndi 3 x 10 ml ya madzi.The zigawo amadzimadzi anali pamodzi ndi yotengedwa ndi 10 ml ethyl acetate, ndiye zigawo organic anali pamodzi, kutsukidwa ndi 3 × 10 ml brine, zouma pa MgSO 4 ndi osasankhidwa, ndiye zosungunulira anachotsedwa vacuo.Zitsanzo zidayeretsedwa ndi silica gel column chromatography pogwiritsa ntchito ethyl acetate asanaunike ndi kuphatikiza kwa HPLC, 1H NMR, 13C NMR ndi high resolution mass spectrometry (HR-MS).
Zowonera zonse zidapezedwa pogwiritsa ntchito Thermofischer Precision Orbitrap mass spectrometer yokhala ndi ESI ngati gwero la ionization.Zitsanzo zonse zidakonzedwa pogwiritsa ntchito acetonitrile monga zosungunulira.
Kusanthula kwa TLC kunachitika pama mbale a silika okhala ndi gawo lapansi la aluminiyamu.Mabalawa adawonetsedwa ndi kuwala kwa UV (254 nm) kapena madontho a vanillin ndi kutentha.
Zitsanzo zonse zidawunikidwa pogwiritsa ntchito VWR Chromaster system (VWR International Ltd., Leighton Buzzard, UK) yokhala ndi autosampler, pampu ya binary yokhala ndi ng'anjo yamzanja ndi chowunikira chimodzi chawavelength.Chigawo cha ACE Equivalence 5 C18 (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland) chinagwiritsidwa ntchito.
jakisoni (5 µl) anapangidwa mwachindunji kuchepetsedwa zosakayikitsa anachita osakaniza (1:10 dilution) ndi kusanthula ndi madzi: methanol (50:50 kapena 70:30), kupatulapo zitsanzo ntchito 70:30 zosungunulira dongosolo (amatanthauza nyenyezi nambala ) pa otaya mlingo wa 1.5 ml/mphindi.Mzerewu unasungidwa pa 40 ° C.Kutalika kwa detector ndi 254 nm.
Dera lapamwamba la % lachitsanzo lidawerengedwa kuchokera pachimake cha alkyne yotsalira, mankhwala a triazole okha, ndipo kuyambitsidwa kwa zinthu zoyambira kunapangitsa kuti zitheke kuzindikira nsonga zofananira.
Zitsanzo zonse zidawunikidwa pogwiritsa ntchito Thermo iCAP 6000 ICP-OES.Miyezo yonse yoyezera idakonzedwa pogwiritsa ntchito njira yokhazikika ya 1000 ppm Cu mu 2% nitric acid (SPEX Certi Prep).Mfundo zonse zinakonzedwa mu njira ya 5% DMF ndi 2% HNO3, ndipo zitsanzo zonse anali kuchepetsedwa 20 zina ndi chitsanzo cha DMF-HNO3.
UAM imagwiritsa ntchito kuwotcherera kwachitsulo akupanga ngati njira yolumikizira zitsulo zomwe zimagwiritsidwa ntchito popanga msonkhano womaliza.Akupanga zitsulo kuwotcherera kumagwiritsa ntchito chitsulo chogwedeza chida (chotchedwa nyanga kapena nyanga ya akupanga) kuti agwiritse ntchito kukakamiza kwa zojambulazo / zosanjikiza zomwe zidaphatikizidwa kale kuti zimangiridwe / zophatikizidwa kale ndi kugwedeza zakuthupi.Pakuti mosalekeza ntchito, ndi sonotrode ali cylindrical mawonekedwe ndi ipitirirabe pamwamba pa zinthu, gluing m'dera lonse.Pamene kupanikizika ndi kugwedezeka kumagwiritsidwa ntchito, ma oxides pamwamba pa zinthuzo amatha kusweka.Kupanikizika kosalekeza ndi kugwedezeka kungayambitse chiwonongeko cha roughness ya zinthu 36 .Kulumikizana kwapafupi ndi kutentha komweko ndi kukakamizidwa ndiye kumatsogolera ku mgwirizano wokhazikika pamagulu azinthu;Zingathenso kulimbikitsa mgwirizano mwa kusintha mphamvu ya pamwamba48.Chikhalidwe cha makina omangira amagonjetsa mavuto ambiri okhudzana ndi kutentha kwa kutentha kwa kutentha ndi kutentha kwakukulu komwe kumatchulidwa muzinthu zina zamakono zopangira zowonjezera.Izi zimathandiza kugwirizana mwachindunji (ie popanda pamwamba kusinthidwa, fillers kapena zomatira) angapo zigawo za zipangizo zosiyanasiyana mu umodzi consolidated dongosolo.
Chinthu chachiwiri chabwino cha CAM ndi kuchuluka kwa pulasitiki yotuluka muzinthu zachitsulo ngakhale kutentha kochepa, mwachitsanzo, pansi pa malo osungunuka azitsulo.Kuphatikiza akupanga kugwedera ndi kuthamanga kumayambitsa mkulu mlingo wa m'deralo tirigu malire kusamuka ndi recrystallization popanda kwambiri kutentha kuwonjezeka miyambo kugwirizana ndi chochuluka zipangizo.Pakupanga msonkhano womaliza, chodabwitsa ichi chingagwiritsidwe ntchito kuyika zigawo zogwira ntchito komanso zopanda pake pakati pa zigawo zazitsulo zachitsulo, zosanjikiza ndi zosanjikiza.Zinthu monga optical fiber 49, reinforcement 46, electronics 50 ndi thermocouples (ntchitoyi) zaphatikizidwa bwino mumagulu a UAM kuti apange misonkhano yogwira ntchito komanso yopanda pake.
Pantchitoyi, kuthekera kophatikizana kwazinthu zosiyanasiyana komanso kuthekera kolumikizana kwa UAM kudagwiritsidwa ntchito kupanga chowongolera chowongolera kutentha kwamphamvu.
Poyerekeza ndi palladium (Pd) ndi zina zambiri ntchito zitsulo zothandizira, Cu catalysis ali ndi ubwino angapo: (i) Pachuma, Cu ndi wotsika mtengo kuposa zitsulo zina zambiri ntchito catalysis choncho ndi njira yokongola kwa makampani mankhwala (ii) osiyanasiyana Cu-catalyzed mtanda kugwirizana zochita ndi kukula ndipo zikuoneka kuti Pd2,5caary -3 Culogies -3, 51-ochokera njira zochita za talyzed zimagwira ntchito bwino popanda ma ligand ena.Ma ligand awa nthawi zambiri amakhala osavuta komanso otsika mtengo.ngati angafune, pamene omwe amagwiritsidwa ntchito mu Pd chemistry nthawi zambiri amakhala ovuta, okwera mtengo, komanso okhudzidwa ndi mpweya (iv) Cu, makamaka omwe amadziwika kuti amatha kugwirizanitsa alkynes mu kaphatikizidwe, monga Sonogashira's bimetallic catalyzed coupling ndi cycloaddition ndi azides (dinani chemistry) (v) Cu ikhoza kulimbikitsanso arylation ya nuclelotype ya Usmann-phile reaction.
Posachedwapa, zitsanzo za heterogenization za zochitika zonsezi pamaso pa Cu(0) zasonyezedwa.Izi zachitika makamaka chifukwa chamakampani opanga mankhwala komanso kukulitsa chidwi pakuchira ndikugwiritsanso ntchito zopangira zitsulo55,56.
1,3-dipolar cycloaddition reaction pakati pa acetylene ndi azide kupita ku 1,2,3-triazole, yomwe idaperekedwa koyamba ndi Huisgen mu 1960s57, imawonedwa ngati synergistic demonstration reaction.Zotsatira za 1,2,3 triazole zidutswa zimakhala zochititsa chidwi kwambiri monga pharmacophore pakupeza mankhwala osokoneza bongo chifukwa cha ntchito zawo zamoyo ndikugwiritsa ntchito mankhwala osiyanasiyana 58.
Izi zidathandizidwanso pomwe Sharpless ndi ena adayambitsa lingaliro la "click chemistry"59.Mawu oti "click chemistry" amagwiritsidwa ntchito kutanthauza machitidwe amphamvu komanso osankhidwa a kaphatikizidwe katsopano kazinthu zatsopano ndi malaibulale ophatikizika pogwiritsa ntchito heteroatomic bonding (CXC)60.Kukopa kopanga kwa machitidwewa ndi chifukwa cha zokolola zambiri zomwe zimagwirizanitsidwa nazo.mikhalidwe ndi yosavuta, kukana mpweya ndi madzi, ndipo kulekanitsa mankhwala ndikosavuta61.
Gulu lachikale la 1,3-dipole Huisgen cycloaddition siligwera mugulu la "click chemistry".Komabe, Medal ndi Sharpless adawonetsa kuti chochitika chophatikizira cha azide-alkyne chikudutsa 107-108 pamaso pa Cu (I) poyerekeza ndi kuthamanga kwakukulu pamlingo wa non-catalytic 1,3-dipolar cycloaddition 62,63.Izi zapamwamba anachita limagwirira sikutanthauza kuteteza magulu kapena zinthu nkhanza anachita ndipo amapereka pafupifupi wathunthu kutembenuka ndi selectivity kwa 1,4-disubstituted 1,2,3-triazoles (anti-1,2,3-triazoles) pa nthawi (mkuyu 3).
Zotsatira za Isometric za Huisgen cycloadditions wamba komanso zamkuwa.Cu(I)-catalyzed Huisgen cycloadditions amapereka 1,4-disubstituted 1,2,3-triazoles okha, pamene ma cycloadditions a Huisgen omwe amapangidwa ndi thermally amapereka 1,4- ndi 1,5-triazoles chisakanizo cha 1: 1 cha azole stereoisomers.
Mapulogalamu ambiri amaphatikizapo kuchepetsa magwero okhazikika a Cu (II), monga kuchepetsa CuSO4 kapena Cu (II) / Cu (0) pawiri pamodzi ndi mchere wa sodium.Poyerekeza ndi machitidwe ena achitsulo, kugwiritsa ntchito Cu(I) kuli ndi ubwino waukulu wokhala wotchipa komanso wosavuta kugwira.
Maphunziro a Kinetic ndi isotopic a Worrell et al.65 awonetsa kuti pankhani ya ma alkynes omaliza, zofananira ziwiri zamkuwa zimakhudzidwa ndikuyambitsanso kuyambiranso kwa molekyulu iliyonse polemekeza azide.Njira yomwe ikuyembekezeredwa imadutsa mu mphete yazitsulo yamkuwa yokhala ndi mamembala asanu ndi limodzi yopangidwa ndi kulumikizana kwa azide kupita ku σ-bonded copper acetylide yokhala ndi π-bonded mkuwa ngati ligand yokhazikika yopereka.Zotengera zamkuwa za triazolyl zimapangidwa chifukwa cha kutsika kwa mphete kutsatiridwa ndi kuwonongeka kwa pulotoni kupanga zinthu za triazole ndikutseka kuzungulira kothandizira.
Ngakhale kuti ubwino wa zipangizo zamakina othamanga ndi zolembedwa bwino, pakhala pali chikhumbo chophatikiza zida zowunikira m'makinawa kuti awonetsere zochitika zenizeni mu situ66,67.UAM yatsimikizira kukhala njira yoyenera yopangira ndi kupanga zovuta kwambiri za 3D otaya reactors kuchokera ku catalytically yogwira, thermally conductive zipangizo ndi mwachindunji ophatikizidwa zomverera zinthu (mkuyu. 4).
Aluminiyamu-mkuwa otaya riyakitala chopangidwa ndi akupanga zowonjezera kupanga (UAM) ndi zovuta mkati njira dongosolo, anamanga-thermocouples ndi chothandizira anachita chipinda.Kuti muwone njira zamadzimadzi zamkati, chiwonetsero chowonekera chopangidwa pogwiritsa ntchito stereolithography chimawonetsedwanso.
Kuonetsetsa kuti ma reactors amapangidwira mtsogolo momwe zimachitikira, zosungunulira ziyenera kutenthedwa bwino pamwamba pa kuwira;iwo ndi kuthamanga ndi kutentha kuyesedwa.Kuyesedwa kwapanikizi kunawonetsa kuti dongosololi limakhalabe lokhazikika komanso lokhazikika ngakhale pazovuta kwambiri mu dongosolo (1.7 MPa).Mayeso a Hydrostatic adachitika kutentha kwa chipinda pogwiritsa ntchito H2O ngati madzi.
Kulumikiza zomangira (Chithunzi 1) ku thermocouple ku cholembera cha data cha kutentha kunawonetsa kuti kutentha kwa thermocouple kunali 6 °C (± 1 °C) pansi pa kutentha kwadongosolo mu FlowSyn system.Nthawi zambiri, kutentha kwa 10 ° C kumachulukitsa kuchuluka kwa zomwe zimachitika, kotero kusiyana kwa kutentha kwa madigiri ochepa kumatha kusintha momwe zimachitikira kwambiri.Kusiyanaku kumachitika chifukwa cha kuchepa kwa kutentha mu RPV yonse chifukwa cha kutentha kwakukulu kwazinthu zomwe zimagwiritsidwa ntchito popanga.Kuthamanga kwa kutentha kumeneku kumakhala kosalekeza ndipo kungathe kuganiziridwa pokhazikitsa zipangizo kuti zitsimikizire kuti kutentha kolondola kumafika ndikuyezedwa panthawiyi.Chifukwa chake, chida chowunikira ichi pa intaneti chimathandizira kuwongolera mwamphamvu momwe kutentha kumachitikira ndipo kumathandizira kukhathamiritsa kwatsatanetsatane komanso kukulitsa mikhalidwe yabwino.masensa awa angagwiritsidwenso ntchito kudziwa zochita exothermic ndi kuteteza anathawa zochita mu lalikulu lonse machitidwe.
The riyakitala zomwe zaperekedwa mu pepala ili ndi chitsanzo choyamba cha ntchito UAM luso kupanga riyakitala mankhwala ndi maadiresi zofooka zingapo zazikulu panopa kugwirizana ndi AM/3D kusindikiza zipangizo zimenezi, monga: (i) Kugonjetsa mavuto odziwika kugwirizana ndi processing wa mkuwa kapena zitsulo zotayidwa aloyi (ii) bwino mkati njira kusamvana poyerekeza ndi ufa bedi kusungunuka (PBive6 otaya otaya njira, PBF6 laser otaya)2 njira zosungunulira pamwamba (PB9M) ng'anjo yamtundu wa SLM 5 kapena kusungunuka kwa laser 26 (iii) kutentha kwa kutentha kwapansi, komwe kumathandizira kulumikiza kwachindunji masensa, zomwe sizingatheke muukadaulo wa bedi la ufa, (v) kugonjetsa zinthu zosauka zamakina ndi kukhudzidwa kwa zigawo za polima kuzinthu zosiyanasiyana zosungunulira organic17,19.
The magwiridwe a riyakitala anasonyeza ndi angapo mkuwa-catalyzed alkinazide cycloaddition zimachitikira pansi mosalekeza otaya zinthu (mkuyu. 2).The akupanga kusindikizidwa mkuwa riyakitala anasonyeza mkuyu.4 inaphatikizidwa ndi kayendedwe ka malonda ndipo imagwiritsidwa ntchito popanga laibulale ya azide ya 1,4-disubstituted 1,2,3-triazoles pogwiritsa ntchito kutentha komwe kumayendetsedwa ndi acetylene ndi alkyl gulu halides pamaso pa sodium kolorayidi (mkuyu 3).Kugwiritsiridwa ntchito kwa njira yopitira mosalekeza kumachepetsa zovuta zachitetezo zomwe zingabwere munjira za batch, popeza izi zimatulutsa zowopsa komanso zowopsa za azide intermediates [317], [318].Poyamba, anachita wokometsedwa kwa cycloaddition wa phenylacetylene ndi iodoethane (Scheme 1 - Cycloaddition wa phenylacetylene ndi iodoethane) (onani mkuyu. 5).
(Kumtunda kumanzere) Schematic wa khwekhwe ntchito kuphatikizira 3DP riyakitala mu otaya dongosolo (chapamwamba kumanja) zopezedwa wokometsedwa (m'munsi) chiwembu cha Huisgen 57 cycloaddition scheme pakati phenylacetylene ndi iodoethane kukhathamiritsa ndi kusonyeza wokometsedwa kutembenuka mlingo magawo a anachita.
Ndi kulamulira zogona nthawi ya reactants mu gawo chothandizira wa riyakitala ndi mosamala kuyan'ana kutentha anachita ndi mwachindunji Integrated thermocouple sensa, zinthu anachita akhoza mofulumira ndi molondola wokometsedwa ndi osachepera nthawi ndi zipangizo.Zinapezeka mwachangu kuti kutembenuka kwakukulu kunakwaniritsidwa pogwiritsa ntchito nthawi yokhalamo ya mphindi 15 ndi kutentha kwa 150 ° C.Zitha kuwoneka kuchokera ku chiwembu chokhazikika cha pulogalamu ya MODDE kuti nthawi yokhalamo komanso kutentha komwe kumawonedwa kumawonedwa ngati zofunikira zachitsanzo.Kuthamangitsa chowonjezera chokhazikika pogwiritsa ntchito zinthu zosankhidwazi kumapangitsa kuti pakhale zochitika zomwe zimapangidwira kuti ziwonjezeke madera apamwamba kwambiri ndikuchepetsa madera oyambira.Kukhathamiritsa kumeneku kunabweretsa kutembenuka kwa 53% kwa mankhwala a triazole, omwe amafanana ndendende ndi zomwe zanenedweratu za 54%.