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Mgbakwunye n'ichepụta na-agbanwe ụzọ na-eme nnyocha na industrialists chepụta na-arụpụta chemical ngwaọrụ izute ha kpọmkwem mkpa.In ọrụ a, anyị na-akọ mbụ ihe atụ nke a eruba reactor kpụrụ site siri ike-ala metal mpempe akwụkwọ lamination Usoro Ultrasonic Additive Manufacturing (UAM) na kpọmkwem Integrated catalytic akụkụ na sensing element.Ọ bụghị nanị na UAM technology imeri ọtụtụ n'ime adịghị ike ugbu a jikọtara ya na mgbakwunye, ma kemịkalụ reactors nke dị otú ahụ na-abawanye nke ukwuu usoro nke usoro nke chemical reactors. Ihe dị mkpa dị mkpa nke 1,4-disubstituted 1,2,3-triazole ogige na-arụ ọrụ nke ọma ma kwalite ya site na mmeghachi omume Cu-mediated Huisgen 1,3-dipolar cycloaddition mmeghachi omume site na iji UAM chemistry set-up. Site n'iji ihe pụrụ iche nke UAM na nhazi na-aga n'ihu na-aga n'ihu, ngwaọrụ ahụ na-enwe ike ịmepụta nzaghachi na-aga n'ihu na nzaghachi na-aga n'ihu.
N'ihi na ya ịrịba uru n'elu ya nnukwu counterpart, eruba kemịkalụ bụ ihe dị mkpa na-eto eto ubi na ma agụmakwụkwọ na ulo oru ntọala n'ihi ya ike dịkwuo selectivity na arụmọrụ nke chemical synthesis.This gbatịrị si mfe organic molekul formation1 ka ọgwụ ogige2,3 na eke ngwaahịa4,5,6. Ihe karịrị 50% mmeghachi omume na kemịkalụ dị mma na ụlọ ọrụ ọgwụ nwere ike irite uru site na iji nhazi nhazi na-aga n'ihu7.
N'ime afọ ndị na-adịbeghị anya, e nwere a na-eto eto na-emekarị nke otu na-achọ iji dochie omenala glassware ma ọ bụ eruba kemịkalụ akụrụngwa na customizable mmako n'ichepụta (AM) chemistry "reaction arịa"8.The iterative imewe, ngwa ngwa mmepụta, na 3-dimensional (3D) ike nke usoro ndị a bara uru n'ihi na ndị chọrọ hazie ha ngwaọrụ ka a kpọmkwem set nke mmeghachi omume, ụbọchị, ma ọ bụ polymer dabeere na ọnọdụ na-eji ihe fọrọ nke nta ka ọ rụọ ọrụ. Usoro obibi akwụkwọ 3D dị ka stereolithography (SL) 9,10,11, fused deposition modeling (FDM) 8,12,13,14 na inkjet printing 7, 15, 16. Enweghi ike na ikike nke ngwaọrụ ndị dị otú ahụ iji rụọ ọrụ dịgasị iche iche nke mmeghachi omume kemịkalụ / nyocha 17, 19, 01 nke ukwuu na njedebe AM nke a bụ njedebe nke ukwuu. ubi17, 18, 19, 20 .
N'ihi na-amụba ojiji nke eruba kemịkalụ na mma Njirimara metụtara AM, e nwere mkpa inyocha ọzọ elu usoro na-enyere ndị ọrụ na-emepụta eruba mmeghachi omume arịa na enwekwukwa chemical na analytical capabilities.These usoro kwesịrị ime ka ndị ọrụ họrọ si a nso nke ukwuu siri ike ma ọ bụ arụ ọrụ ihe ike nke na-ejizi a dịgasị iche iche nke mmeghachi omume ọnọdụ, ma na-kwado dị iche iche mmepụta si na ngwaọrụ na-ekwe ka mmepụta ụdị na nyocha.
Otu mmako n'ichepụta usoro nke nwere ikike ịzụlite omenala chemical reactors bụ Ultrasonic Additive Manufacturing (UAM) .This siri ike-ala mpempe akwụkwọ lamination Usoro na-emetụta ultrasonic oscillations ka mkpa metal foils ka isonyere ha ọnụ oyi akwa site oyi akwa na minimal nnukwu kpo oku na a elu ogo nke plastic eruba 21 , 22 , 23 .N'adịghị ka ọtụtụ ndị ọzọ na-arụ ọrụ hybri nwere ike ịbụ n'ichepụta teknụzụ AM, n'adịghị ka ọtụtụ ndị ọzọ AM n'ichepụta teknụzụ, . usoro, nke in-situ periodic kọmputa numerical control (CNC) egwe ọka ma ọ bụ laser machining na-akọwa net udi nke a oyi akwa nke bonded ihe 24, 25. Nke a pụtara na onye ọrụ na-adịghị ejedebeghị site na nsogbu ndị metụtara wepụ ihe fọdụrụ raw ewu ihe site na obere mmiri mmiri ọwa, nke na-abụkarị ikpe na ntụ ntụ na mmiri mmiri AM Systems26,27,28 - Nke a imewe nhọrọ nwekwara ike ịgbatị ihe onwunwe UAM na nnwere onwe nke nwere ike ịgbatị ihe onwunwe UAM. dissimilar ihe nchikota na otu usoro step.The oke nke ihe nchikota n'ofè gbazee usoro pụtara na n'ibu na kemịkalụ chọrọ nke kpọmkwem ngwa nwere ike mma izute.In mgbakwunye na siri ike steeti bonding, ọzọ onu zutere n'oge ultrasonic bonding bụ elu eruba nke plastic ihe na dịtụ ala okpomọkụ29,30,31,32,33.Nke a pụrụ iche atụmatụ nke UAM / embed metal mebiri emebi ihe dị n'etiti igwe ihe mmetụta nke UAM nwere ike ikwado na-enweghị n'ihi na embeded metal. nwere ike ikwado ịnyefe ozi ozugbo site na ngwaọrụ gaa na onye ọrụ site na nyocha agbakwunyere.
Ọrụ ndị na-ede akwụkwọ gara aga32 gosipụtara ikike nke usoro UAM iji mepụta ihe owuwu microfluidic 3D dị mma na ikike nghọta jikọtara ọnụ. Nke a bụ ngwaọrụ nlekota naanị. Akwụkwọ a na-egosi ihe atụ mbụ nke microfluidic chemical reactor nke UAM mere; ngwaọrụ na-arụ ọrụ nke na-abụghị nanị na-enyocha kamakwa na-eme ka njikọ kemịkal na-emepụta ihe site na ihe ndị na-emepụta ihe na-emepụta ihe. Ngwa ahụ na-ejikọta ọtụtụ uru jikọtara ya na nkà na ụzụ UAM na 3D chemical ngwaọrụ n'ichepụta, dị ka: ikike iji tọghata zuru ezu 3D aghụghọ kpọmkwem site na kọmputa-enyere imewe (CAD) ụdị n'ime ngwaahịa; ọtụtụ ihe na-emepụta ihe iji jikọta elu okpomọkụ conductivity na catalytic ihe; na embedding thermal sensọ ozugbo n'etiti reagent iyi maka kpọmkwem mmeghachi omume okpomọkụ nlekota na control.To igosi na ọrụ nke chernobyl, a ọbá akwụkwọ nke pharmaceutically mkpa 1,4-disubstituted 1,2,3-triazole ogige e synthesized site ọla kọpa-catalyzed Huisgen 1,3-dipolar cycloadization ihe na-eme ka kọmputa na-eme ka nkà mmụta sayensị pụta ìhè na-arụ ọrụ nkà mmụta sayensị. kwalite ohere na ohere ọhụrụ maka kemistri site na nyocha multidisciplinary.
A zụrụ ihe mgbaze niile na reagents n'aka Sigma-Aldrich, Alfa Aesar, TCI ma ọ bụ Fischer Scientific ma jiri ya mee ihe n'ebughị ụzọ mee ka ọ dị ọcha. CDCl3 ma ọ bụ (CD3)2SO dị ka ihe mgbaze. Emere mmeghachi omume niile site na iji Uniqsis FlowSyn flow chemistry platform.
A na-eji UAM na-emepụta ngwaọrụ niile n'ime ọmụmụ ihe a. A na-emepụta nkà na ụzụ na 1999, na nkọwa nkà na ụzụ ya, ihe ndị na-arụ ọrụ na mmepe ebe ọ bụ na e nwere ike mụọ ya site na ihe ndị a na-ebipụta 34,35,36,37. A na-emejuputa ngwaọrụ ahụ site na iji ike ultra-high, 9kW SonicLayer 4000s® USA, usoro ihe eji eme ihe maka usoro OAM. eruba ngwaọrụ ndị Cu-110 na Al 6061.Cu-110 nwere nnukwu ọla kọpa ọdịnaya (opekempe 99.9% ọla kọpa), na-eme ka ọ bụrụ ezigbo nwa akwukwo maka ọla kọpa-catalyzed mmeghachi omume, na ya mere eji dị ka ihe "ọrụ oyi akwa n'ime a microreactor. Al 6061 O na-eji dị ka a" nnukwu "ihe onwunwe, nakwa Embedding oyi akwa a na-eji na-eme ihe niile embeoy ọnọdụ na analysis; Cu-110 Layer n'okpuru.
Usoro nrụpụta ihe nrụpụta (1) Al 6061 mkpụrụ (2) imepụta ọwa ala ka edobere ka ọ bụrụ ọla kọpa (3) Ntinye nke thermocouples n'etiti ọkwa (4) Ọwa kachasị (5) Ntinye na ntinye (6) Monolithic reactor.
Nkà ihe ọmụma nke imewe nke mmiri mmiri ụzọ bụ iji a convoluted ụzọ mee ka mmiri dị anya na-ejegharị n'ime mgbawa, mgbe na-edebe mgbawa na a njikwa size. Nke a na-abawanye na anya na-achọsi ike na-amụba catalyst / reagent mmekọrịta oge na-enye magburu onwe ngwaahịa na-amịpụta.The ibe na-eji 90 ° ehulata na nsọtụ nke ụzọ kwụ ọtọ na-eme ka ọgba aghara nke oge 4 na-amụba na kọntaktị n'ime ngwaọrụ. n'ihu dịkwuo Ịgwakọta nke nwere ike nweta, ndị reactor imewe atụmatụ abụọ reagent inlets jikọtara na Y-junction tupu abanye serpentine Ịgwakọta ngalaba. Nke atọ mbata, nke intersects iyi nke ọkara site na ebe obibi ya, gụnyere na imewe nke ga-eme n'ọdịnihu multistep mmeghachi omume syntheses.
Ọwa niile nwere profaịlụ square (enweghị akụkụ akụkụ), nsonaazụ nke igwe igwe CNC nke oge a na-eji mepụta geometry ọwa. A na-ahọrọ akụkụ ọwa iji hụ na mmepụta olu dị elu (maka microreactor), ebe ọ bụ obere iji kwado mmekọrịta elu (catalysts) maka ọtụtụ mmiri mmiri dị n'ime ya. nha kwesịrị ekwesị dabere na ahụmịhe ndị ode akwụkwọ gara aga na ọwa igwe-fluidic nke 7 bụ ihe mmeghachi omume nke 7. x 750 µm na mkpokọta reactor olu bụ 1 ml. Njikọ agbakwunyere (1/4″ — 28 UNF eri) gụnyere n'ime imewe iji mee ka ngwa ngwa kemịkalụ na-eruba na-emekọrịta ihe. Ogo nke ọwa na-ejedebe site na ọkpụrụkpụ nke ihe foil, ihe eji arụ ọrụ ya, na njikọ njikọ ejiri na ultrasonics. N'otu obosara dị iche iche maka ihe e nyere, ihe ahụ "ga-adaba" n'ime ọwa ahụ e kere eke. E nwere ugbu a ọ dịghị kpọmkwem ihe nlereanya maka nke a ngụkọta oge, otú kacha ọwa obosara maka a nyere ihe na imewe kpebisiri ike experimentally; na nke a, obosara nke 750 μm agaghị eme ka sag.
A na-ekpebi ụdị (square) nke ọwa site na iji onye na-egbu osisi square. Ụdị na nha nke ọwa nwere ike gbanwee site na igwe CNC na-eji ngwá ọrụ ịkpụ dị iche iche iji nweta ọnụọgụ na njirimara dị iche iche. Ihe atụ nke ịmepụta ọwa nke na-agbagharị agbagharị na-eji 125 μm ngwá ọrụ nwere ike ịchọta ọrụ nke Monaghan45. Mgbe a na-etinye akwa oyi akwa n'ime ihe eji eme ihe n'elu ọwa nke ejiji ga-enwe ihe eji eme ihe n'elu ihe eji eme ihe eji eme ihe (planar foil). imecha. N'ọrụ a, iji nọgide na-enwe symmetry nke ọwa ahụ, a na-eji ihe ngosi square mee ihe.
N'oge a na-eme atụmatụ nkwụsịtụ n'ichepụta, thermocouple okpomọkụ nyocha (Ụdị K) na-agbanye ozugbo n'ime ngwaọrụ n'etiti otu ọwa elu na nke dị ala (Nyocha 1 - Nkeji 3) Ndị a thermocouples nwere ike nyochaa mgbanwe okpomọkụ site na -200 ruo 1350 Celsius.
A na-eme usoro ntinye nke ígwè site na mpi UAM na-eji 25.4 mm n'obosara, 150 micron nnukwu mpempe akwụkwọ. nha nke ihe nkwụnye ego buru ibu karịa ngwaahịa ikpeazụ dị ka usoro nkwụsịtụ na-emepụta ihe ntanetị ikpeazụ. A na-eji machining CNC na-emepụta ihe na-emepụta ihe na-emepụta ihe na-emepụta ihe na-emepụta ihe na-emepụta ihe na-emepụta ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-emepụta ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ngwá ọrụ na ọwa dị nhata na ngwá ọrụ ahọrọ na CNC usoro parameters (ihe dị ka 1.6 μm Rat na ihe atụ a) .Na-aga n'ihu, na-aga n'ihu na-eji ngwaọrụ ultrasonic na-emepụta ihe ziri ezi na nhazi usoro nhazi oge niile. na-nọgidere na okokụre akụkụ ga-ezute CNC imecha egwe ọka ziri ezi ọkwa.The ọwa obosara eji maka ngwaọrụ a bụ obere iji hụ na foil ihe adịghị "sag" n'ime mmiri mmiri ọwa, otú ọwa na-ekwusi a square cross-section.Possible gaps na foil ihe na UAM usoro parameters e kpebisiri ike experimentally site a n'ichepụta ibe (Fabrisonic LLC, USA).
Nnyocha egosiwo na obere mgbasa ozi elemental na-eme na UAM bonding interface 46, 47 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 na mberede.
Wụnye pre-calibrated 250 psi (1724 kPa) back pressure regulator (BPR) na ntinye nke reactor na mgbapụta mmiri site na reactor na ọnụego nke 0.1 ka 1 mL min-1. A na-enyocha nrụgide na-arụ ọrụ site na iji FlowSyn wuru n'ime usoro nrụgide ihe mmetụta iji chọpụta na usoro ahụ nwere ike ịnọgide na-enwe nrụgide na-aga n'ihu na-eme ka okpomọkụ na-aga n'ihu. na-achọpụta ihe ọ bụla dị iche n'etiti thermocouples agbakwunyere n'ime reactor na ndị agbakwunyere n'ime FlowSyn mgbawa kpo oku efere. Nke a na-enweta site n'ịgbanwe na programmable hotplate okpomọkụ n'etiti 100 na 150 Celsius C na 25 Celsius C increments na-achọpụta ihe ọ bụla dị iche n'etiti mmemme na ndekọ okpomọkụ. Nke a na-enweta site na iji a lochgger (Pccony UK) data na Techgger (Pcccony UK). PicoLog software.
A na-emezi ọnọdụ mmeghachi omume cycloaddition nke phenylacetylene na iodoethane (Atụmatụ 1-Cycloaddition of phenylacetylene na iodoethane Scheme 1- Cycloaddition of phenylacetylene na iodoethane) Nke a kacha mma rụrụ site a zuru factorial imewe nke nnwale (DOE) na-abịaru nso dị ka okpomọkụ na-abịaru nso dị ka okpomọkụ factorial imewe nke nnwale (DOE). na 1:2.
A na-akwadebe 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 1.5 mL aliquot nke ọ bụla ngwọta na-agwakọta na pumped site reactor na ihe nlereanya eruba ọnụego na okpomọkụ nke triazole. phenylacetylene mmalite ihe ma kpebisie ike site na elu arụmọrụ chromatography mmiri mmiri (HPLC) .N'ihi na agbanwe agbanwe nke analysis, niile mmeghachi omume e sampled nanị mgbe mmeghachi omume ngwakọta hapụrụ reactor. The parameter ranges ahọrọ maka njikarịcha na-egosi na Isiokwu 2.
All samples e nyochara iji a Chromaster HPLC usoro (VWR, PA, USA) esịnede a quaternary mgbapụta, kọlụm oven, variable wavelength UV detector na autosampler.The kọlụm bụ ihe nhata 5 C18 (VWR, PA, USA), 4.6 × 100 mm na size, 5 µm . 50:50 methanol: mmiri na a eruba ọnụego nke 1.5 mL.min-1.The injection olu bụ 5 µL na detector wavelength bụ 254 nm. The% elu ebe maka DOE sample e gbakọọ si n'ọnụ ọnụ ebe nke residual alkyne na triazole ngwaahịa naanị.Injection nke mmalite ihe dị mkpa na-enye ohere ident.
Njikọta mmepụta nyocha nke reactor na software MODDE DOE (Umetrics, Malmö, Sweden) kwere ka nyocha nke ọma nke usoro nsonaazụ na mkpebi siri ike nke ọnọdụ mmeghachi omume kachasị mma maka cycloaddition a. Ịgba ọsọ na-arụ ọrụ na-arụ ọrụ na ịhọrọ usoro ihe nlereanya niile dị mkpa na-ewepụta usoro mmeghachi omume nke e mere iji mee ka ebe kachasị elu nke ngwaahịa dị elu mgbe ị na-ebelata ebe mmalite nke acety.
A na-enweta oxidation nke ọla kọpa n'elu n'ime ụlọ mmeghachi omume catalytic site na iji ngwọta nke hydrogen peroxide (36%) na-asọfe site na ọnụ ụlọ mmeghachi omume (ọnụego ntinye = 0.4 mL min-1, oge obibi = 2.5 min) tupu njikọ nke ọbá akwụkwọ triazole ọ bụla.
Ozugbo achọpụtara ọnọdụ kachasị mma, a na-etinye ha n'ụdị acetylene na haloalkane dị iche iche iji kwe ka nchịkọta nke obere ụlọ akwụkwọ ọbá akwụkwọ, si otú a na-eme ka ikike itinye ọnọdụ ndị a n'ọtụtụ dịgasị iche iche nke reagents (Nyocha 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) .3 mL aliquots nke ihe ngwọta ọ bụla e gwakọtara na pumped site na reactor na 75 µL.min-1 na 150 Celsius C na-anakọta na ngụkọta nke vilu. mL nke ethyl acetate. A na-asacha ihe nlele ahụ na mmiri 3 × 10. A na-ejikọta akwa mmiri na-ekpo ọkụ ma wepụ ya na 10 ml nke ethyl acetate; Mgbe ahụ, a na-ejikọta akwa akwa organic, na-asa ya na 3 x 10 mL nke brine, nke a mịrị amị n'elu MgSO4 ma kpochaa, mgbe ahụ, a na-ewepụ ihe mgbaze na vacuo. A na-ehichapụ ihe nlele ahụ site na kọlụm chromatography na silica gel site na iji ethyl acetate tupu nyocha site na nchikota HPLC, 1H NMR, 13C NMR na nnukwu mkpebi HR-MS.
Enwetara ụdịdị ụdịdị niile site na iji Thermofischer precision Orbitrap mkpebi mass spectrometer nwere ESI dị ka isi iyi ionization. A na-eji acetonitrile kwadebere ihe nlele niile dịka ihe mgbaze.
A na-eme nyocha TLC na efere silica na-akwado aluminom. A na-ahụta efere site na ìhè UV (254 nm) ma ọ bụ vanillin ntụpọ na kpo oku.
A na-enyocha ihe nlele niile site na iji usoro VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) nke nwere autosampler, kọlụm oven oven binary pump and one wavelength detector.The kọlụm eji bụ ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland).
Injections (5 µL) e mere kpọmkwem site diluted crude mmeghachi omume ngwakọta (1:10 dilution) na nyochaa na mmiri: methanol (50:50 ma ọ bụ 70:30), ma e wezụga n'ihi na ụfọdụ samples iji 70:30 ihe mgbaze usoro (pụtara dị ka kpakpando nọmba) na eruba ọnụego nke 1.5 mL / min. The kọlụm na-na-40 C. nm.
A na-agbakọ mpaghara % kacha elu nke ihe nlele ahụ site na mpaghara kacha elu nke alkyne fọdụrụnụ, naanị ngwaahịa triazole, yana ntụtụ nke ihe mmalite nyere ohere ka amata ọnụ ọgụgụ dị mkpa.
A na-enyocha ihe nlele niile site na iji Thermo iCAP 6000 ICP-OES. A na-akwado ụkpụrụ nhazi niile site na iji 1000 ppm Cu ọkọlọtọ ngwọta na 2% nitric acid (SPEX Certi Prep) .A na-akwado ụkpụrụ niile na 5% DMF na 2% HNO3 ngwọta, na ihe nlele niile na-agbaze 200.
UAM na-eji ultrasonic metal ịgbado ọkụ dị ka a bonding Usoro maka metal foil ihe eji wuo ikpeazụ mgbakọ.Ultrasonic metal ịgbado ọkụ utilizes a vibrating metal ngwá ọrụ (a na-akpọ mpi ma ọ bụ ultrasonic mpi) na-etinye nrụgide na foil oyi akwa / mbụ consolidated oyi akwa ka bonded mgbe ịma jijiji na material.N'ihi na-aga n'ihu na-arụ ọrụ, na sonotrode na-aga n'ihu na-arụ ọrụ n'elu cylin n'elu ebe cylin. na vibration na-etinyere, oxides n'elu nke ihe nwere ike ịgbawa. Ịga n'ihu na nrụgide na vibration nwere ike ime ka asperities nke ihe na-ada 36 .Mmetụta mmekọrịta chiri anya na mpaghara na-ebute okpomọkụ na nrụgide mgbe ahụ na-eduga ná njikọ siri ike-ala na ntanetị ihe; ọ nwekwara ike inye aka adhesion site mgbanwe na elu energy48.The ọdịdị nke bonding usoro merie ọtụtụ n'ime nsogbu ndị metụtara na agbanwe agbaze okpomọkụ na elu okpomọkụ mgbe-mmetụta kwuru na ndị ọzọ mmako n'ichepụta techniques.This na-enye ohere maka kpọmkwem bonding (ie, na-enweghị elu mgbanwe, fillers ma ọ bụ adhesives) nke otutu n'ígwé nke dị iche iche ihe n'ime otu consolidated Ọdịdị.
A abụọ mma ihe maka UAM bụ elu ogo nke plastic eruba hụrụ na dara ihe, ọbụna na ala okpomọkụ, ie ọma n'okpuru agbaze ebe nke dara material.The Nchikota ultrasonic oscillation na nrụgide induces elu etoju nke obodo ọka ókè Mbugharị na recrystallization na-enweghị nnukwu okpomọkụ na-abawanye omenala jikọtara na nnukwu material.N'oge na-ewu nke ikpeazụ mgbakọ, nke a na-arụ ọrụ oyi akwa nwere ike ịgafe n'etiti ihe na-arụsi ọrụ ike oyi akwa n'etiti ndị na-arụ ọrụ n'ikuku na-arụ ọrụ na-eme njem n'etiti ihe na-arụsi ọrụ ike na-eme njem n'etiti ihe na-arụ ọrụ oyi akwa n'etiti phenomenon. metal foil, oyi akwa site oyi akwa.Elements dị ka ngwa anya emep uta eri 49, reinforcements 46, electronics 50, na thermocouples (ọrụ a) niile e ọma agbakwunyere n'ime UAM Ọdịdị ike na-arụsi ọrụ ike na-agafe agafe mejupụtara mgbakọ.
N'ime ọrụ a, ejirila ma ihe jikọrọ ihe dị iche iche yana ohere ịmekọrịta nke UAM iji mepụta microreactor na-ahụ maka ọnọdụ okpomọkụ kacha mma.
E jiri ya tụnyere palladium (Pd) na ihe ndị ọzọ na-emepụta ígwè na-ejikarị eme ihe, Cu catalysis nwere ọtụtụ uru: (i) Akụ na ụba, Cu dị ọnụ ala karịa ọtụtụ ọla ndị ọzọ a na-eji na-emepụta ihe na ya mere nhọrọ mara mma maka ụlọ ọrụ nhazi kemịkalụ (ii) Ọnụ ọgụgụ nke mmeghachi omume njikọ nke Cu-catalyzed cross-coupling na-abawanye ma na-egosi na ọ bụ ihe na-akwado Pd53 (551) Mmeghachi omume Cu-catalyzed na-arụ ọrụ nke ọma na enweghị njikọ ndị ọzọ, Njikọ ndị a na-adịkarị mfe nhazi na ọnụ ala ma ọ bụrụ na achọrọ ya, ebe ndị a na-eji na Pd chemistry na-adịkarị mgbagwoju anya, dị oke ọnụ, na ikuku-sensitive (iv) Cu, karịsịa maka ike ijikọta alkynes na synthesis, Dịka ọmụmaatụ, bimetallic-catalyzed Sonogashirazid. (v) Cu nwekwara ike ịkwalite arylation nke ọtụtụ nucleophiles na mmeghachi omume ụdị Ullmann.
Ihe atụ nke heterogenization nke mmeghachi omume ndị a niile ka egosipụtara n'oge na-adịbeghị anya n'ihu Cu (0) .Nke a bụ n'ụzọ dị ukwuu n'ihi ụlọ ọrụ na-emepụta ọgwụ na mmụba na-elekwasị anya na mgbake metal catalyst mgbake na reuse55,56.
Ọsụ ụzọ Huisgen na 1960s57, 1,3-dipolar cycloaddition mmeghachi omume n'etiti acetylene na azide ka 1,2,3-triazole a na-ewere a synergistic ngosi mmeghachi omume.The pụta 1,2,3 triazole moieties bụ nke akpan akpan mmasị dị ka pharmacophore na ubi nke ọgwụ nchoputa ngwa dị iche iche nke 8.
Mmeghachi omume a bịara na-elekwasị anya ọzọ mgbe Sharpless na ndị ọzọ webatara echiche nke "click chemistry" 59. A na-eji okwu ahụ bụ "click chemistry" akọwa usoro mmeghachi omume siri ike, nke a pụrụ ịdabere na ya na nke nhọrọ maka ngwa ngwa ngwa ngwa nke ogige ọhụrụ na ụlọ akwụkwọ combinatorial site na heteroatom linkage (CXC) 60 The synthetic mkpesa nke ihe ndị a mmeghachi omume, oxygen na-esi na ya pụta, mmeghachi omume dị mfe na ọnọdụ ndị a, mmeghachi omume oxygen na-esi na ya pụta. nkewa dị mfe61.
The oge gboo Huisgen 1,3-dipole cycloaddition esoghị na udi nke "click chemistry" Otú ọ dị, Medal na Sharpless gosipụtara na nke a azide-alkyne njikọ ihe omume na-enweta 107 ka 108 na ọnụnọ nke Cu (I) tụnyere uncatalyzed 1,3-dipolar 6 usoro mmeghachi omume accedled. Achọghị ichebe otu ma ọ bụ ọnọdụ mmeghachi omume siri ike ma na-amịpụta nso ngbanwe zuru oke na nhọrọ na 1,4-disubstituted 1,2,3-triazoles (anti- 1,2,3-triazole) n'ogo oge (Nyocha 3).
Nsonaazụ nke isometric nke omenala na ọla kọpa-catalyzed Huisgen cycloadditions.Cu (I) -catalyzed Huisgen cycloadditions na-enye naanị 1,4-disubstituted 1,2,3-triazoles, ebe Huisgen cycloadditions nke na-ekpo ọkụ na-emepụta 1,4- na 1,5-triazoles.
Ọtụtụ usoro iwu gụnyere mbelata isi mmalite Cu (II), dị ka mbelata CuSO4 ma ọ bụ Cu (II)/Cu(0) ụdị njikọ na sodium salts. Tụnyere mmeghachi omume metal-catalyzed ndị ọzọ, ojiji nke Cu (I) nwere uru bụ isi nke ịbụ ọnụ ala ma dị mfe ijikwa.
Kinetic na isotopic labeling ọmụmụ nke Worrell et al. 65 gosiri na, n'ihe banyere ọnụ alkynes, abụọ nhata ọla kọpa na-etinye aka na ịgbalite reactivity nke molekul ọ bụla kwupụta azide. Usoro a tụrụ aro na-enweta site na mgbanaka ọla kọpa isii nwere akụkụ isii nke kpụrụ site na nchikota nke azide na σ-bonded ọla kọpa acetylide na π-bonded ọla dị ka a kwụsiri ike Donor ligazone. Mbelata, na-esote proton decomposition iji nye ngwaahịa triazole ma mechie okirikiri catalytic.
Ezie na uru nke eruba kemịkalụ ngwaọrụ na-ọma akwụkwọ, e nwere a ọchịchọ iwekota analytical ngwaọrụ n'ime ndị a usoro maka in-line, na-n'ọnọdụ, usoro monitoring66,67.UAM gosiri na-a dabara adaba usoro maka emebe na-amị ukwuu mgbagwoju 3D eruba reactors mere nke catalytically arụ ọrụ, thermally conductive ihe na ozugbo agbakwunyere sensing ọcha 4 (Fig).
Aluminom-ọla kọpa eruba reactor ekepụtara site ultrasonic mgbakwunye n'ichepụta (UAM) na mgbagwoju esịtidem ọwa Ọdịdị, agbakwunyere thermocouples na catalytic mmeghachi omume chamber.Iji anya n'ime ime mmiri ụzọ ụzọ, a transperent prototype ekepụtara site na iji stereolithography na-egosikwa.
Iji hụ na a na-emepụta reactors maka mmeghachi omume organic n'ọdịnihu, ihe mgbaze kwesịrị ikpo ọkụ n'enweghị ihe ọ bụla n'elu ebe esi mmiri; ha bụ nrụgide na okpomọkụ a nwalere. Nnwale nrụgide ahụ gosipụtara na usoro ahụ na-ejigide nrụgide siri ike ma na-adịgide adịgide ọbụna na-eme ka usoro nrụgide na-arịwanye elu (1.7 MPa) . A na-eme nyocha nke hydrostatic na ụlọ okpomọkụ na-eji H2O dị ka mmiri mmiri.
Ijikọ agbakwunyere (Ọnụ ọgụgụ 1) thermocouple na data data okpomọkụ gosiri na thermocouple bụ 6 Celsius C (± 1 Celsius C) jụrụ oyi karịa mmemme okpomọkụ na usoro FlowSyn. A na-ahụkarị, 10 Celsius C na-abawanye na okpomọkụ na-arụpụta okpukpu abụọ nke mmeghachi omume mmeghachi omume, ya mere, ọdịiche okpomọkụ nke dị nnọọ ole na ole degrees nwere ike dị iche iche nke okpomọkụ dị iche iche n'ihi na ọnụ ọgụgụ dị elu nke na-emeghachi omume n'ihi okpomọkụ. Thermal diffusivity nke ihe eji eme ihe na mmepụta usoro. Nke a thermal drift na-agbanwe agbanwe na ike ya mere a ga-aza maka na ngwá setup iji hụ na ezi okpomọkụ na-ruru na tụrụ n'oge mmeghachi omume. Ya mere, a online nlekota ngwá ọrụ na-eme ka uko akara nke mmeghachi omume okpomọkụ na-eme ka ndị ọzọ ziri ezi usoro njikarịcha na mmepe nke ezigbo ọnọdụ.These sensọ nwekwara ike-eji na-achọpụta na nnukwu mmeghachi omume-agba ọsọ usoro exoscale.
The reactor ewepụtara na ọrụ a bụ ihe atụ mbụ nke ngwa nke UAM technology na-emepụta nke kemịkalụ reactors na adreesị ọtụtụ isi adịghị ike ugbu a metụtara AM / 3D mbipụta nke ndị a ngwaọrụ, dị ka: (i) imeri kọrọ nsogbu metụtara ọla kọpa ma ọ bụ aluminom alloy nhazi (ii) mma esịtidem ọwa mkpebi tụnyere ntụ ntụ bed fusion (PBF) usoro dị ka nhọrọ nke laser agbaze 6 (PBF) usoro dị ka nhọrọ laser agbaze5 (PBF) 6. (iii) Mbelata nhazi okpomọkụ, nke mmemmem kpọmkwem bonding nke sensọ, nke na-agaghị ekwe omume na ntụ ntụ bed technology, (v) merie ogbenye n'ibu Njirimara na uche nke polymer dabeere components ka a dịgasị iche iche nke nkịtị organic solvents17,19.
E gosipụtara arụmọrụ nke reactor site na usoro ọla kọpa-catalyzed alkyne azide cycloaddition mmeghachi omume n'okpuru ọnọdụ eruba na-aga n'ihu (Fig 2) .The ultrasonic-e biri ebi ọla kọpa reactor zuru ezu na Figure 4 e integrated na a azụmahịa eruba usoro na-eji na synthesize ọba akwụkwọ azides nke dị iche iche 1,4-disubstituted 1,2,3-disubstituted 1,2,3-3-lene okpomọkụ mmeghachi omume na okpomọkụ nke 1,2,3-triazoles na-achịkwa okpomọkụ na-eme ka ọnọdụ okpomọkụ nke triazoles dị iche iche. ọnụnọ nke sodium chloride (Figure 3) . Iji usoro na-aga n'ihu na-aga n'ihu na-ebelata nchegbu nchekwa nke nwere ike ibili na usoro nhazi, dịka mmeghachi omume a na-emepụta ihe na-arụ ọrụ nke ọma na nke dị ize ndụ azide intermediates [317], [318] .Na mbụ, a na-emezi mmeghachi omume maka cycloaddition nke phenylacetylene na iodoethylene phenylacetylene na iodoethylene phenylacetylene -chylene. iodoethane) (lee foto 5).
(N'elu aka ekpe) Atụmatụ nhazi nke ejiri tinye 3DP reactor n'ime usoro eruba (n'elu aka nri) enwetara na atụmatụ kachasị (ala) nke atụmatụ Huisgen cycloaddition 57 n'etiti phenylacetylene na iodoethane maka njikarịcha na igosi ọnụọgụ ntụgharị nzaghachi kachasị mma.
Site n'ịchịkwa oge obibi nke reagents na akụkụ catalytic nke reactor na nlezianya nyochaa okpomọkụ mmeghachi omume na nyocha nke thermocouple ozugbo, enwere ike ịhazi ọnọdụ mmeghachi omume ngwa ngwa na n'ụzọ ziri ezi na obere oge na ihe oriri. E kpebisiri ike ngwa ngwa na mgbanwe ndị kachasị elu nwetara mgbe oge obibi nke 15 nkeji na mmeghachi omume okpomọkụ nke 150 Celsius C na-eji ya ma ọ bụ ọnọdụ okpomọkụ nke MOD na ọnọdụ okpomọkụ. A na-ewere ya dị ka usoro ihe atụ dị mkpa. Ịgba ngwa ngwa na-arụ ọrụ na-eji usoro ndị a ahọpụtara na-emepụta usoro mmeghachi omume nke e mere iji mee ka ebe kachasị elu ngwaahịa dị elu ma na-ebelata ebe mmalite ihe kachasị elu. Nkwalite a na-emepụta 53% ntụgharị nke ngwaahịa triazole, nke kwekọrọ na amụma nlereanya nke 54%.
Dabere na akwụkwọ ndị na-egosi na ọla kọpa (I) oxide (Cu2O) nwere ike na-eme dị ka ihe dị irè catalytic umu on efu-valent ọla kọpa na-ebupụta na ndị a Jeremaya mere, ikike nke pre-oxidize na reactor elu tupu arụpụta mmeghachi omume na eruba e nyochara70,71. The mmeghachi omume n'etiti phenylacetylene na iodoethane e wee rụrụ ọzọ n'okpuru ezigbo ọnọdụ na-eme ka e jiri ya tụnyere nke a dị ịrịba ama n'ihi na e jiri ya tụnyere ihe dị ịrịba ama. ntughari nke mmalite ihe, nke a gbakọọ na-> 99% . Otú ọ dị, nlekota nke HPLC gosiri na nke a ntughari budata belata ókè ogologo oge mmeghachi omume oge ruo ihe dị ka 90 nkeji, ebe ọrụ pụtara larịị anya wee rute a "otu ebe" .Nke a chọpụtara na-egosi na isi iyi nke catalytic ọrụ na-enweta site n'elu ọla kọpa oxide kama zero-valentized metal okpomọkụ na-adị mfe n'ime ụlọ Cucu. nke na-adịghị echebe onwe ya.