Daalụ maka ileta Nature.com.Ụdị ihe nchọgharị ị na-eji nwere nkwado CSS nwere oke.Maka ahụmịhe kachasị mma, anyị na-akwado ka ị jiri ihe nchọgharị emelitere (ma ọ bụ gbanyụọ ọnọdụ ndakọrịta na Internet Explorer).Ka ọ dị ugbu a, iji hụ na nkwado na-aga n'ihu, anyị ga-enye saịtị ahụ na-enweghị ụdị na Javascript.
Carousel na-egosi slide atọ n'otu oge.Jiri bọtịnụ gara aga na nke na-esote ịgafe na slide atọ n'otu oge, ma ọ bụ jiri bọtịnụ mmịfe na njedebe ka ịgafe slide atọ n'otu oge.
Nrụpụta ihe mgbakwunye na-agbanwe ụzọ ndị nyocha na ndị na-emepụta ihe na-emepụta na imepụta ngwaọrụ kemịkal iji gboo mkpa ha.N'ime akwụkwọ a, anyị na-akọ ihe atụ mbụ nke reactor na-asọpụta nke ultrasonic mgbakwunye n'ichepụta (UAM) lamination nke a siri ike metal mpempe akwụkwọ na ozugbo integrated catalytic akụkụ na-aghọta ihe.Nkà na ụzụ UAM abụghị naanị na-emeri ọtụtụ njedebe ugbu a na mmepụta nke ihe nrụpụta kemịkalụ, kamakwa na-agbasawanye ike nke ngwaọrụ ndị dị otú ahụ.Ọnụ ọgụgụ nke ihe dị mkpa dị mkpa 1,4-disubstituted 1,2,3-triazole ogige ejiriwo nke ọma na-arụ ọrụ nke ọma site na mmeghachi omume 1,3-dipolar Huisgen cycloaddition nke Cu-mediated site na iji ụlọ ọrụ UAM chemistry.N'iji njirimara pụrụ iche nke UAM na nhazi nhazi na-aga n'ihu, ngwaọrụ ahụ nwere ike ịmepụta mmeghachi omume na-aga n'ihu yana inye nzaghachi ozugbo iji nyochaa ma kwalite mmeghachi omume.
N'ihi uru ya dị ịrịba ama karịa nnukwu onye otu ya, kemịkalụ na-asọ asọ bụ ubi dị mkpa ma na-eto eto na ntọala agụmakwụkwọ na ụlọ ọrụ mmepụta ihe n'ihi ikike ya ịbawanye nhọrọ na arụmọrụ nke njikọ kemịkal.Nke a na-esite na nguzobe nke molekul organic dị mfe1 ruo ogige ọgwụ2,3 na ngwaahịa eke4,5,6.Ihe karịrị 50% nke mmeghachi omume na kemịkalụ dị mma na ụlọ ọrụ ọgwụ nwere ike irite uru site na ọsọ na-aga n'ihu7.
N'afọ ndị na-adịbeghị anya, enweela ọganihu na-eto eto nke otu dị iche iche na-achọ iji "reactors" kemịkalụ na-emegharị emegharị.Nhazi usoro, nrụpụta ngwa ngwa, na ike akụkụ atọ (3D) nke ụzọ ndị a bara uru maka ndị chọrọ ịhazi ngwaọrụ ha maka otu mmeghachi omume, ngwaọrụ, ma ọ bụ ọnọdụ.Ka ọ dị ugbu a, ọrụ a lekwasịrị anya n'ihe fọrọ nke nta ka ọ bụrụ naanị iji usoro obibi akwụkwọ 3D dabere na polymer dị ka stereolithography (SL) 9,10,11, Fused Deposition Modeling (FDM) 8,12,13,14 na inkjet printing7,15., 16. Enweghị ntụkwasị obi na ikike nke ngwaọrụ ndị dị otú ahụ iji mee ọtụtụ mmeghachi omume kemịkalụ / nyocha17, 18, 19, 20 bụ ihe na-amachi isi maka ngwa ngwa AM na mpaghara a17, 18, 19, 20.
N'ihi mmụba nke kemịkalụ na-asọpụta na ihe ndị dị mma jikọtara ya na AM, ọ dị mkpa ka enyocha usoro ka mma nke ga-enye ndị ọrụ ohere imepụta arịa mmeghachi omume na-asọpụta na kemịkalụ ka mma na ike nyocha.Ụzọ ndị a kwesịrị ikwe ka ndị ọrụ họrọ site na oke ike dị elu ma ọ bụ ihe arụ ọrụ nwere ike ịrụ ọrụ n'okpuru ọnọdụ mmeghachi omume dịgasị iche iche, yana ịkwado ụdị dị iche iche nke mmepụta ihe nyocha site na ngwaọrụ iji mee ka nlekota na ịchịkwa mmeghachi omume.
Otu ihe mgbakwunye n'ichepụta usoro nwere ike iji mepụta omenala chemical reactors bụ Ultrasonic Additive Manufacturing (UAM).Nke a siri ike-ala mpempe akwụkwọ usoro na-emetụta ultrasonic vibrations ka mkpa metal foils ijikọ ha ọnụ oyi akwa site oyi akwa na minimal volumetric kpo oku na a elu ogo nke plastic eruba 21, 22, 23. N'adịghị ka ọtụtụ ndị ọzọ AM teknụzụ, UAM nwere ike ozugbo Integrated na subtractive mmepụta, mara dị ka a ngwakọ n'ichepụta usoro, nke oge n'ime-n'ọnọdụ numerical akara (CNC) na-ekpebi oyi akwa nke 21, 22, 23. pụtara na onye ọrụ ahụ ejedebeghị na nsogbu ndị metụtara iwepụ ihe nrụpụta ụlọ mbụ sitere na obere ọwa mmiri mmiri, nke na-abụkarị ntụ ntụ na usoro mmiri AM26,27,28.Nnwere onwe imewe a gbatịkwara na nhọrọ nke ihe dịnụ - UAM nwere ike jikọta ngwakọta nke ihe ndị yiri ya na ihe ndị yiri ya n'otu usoro.Nhọrọ nke ngwakọta ihe karịrị usoro ịgbaze pụtara na a ga-emerịrị ihe ndị chọrọ n'ibu na kemịkalụ nke ngwa ụfọdụ.Na mgbakwunye na njikọ siri ike, ihe ọzọ na-eme na ultrasonic bonding bụ mmiri dị elu nke ihe plastik na obere okpomọkụ29,30,31,32,33.Akụkụ pụrụ iche nke UAM na-enye ohere ka etinye ihe ndị na-arụ ọrụ / thermal n'etiti ọkwa ígwè na-enweghị mmebi.Ihe mmetụta UAM agbakwunyere nwere ike ịkwado ịnyefe ozi ozugbo site na ngwaọrụ ahụ nye onye ọrụ site na nyocha agbakwunyere.
Ọrụ gara aga nke ndị ode akwụkwọ32 gosipụtara ike nke usoro UAM imepụta ihe owuwu microfluidic 3D dara dara na ikike nghọta agbakwunyere.Ngwaọrụ a bụ naanị maka nleba anya.Edemede a na-egosi ihe atụ mbụ nke igwe na-ahụ maka kemịkalụ microfluidic nke UAM rụpụtara, ngwaọrụ na-arụ ọrụ na-abụghị naanị njikwa kamakwa na-ebute njikọ kemịkalụ yana ihe nrụkọba nke catalytic.Ngwa ahụ na-ejikọta ọtụtụ uru jikọtara ya na nkà na ụzụ UAM n'imepụta ngwaọrụ kemịkalụ 3D, dị ka: ikike ịmegharị ihe nhazi 3D zuru ezu ozugbo site na ụdị kọmputa na-enyere aka (CAD) n'ime ngwaahịa;Nrụpụta ihe dị iche iche maka nchikota nke ịdị elu thermal conductivity na ihe catalytic, yana ihe mmetụta thermal agbakwunyere ozugbo n'etiti iyi ndị na-emeghachi omume maka njikwa ziri ezi na njikwa okpomọkụ mmeghachi omume.Iji gosi ọrụ nke reactor, ọbá akwụkwọ nke ọgwụ dị mkpa 1,4-disubstituted 1,2,3-triazole ogige bụ synthesized site ọla-catalyzed 1,3-dipolar Huisgen cycloaddition.Ọrụ a na-akọwapụta ka iji sayensị ihe na imepụta ihe na-enyere aka na kọmpụta nwere ike isi meghee ohere ọhụrụ na ohere maka kemịkalụ site na nyocha dị iche iche.
A zụtara ihe mgbaze na reagents niile n'aka Sigma-Aldrich, Alfa Aesar, TCI, ma ọ bụ Fischer Scientific ma jiri ya mee ihe n'ebughị ụzọ dị ọcha.1H na 13C NMR spectra nke edere na 400 na 100 MHz, n'otu n'otu, nwetara na JEOL ECS-400 400 MHz spectrometer ma ọ bụ Bruker Avance II 400 MHz spectrometer nwere CDCl3 ma ọ bụ (CD3) 2SO dị ka ihe mgbaze.Emere mmeghachi omume niile site na iji usoro kemịkalụ Uniqsis FlowSyn.
Ejiri UAM mepụta ngwaọrụ niile n'ime ọmụmụ ihe a.Emepụtara teknụzụ ahụ na 1999 yana nkọwa teknụzụ ya, paramita arụ ọrụ na mmepe ebe ọ bụ na enwere ike mụọ ya site na iji ihe ndị a ebipụtara34,35,36,37.Emebere ngwaọrụ ahụ (Fig 1) site na iji ọrụ dị arọ 9 kW SonicLayer 4000® UAM system (Fabrisonic, Ohio, USA).Ihe ndị a họọrọ maka ngwaọrụ eruba bụ Cu-110 na Al 6061. Cu-110 nwere ọdịnaya ọla kọpa dị elu (opekempe 99.9% ọla kọpa), na-eme ka ọ bụrụ ezigbo onye nyocha maka mmeghachi omume catalyzed ọla kọpa ma jiri ya mee ihe dị ka " oyi akwa na-arụ ọrụ n'ime microreactor.A na-eji Al 6061 O dị ka ihe "oke"., nakwa dị ka intercalation oyi akwa eji maka nyocha;intercalation nke inyeaka alloy components na annealed ala na Nchikota Cu-110 oyi akwa.chọpụtara na ọ kwụsiri ike na reagents eji arụ ọrụ a.Al 6061 O jikọtara ya na Cu-110 ka a na-ewerekwa na ọ bụ ngwakọta ihe na-adaba adaba maka UAM ma bụrụkwa ihe kwesịrị ekwesị maka ọmụmụ ihe a38,42.Edepụtara ngwaọrụ ndị a na tebụl 1 n'okpuru.
Usoro nrụpụta ihe nrụpụta (1) 6061 aluminum alloy substrate (2) imepụta ọwa ala sitere na foil ọla kọpa (3) Ntinye nke thermocouples n'etiti akwa (4) Ọwa elu (5) Ntinye na ntinye (6) Monolithic reactor.
Nkà ihe ọmụma imewe ọwa mmiri mmiri bụ iji ụzọ tortuous iji mee ka ogologo mmiri na-aga n'ime mgbawa ahụ ka ị na-ejigide nha mgbawa nwere ike ijikwa.Mmụba a dị anya bụ ihe na-achọsi ike iji mee ka oge kọntaktị na-emeghachi omume ma weta ezigbo ngwaahịa.Ihe ibe ahụ na-eji 90º na-ehulata na nsọtụ nke ụzọ kwụ ọtọ iji kpalite ngwakọta mgbagwoju anya n'ime ngwaọrụ44 wee mụbaa oge kọntaktị nke mmiri mmiri na elu (catalyst).Iji mee ka ngwakọta nke enwere ike nwetakwuo, nhazi nke reactor na-agụnye inlets abụọ reactant jikọtara na njikọ Y tupu abanye n'ime akụkụ eriri igwe.Ọnụ ụzọ nke atọ, nke na-agafe na ọkara nke ebe obibi ya, gụnyere na atụmatụ maka mmeghachi omume nhazi nke ọtụtụ ọkwa n'ọdịnihu.
Ọwa niile nwere profaịlụ square (enweghị akụkụ taper), nke bụ nsonaazụ nke igwe igwe CNC oge nke ejiri mepụta geometry ọwa.A na-ahọrọ akụkụ ọwa ahụ iji nye mkpụrụ dị elu (maka microreactor) volumetric, ma ọ dị ntakịrị iji kwado mmekọrịta na elu (ihe na-eme ka ọ dị elu) maka ọtụtụ mmiri mmiri dị n'ime ya.Ogo kwesịrị ekwesị dabere na ahụmịhe nke ndị ode akwụkwọ gara aga na ngwaọrụ mmeghachi mmiri nke igwe.Akụkụ dị n'ime nke ọwa ikpeazụ bụ 750 µm x 750 µm yana mkpokọta reactor bụ 1 ml.Njikọ arụnyere arụnyere (1/4 ″-28 UNF eri) gụnyere n'ime imewe ahụ iji mee ka ngwa kemịkalụ na-erugharị azụmahịa na-emekọrịta ngwa ngwa.Ogo nke ọwa na-ejedebe site na ọkpụrụkpụ nke ihe foil, ihe eji arụ ọrụ ya, na njikọ njikọ ejiri na ultrasonics.N'ebe ụfọdụ obosara maka ihe e nyere, ihe ahụ ga-abụ "sag" n'ime ọwa ahụ emepụtara.Enweghị ụdị ọ bụla akọwapụtara maka ngụkọ a ugbu a, yabụ a na-ekpebi obosara ọwa kachasị maka ihe enyere na imepụta ya na nnwale, nke obosara nke 750 µm agaghị eme ka sag.
A na-ekpebi ụdị (square) nke ọwa ahụ site na iji onye na-egbu osisi.Ụdị na nha nke ọwa nwere ike gbanwee na igwe CNC na-eji ngwá ọrụ ịkpụ dị iche iche iji nweta ọnụọgụ na njirimara dị iche iche.Enwere ike ịchọta ọmụmaatụ nke ịmepụta ọwa gbagọrọ agbagọ nwere ngwa 125 µm na Monaghan45.Mgbe a na-etinye akwa mkpuchi ahụ n'ụzọ dị larịị, ntinye nke ihe eji eme ihe na ọwa ga-enwe ebe dị larịị (square).N'ime ọrụ a, a na-eji contour square iji chekwaa ihe ngosi ọwa.
N'oge a na-akwụsịtụ na mmepụta, thermocouple okpomọkụ sensọ (ụdị K) na-wuru ozugbo na ngwaọrụ n'etiti elu na ala ọwa otu (Fig. 1 - ogbo 3).Igwe ọkụ ọkụ ndị a nwere ike ịchịkwa mgbanwe okpomọkụ site na -200 ruo 1350 Celsius.
A na-eji mpi UAM na-eme usoro ntinye igwe a na-eji ígwè foil 25.4 mm n'obosara na 150 microns.A na-ejikọta akwa mpempe akwụkwọ ndị a n'usoro nke dị n'akụkụ iji kpuchie ebe a na-ewu ụlọ dum;nha nke ihe nkwụnye ego buru ibu karịa ngwaahịa ikpeazụ ka usoro mwepu na-emepụta ọdịdị dị ọcha ikpeazụ.A na-eji machining CNC na-arụ ọrụ n'èzí na n'ime ime nke akụrụngwa, na-eme ka njedebe elu nke akụrụngwa na ọwa kwekọrọ na ngwaọrụ ahọpụtara na usoro usoro CNC (na ihe atụ a, ihe dị ka 1.6 µm Ra).Na-aga n'ihu, na-aga n'ihu ultrasonic ihe spraying na machining cycles na-eji n'oge usoro nrụpụta nke ngwaọrụ ahụ iji hụ na a na-edobe nha nha na akụkụ nke emechara na-ezute ọkwa CNC dị mma.Ogologo nke ọwa a na-eji maka ngwaọrụ a dị ntakịrị iji hụ na ihe foil adịghị "sag" na ọwa mmiri mmiri, ya mere ọwa ahụ nwere akụkụ cross square.Ndị mmekọ na-emepụta ihe (Fabrisonic LLC, USA).
Nnyocha egosiwo na na interface 46, 47 nke UAM compound na-enwe ntakịrị mgbasa nke ihe na-enweghị ọgwụgwọ okpomọkụ ọzọ, ya mere maka ngwaọrụ ndị dị na ọrụ a Cu-110 oyi akwa na-anọgide na-adị iche na Al 6061 oyi akwa na-agbanwe n'ụzọ dị ịrịba ama.
Wụnye onye na-ahụ maka nrụgide azụ azụ (BPR) na 250 psi (1724 kPa) na mgbada nke reactor wee gbapụta mmiri site na reactor na ọnụego 0.1 ruo 1 ml min-1.A na-enyocha nrụgide reactor site na iji FlowSyn pressure transducer arụnyere n'ime sistemụ ahụ iji hụ na sistemụ ahụ nwere ike ịnọgide na-enwe nrụgide mgbe niile.A nwalere gradients okpomọkụ nwere ike na reactor na-asọpụta site n'ịchọ ọdịiche ọ bụla n'etiti thermocouples arụnyere n'ime reactor na thermocouples arụnyere n'ime efere ọkụ nke FlowSyn mgbawa.A na-enweta nke a site n'ịgbanwe ọnọdụ okpomọkụ dị n'etiti 100 na 150 Celsius C na mmụba 25 Celsius C yana nyochaa ọdịiche ọ bụla dị n'etiti okpomọkụ akwadoro na nke edere.Emere nke a site na iji tc-08 data logger (PicoTech, Cambridge, UK) na ngwanro PicoLog so ya.
A na-emezi ọnọdụ maka mmeghachi omume cycloaddition nke phenylacetylene na iodoethane (Atụmatụ 1-Cycloaddition nke phenylacetylene na iodoethane, Atụmatụ 1-Cycloaddition nke phenylacetylene na iodoethane).Emere njikarịcha a site na iji usoro nnwale zuru oke nke nnwale (DOE), na-eji oge okpomọkụ na oge obibi dị ka mgbanwe mgbe a na-edozi oke alkyne: azide na 1: 2.
A kwadebere ihe ngwọta dị iche iche nke sodium azide (0.25 M, 4: 1 DMF: H2O), iodoethane (0.25 M, DMF), na phenylacetylene (0.125 M, DMF).A na-agwakọta aliquot 1.5 ml nke ihe ngwọta ọ bụla wee gbanye ya site na reactor n'ogo ọsọ na okpomọkụ achọrọ.A na-ewere nzaghachi nke ihe nlereanya ahụ dị ka oke mpaghara kachasị elu nke ngwaahịa triazole na mmalite nke phenylacetylene ma kpebisie ike site na iji chromatography mmiri mmiri dị elu (HPLC).Maka ngbanwe nyocha, a na-emeghachi mmeghachi omume niile ozugbo ngwakọta mmeghachi omume hapụrụ reactor.Egosiri oke oke ahọpụtara maka nkwalite ya na Tebụl 2.
A na-enyocha ihe nlele niile site na iji usoro Chromaster HPLC (VWR, PA, USA) nke nwere mgbapụta quaternary, oven kọlụm, ihe nchọta UV na-agbanwe agbanwe na autosampler.Kọlụm ahụ bụ nha nha 5 C18 (VWR, PA, USA), 4.6 x 100 mm, nha 5 µm, nke edobere na 40°C.Ihe mgbaze bụ methanol isocratic: mmiri 50:50 na ọnụego erute nke 1.5 ml·min-1.Olu ntụtụ ahụ bụ 5 μl na ogologo ogologo ihe nchọta bụ 254 nm.A gbakọrọ mpaghara % kacha elu maka nlele DOE site na mpaghara kacha elu nke ngwaahịa alkyne na triazole naanị.Ntinye nke ihe mmalite na-eme ka o kwe omume ịchọpụta ọnụ ọgụgụ ndị kwekọrọ.
Ijikọta nsonaazụ nke nyocha reactor na sọftụ MODDE DOE (Umetrics, Malmö, Sweden) kwere ka nyocha nke ọma nke nsonaazụ na mkpebi nke ọnọdụ mmeghachi omume kacha mma maka cycloaddition a.Na-agba ọsọ ngwa ngwa arụnyere na ịhọrọ usoro ihe atụ niile dị mkpa na-emepụta usoro mmeghachi omume emebere iji bulie mpaghara kacha elu nke ngwaahịa ahụ ka ọ na-ebelata ebe kacha elu maka nri nri acetylene.
A na-enweta oxidation nke elu ọla kọpa n'ime ụlọ mmeghachi omume catalytic site na iji ngwọta hydrogen peroxide (36%) na-agafe n'ime ụlọ mmeghachi omume (ọnụego ntinye = 0.4 ml min-1, oge obibi = 2.5 min) tupu njikọ nke ogige triazole ọ bụla.ụlọ akwụkwọ.
Ozugbo achọpụtara ọnọdụ kachasị mma, a na-etinye ha n'ụdị acetylene na haloalkane dị iche iche iji kwe ka nchịkọta nke obere ọbá akwụkwọ synthesis, si otú ahụ guzobe ohere nke itinye ọnọdụ ndị a n'ọtụtụ dịgasị iche iche nke reagents (Fig 1).2).
Kwadebe ngwọta dị iche iche nke sodium azide (0.25 M, 4: 1 DMF: H2O), haloalkanes (0.25 M, DMF), na alkynes (0.125 M, DMF).A na-agwakọta Aliquots nke 3 ml nke ngwọta nke ọ bụla ma fesa ya na reactor na ọnụego 75 µl / min yana okpomọkụ nke 150 ° C.A na-anakọta olu ahụ dum na vial ma jiri 10 ml nke ethyl acetate tinye ya.A na-eji mmiri 3 x 10 ml saa ihe nlele ahụ.A na-ejikọta akwa mmiri mmiri ma wepụ ya na 10 ml ethyl acetate, mgbe ahụ, a na-ejikọta ihe ndị dị na organic, na-asa ya na 3 × 10 ml brine, akpọnwụwo n'elu MgSO 4 ma kpochaa, mgbe ahụ, a na-ewepụ ihe mgbaze na vacuo.A na-asachapụ ihe nlele site na chromatography kọlụm silica gel site na iji ethyl acetate tupu nyocha site na nchikota HPLC, 1H NMR, 13C NMR na nnukwu spectrometry mass spectrometry (HR-MS).
Enwetara ụdịdị ụdịdị niile site na iji Thermofischer Precision Orbitrap mass spectrometer nwere ESI dị ka isi iyi ionization.A na-akwadebe ihe nlele niile site na iji acetonitrile dị ka ihe mgbaze.
A na-eme nyocha TLC na efere silica nwere mkpụrụ aluminom.E ji ọkụ UV (254 nm) ma ọ bụ ntụpọ vanillin na kpo oku gosi efere ndị ahụ.
A na-enyocha ihe nlele niile site na iji sistemu VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) nke nwere autosampler, mgbapụta ọnụọgụ abụọ nwere oven kọlụm na otu ihe nchọta ogologo ogologo.Ejiri kọlụm ACE Equivalence 5 C18 (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland).
A na-eme injections (5 µl) ozugbo site na ngwakọta mmeghachi omume crude diluted (1:10 dilution) wee nyochaa ya na mmiri: methanol (50:50 ma ọ bụ 70:30), ma e wezụga maka ụfọdụ ihe atụ na-eji 70:30 ihe mgbaze (nke a na-egosi dị ka kpakpando nọmba) na ọnụego nke 1.5 ml / min.A na-edebe kọlụm ahụ na 40 Celsius.Ogologo ogologo nke ihe nchọta bụ 254 nm.
A na-agbakọ mpaghara % kacha elu nke ihe nlele ahụ site na mpaghara kacha elu nke alkyne residual, ngwaahịa triazole naanị, na iwebata ihe mmalite mere ka o kwe omume ịchọpụta ọnụ ọgụgụ ndị kwekọrọ.
A na-enyocha ihe nlele niile site na iji Thermo iCAP 6000 ICP-OES.A kwadebere ụkpụrụ nhazi niile site na iji ọkọlọtọ 1000 ppm Cu na 2% nitric acid (SPEX Certi Prep).A na-akwado ụkpụrụ niile na ngwọta nke 5% DMF na 2% HNO3, na ihe nlele niile na-agbaze ugboro 20 na ngwọta nlele nke DMF-HNO3.
UAM na-eji ultrasonic metal welding dị ka usoro nke ịbanye na foil ígwè eji emepụta mgbakọ ikpeazụ.Ịgbado ọkụ nke ultrasonic na-eji ngwá ọrụ igwe na-ama jijiji (nke a na-akpọ mpi ma ọ bụ mpi ultrasonic) iji tinye nrụgide na foil / oyi akwa agbadoro ka ọ bụrụ nke a ga-ejikọta / na-ejikọta ya na mbụ site na ịma jijiji ihe.Maka ịrụ ọrụ na-aga n'ihu, sonotrode nwere ọdịdị cylindrical ma na-atụgharị n'elu ihe ahụ, na-ejikọta ebe niile.Mgbe etinyere nrụgide na ịma jijiji, oxides dị n'elu ihe nwere ike ịgbawa.Nrụgide mgbe niile na ịma jijiji nwere ike iduga mbibi nke ihe siri ike nke ihe 36.Mmekọrịta dị nso na okpomọkụ na nrụgide mpaghara na-eduga na njikọ siri ike na akụkụ ihe onwunwe;ọ nwekwara ike ịkwalite ịdị n'otu site n'ịgbanwe ike elu48.Ọdịdị nke usoro njikọ ahụ na-emeri ọtụtụ nsogbu ndị metụtara mgbanwe okpomọkụ na-agbaze na mmetụta okpomọkụ dị elu nke a kpọtụrụ aha na teknụzụ mmepụta ihe ndị ọzọ.Nke a na-enye ohere njikọ kpọmkwem (ntụgharị na-enweghị ngbanwe elu, ihe ndochi ma ọ bụ adhesives) nke ọtụtụ ihe dị iche iche n'ígwé dị iche iche n'ime otu ihe ejikọtara ọnụ.
Ihe nke abụọ dị mma maka CAM bụ ọkwa dị elu nke plastik a na-ahụ n'ime ihe ndị dị na ọla ọbụna na obere okpomọkụ, ya bụ n'okpuru ebe mgbaze nke ihe ọla.Nchikota ultrasonic vibrations na nrụgide na-eme ka ọkwa dị elu nke oke ala ọka na-akwagharị na recrystallization na-enweghị mmụba okpomọkụ dị ịrịba ama na omenala jikọtara ya na nnukwu ihe.N'oge a na-emepụta mgbakọ ikpeazụ, enwere ike iji ihe a mee ihe iji tinye ihe ndị na-arụ ọrụ na nke na-agafe agafe n'etiti akwa mkpuchi ígwè, oyi akwa site na oyi akwa.Ihe ndị dị ka eriri anya 49, mkwado 46, electronics 50 na thermocouples (ọrụ a) abanyela nke ọma n'ime ụlọ UAM iji mepụta mgbakọ na-arụ ọrụ na nke na-agafe agafe.
N'ime ọrụ a, ejiri ike ijikọ ihe dị iche iche yana ikike intercalation UAM iji mepụta microreactor dị mma maka njikwa okpomọkụ catalytic.
E jiri ya tụnyere palladium (Pd) na ihe ndị ọzọ na-eme ka ígwè na-emepụta ihe, Cu catalysis nwere ọtụtụ uru: (i) Akụ na ụba, Cu dị ọnụ ala karịa ọtụtụ ọla ndị ọzọ a na-eji na-eme ihe na-eme ka ọ bụrụ ihe na-adọrọ adọrọ maka ụlọ ọrụ kemịkalụ (ii) nsonso nke mmeghachi omume njikọ nke Cu-catalyzed cross-coupling na-agbasawanye na-egosi na ọ bụ ihe na-akwado, 5251 usoro mmeghachi omume na-adabere na Pd251,525. na-arụ ọrụ nke ọma na enweghị njikọ ndị ọzọ.Njikọ ndị a na-adịkarị mfe n'ụdị na adịghị ọnụ.ma ọ bụrụ na achọrọ, ebe ndị a na-eji Pd chemistry na-adịkarị mgbagwoju anya, dị oke ọnụ, na ikuku mmetụta (iv) Cu, karịsịa mara maka ikike ya ijikọ alkynes na njikọ, dị ka Sonogashira's bimetallic catalyzed coupling na cycloaddition with azides (pịa kemịkalụ) (v) Cu nwekwara ike ịkwalite arylation nke ụfọdụ nuclein-ụdị mmeghachi omume U.
N'oge na-adịbeghị anya, e gosipụtara ihe atụ nke heterogenization nke mmeghachi omume ndị a niile na ọnụnọ Cu (0).Nke a bụ n'ụzọ dị ukwuu n'ihi ụlọ ọrụ na-emepụta ọgwụ na nleba anya na-eto eto na mgbake na iji ígwè eme ihe55,56.
Mmeghachi omume cycloaddition nke 1,3-dipolar n'etiti acetylene na azide na 1,2,3-triazole, nke Huisgen buru ụzọ tụpụtara na 1960s57, a na-ewere dị ka mmeghachi omume ngosipụta synergistic.Ihe na-esi na 1,2,3 triazole iberibe bụ ihe na-adọrọ mmasị dị ka pharmacophore na nchọpụta ọgwụ n'ihi ngwa ngwa ha na-eji na-agwọ ọrịa dị iche iche 58 .
Mmeghachi omume a nwetara nlebara anya ọzọ mgbe Sharpless na ndị ọzọ webatara echiche nke "pịa kemistri"59.A na-eji okwu ahụ bụ "pịa kemistri" kọwaa mmeghachi omume siri ike na nhọrọ maka nchịkọta ngwa ngwa nke ogige ọhụrụ na ọba akwụkwọ nchịkọta na-eji heteroatomic bonding (CXC)60.Mkpesa sịntetik nke mmeghachi omume ndị a bụ n'ihi nnukwu mkpụrụ nke jikọtara ya na ha.ọnọdụ dị mfe, iguzogide oxygen na mmiri, na nkewa ngwaahịa dị mfe61.
Oge gboo 1,3-dipole Huisgen cycloaddition adịghị adaba n'ụdị "pịa kemistri".Otú ọ dị, Medal na Sharpless gosipụtara na ihe omume njikọ njikọ azide-alkyne na-enweta 107-108 na ọnụnọ Cu (I) ma e jiri ya tụnyere mmụba dị ịrịba ama na ọnụego nke 62,3-dipolar cycloaddition na-abụghị catalytic 62,63.Usoro mmeghachi omume a dị elu adịghị achọ ichebe otu ma ọ bụ ọnọdụ mmeghachi omume siri ike ma na-enye ihe fọrọ nke nta ka ọ bụrụ ngbanwe zuru oke na selectivity na 1,4-disubstituted 1,2,3-triazoles (anti-1,2,3-triazoles) na oge (Fig 3).
Nsonaazụ isometric nke cycloadditions Huisgen na-eme ka ọ bụrụ ọla kọpa.Cu (I) -catalyzed Huisgen cycloadditions na-enye naanị 1,4-disubstituted 1,2,3-triazoles, ebe Huisgen cycloadditions na-ekpo ọkụ na-enyekarị 1,4- na 1,5-triazoles a 1: 1 ngwakọta nke azole stereoisomers.
Ọtụtụ ụkpụrụ na-agụnye mbelata isi mmalite nke Cu(II), dị ka mbelata CuSO4 ma ọ bụ Cu(II)/Cu(0) ngwakọta na sodium salts.Tụnyere mmeghachi omume nchara nke igwe ndị ọzọ, iji Cu (I) nwere uru bụ isi nke ịdị ọnụ ala yana dị mfe ijikwa.
Ọmụmụ Kinetic na isotopic nke Worrell et al.65 egosila na n'ihe banyere ọdụ ụgbọ elu alkynes, abụọ nhata ọla kọpa na-etinye aka n'ịkwalite mmeghachi omume nke molekul ọ bụla gbasara azide.Usoro a na-atụ aro na-esi na mgbanaka ọla kọpa nwere akụkụ isii nke kpụrụ site na nhazi nke azide na σ-bonded ọla kọpa acetylide nwere ọla kọpa π-bonded dị ka ligand inye onyinye kwụsiri ike.A na-emepụta ihe mgbanaka ọla kọpa triazolyl n'ihi mgbanaka mgbanaka na-esote proton decomposition iji mepụta ngwaahịa triazole ma mechie okirikiri catalytic.
Ọ bụ ezie na a na-edekọ uru nke ngwaọrụ kemịkalụ na-asọpụta nke ọma, enweela ọchịchọ ijikọ ngwaọrụ nyocha n'ime usoro ndị a maka nleba anya usoro oge na situ66,67.UAM egosila na ọ bụ usoro dabara adaba maka imepụta na imepụta ihe nrụpụta 3D dị mgbagwoju anya sitere na ihe na-arụ ọrụ nke ọma, ihe na-eduzi thermally nwere ihe agbakwunyere ozugbo (Fig 4).
Aluminom-ọla kọpa eruba reactor arụpụtara site ultrasonic mgbakwunye n'ichepụta (UAM) na mgbagwoju esịtidem ọwa Ọdịdị, wuru na thermocouples na a catalytic mmeghachi omume ụlọ.Iji hụ ụzọ mmiri dị n'ime ahụ, a na-egosipụtakwa ihe nlere anya nke ejiri stereolithography mee.
Iji hụ na e mere reactors maka ọdịnihu organic Jeremaya mere, ihe mgbaze ga-n'enweghị ekpo ọkụ n'elu ha esi ebe;a na-anwale nrụgide na okpomọkụ.Nnwale nrụgide ahụ gosipụtara na usoro ahụ na-ejigide nrụgide siri ike ma na-adịgide adịgide ọbụna na nrụgide dị elu na usoro (1.7 MPa).A na-eme nyocha nke hydrostatic na okpomọkụ nke ụlọ site na iji H2O dị ka mmiri mmiri.
Ijikọ ihe arụrụ arụ (Njirimara 1) thermocouple na data data okpomọkụ gosiri na okpomọkụ okpomọkụ dị 6 Celsius C (± 1 Celsius C) n'okpuru ọnọdụ okpomọkụ nke emebere na usoro FlowSyn.Dị ka ọ na-adịkarị, mmụba nke 10 Celsius C na-eme ka mmeghachi omume mmeghachi omume okpukpu abụọ, ya mere ọdịiche okpomọkụ nke dị n'ogo ole na ole nwere ike ịgbanwe ọnụego mmeghachi omume nke ukwuu.Nke a dị iche bụ n'ihi na okpomọkụ na-efunahụ dum RPV n'ihi na elu thermal diffusivity nke ihe eji na-emepụta usoro.Igwe ọkụ a na-ekpo ọkụ na-adịgide adịgide, ya mere enwere ike iburu n'uche mgbe ị na-edozi akụrụngwa iji hụ na a na-enweta okpomọkụ ziri ezi ma tụọ n'oge mmeghachi omume.Ya mere, ngwá ọrụ nleba anya n'ịntanetị a na-eme ka njide siri ike nke okpomọkụ mmeghachi omume ma na-enye aka na njikarịcha usoro na mmepe nke ọnọdụ kachasị mma.Enwere ike iji ihe mmetụta ndị a chọpụta mmeghachi omume exothermic ma gbochie mmeghachi omume agbapụ na nnukwu usoro.
The reactor ewepụtara na akwụkwọ a bụ ihe atụ mbụ nke ngwa nke UAM technology na-emepụta nke kemịkalụ reactors na adreesị ọtụtụ isi adịghị ike ugbu a jikọtara AM / 3D mbipụta nke ndị a ngwaọrụ, dị ka: (i) Imeri kwuru nsogbu metụtara na nhazi nke ọla kọpa ma ọ bụ aluminum alloy (ii) mma esịtidem ọwa mkpebi tụnyere ntụ ntụ bed agbaze (PBF) ụzọ dị ka 6 nhọrọ agbaze laser agbaze ihe (PBF) usoro dị ka 6 Pow lesa agbaze ihe n'elu ala (PBF). ala nhazi okpomọkụ, nke mmemmem kpọmkwem ejikọta sensọ, nke na-agaghị ekwe omume na powder bed technology, (v) imeri ogbenye n'ibu Njirimara na uche nke polymer dabeere components dị iche iche nkịtị organic solvents17,19.
E gosipụtara arụmọrụ nke reactor site na usoro mmeghachi omume alkinazide cycloaddition nke ọla kọpa-catalyzed n'okpuru ọnọdụ na-aga n'ihu (Fig 2).The ultrasonic e biri ebi ọla kọpa reactor egosiri na fig.4 jikọtara ya na usoro mgbasa ozi azụmahịa ma jiri ya mee ihe na-emepụta akwụkwọ azide nke dị iche iche 1,4-disubstituted 1,2,3-triazoles na-eji mmeghachi omume okpomọkụ nke acetylene na alkyl otu halides n'ihu sodium chloride (Fig 3).Iji usoro na-aga n'ihu na-aga n'ihu na-ebelata nsogbu nchekwa nke nwere ike ibili na usoro nhazi, ebe mmeghachi omume a na-emepụta ihe dị n'etiti azide na-emeghachi omume na nke dị ize ndụ [317], [318].Na mbido, a na-emezi mmeghachi omume ahụ maka cycloaddition nke phenylacetylene na iodoethane (Atụmatụ 1 - Cycloaddition nke phenylacetylene na iodoethane) (lee Fig. 5).
(N'elu aka ekpe) Atụmatụ nhazi nke a na-eji ejikọta 3DP reactor n'ime usoro ntinye (n'elu aka nri) nke enwetara site na atụmatụ kachasị (nke dị ala) nke Huisgen 57 cycloaddition atụmatụ n'etiti phenylacetylene na iodoethane maka njikarịcha na igosi nhazi ọnụego mgbanwe kachasị mma nke mmeghachi omume.
Site n'ịchịkwa oge obibi nke ndị na-emegharị ihe na ngalaba catalytic nke reactor ma jiri nlezianya na-enyocha okpomọkụ mmeghachi omume na ihe mmetụta thermocouple agbakwunyere ozugbo, ọnọdụ mmeghachi omume nwere ike ịme ngwa ngwa na nke ọma na obere oge na ihe.Achọpụtara ngwa ngwa na ntụgharị kachasị elu bụ site na iji oge obibi nke 15 nkeji na mmeghachi omume okpomọkụ nke 150 ° C.Enwere ike ịhụ site na ọnụọgụ ọnụọgụ nke sọftụwia MODDE na ma oge obibi na okpomọkụ mmeghachi omume ka a na-ewere ọnọdụ dị mkpa nke ihe nlereanya ahụ.Iji ọnọdụ ndị a ahọpụtara na-agba ọsọ ngwa ngwa arụnyere n'ime ya na-emepụta usoro mmeghachi omume emebere iji bulie mpaghara ọnụ ahịa ngwaahịa ka ọ na-ebelata ebe mmalite ihe kacha elu.Nkwalite a rụpụtara ngbanwe 53% nke ngwaahịa triazole, nke dabara na amụma ihe nlereanya ahụ nke 54%.