Ua tsaug rau koj tuaj xyuas Nature.com.Qhov browser version koj siv tau txwv kev txhawb nqa rau CSS.Rau qhov kev paub zoo tshaj plaws, peb xav kom koj siv qhov browser tshiab (lossis kaw qhov kev sib raug zoo hauv Internet Explorer).
Kev tsim khoom ntxiv tau hloov pauv txoj kev tshawb fawb thiab cov kws tsim khoom tsim thiab tsim cov khoom siv tshuaj lom neeg kom ua tau raws li lawv cov kev xav tau tshwj xeeb. Hauv kev ua haujlwm no, peb tshaj tawm thawj qhov piv txwv ntawm cov dej ntws reactor tsim los ntawm cov txheej txheem hlau-state hlau lamination txheej txheem Ultrasonic Additive Manufacturing (UAM) nrog ncaj qha integrated catalytic qhov chaw thiab sensing hais. Cov cuab yeej siv tshuaj lom neeg tseem ceeb 1,4-disubstituted 1,2,3-triazole tebchaw tau ua tiav thiab ua kom zoo dua los ntawm Cu-mediated Huisgen 1,3-dipolar cycloaddition cov tshuaj tiv thaiv siv UAM chemistry teeb tsa.
Vim nws cov txiaj ntsig tseem ceeb ntawm nws cov khoom lag luam ntau, ntws chemistry yog ib qho tseem ceeb thiab loj hlob hauv ob qho tib si kev kawm thiab kev lag luam vim nws lub peev xwm los ua kom cov kev xaiv thiab kev ua tau zoo ntawm cov tshuaj synthesis.This txuas los ntawm cov organic molecule yooj yim formation1 rau cov tshuaj compounds2,3 thiab natural products4,5,6.Ntau tshaj 50% ntawm cov tshuaj tiv thaiv nyob rau hauv cov tshuaj zoo thiab tshuaj industries tuaj yeem tau txais txiaj ntsig los ntawm kev siv cov kev ua haujlwm tas mus li 7.
Nyob rau hauv xyoo tas los no, muaj kev loj hlob ntawm cov pab pawg tab tom nrhiav los hloov cov iav tsoos los yog cov khoom siv chemistry nrog customizable additive manufacturing (AM) chemistry "reaction hlab ntsha" 8.The iterative design, sai sai, thiab 3-dimensional (3D) muaj peev xwm ntawm cov tswv yim no muaj txiaj ntsig zoo rau cov neeg uas xav kho lawv cov khoom siv rau cov txheej txheem tshwj xeeb ntawm cov tshuaj tiv thaiv hnub no, yuav luag siv cov khoom siv tshwj xeeb. D tshuab luam ntawv xws li stereolithography (SL) 9,10,11, fused deposition modeling (FDM)8,12,13,14 thiab inkjet luam ntawv 7, 15, 16. Qhov tsis muaj zog thiab muaj peev xwm ntawm cov cuab yeej zoo li no los ua ntau yam tshuaj tiv thaiv / tshuaj ntsuam xyuas 17, 18, 19, kev txwv loj hauv kev siv 7, 18, 19 18, 19, 20.
Vim muaj kev siv ntau ntxiv ntawm cov tshuaj lom neeg thiab cov khoom muaj txiaj ntsig zoo txuam nrog AM, yuav tsum tau tshawb nrhiav cov txuj ci siab ntxiv uas pab cov neeg siv los tsim cov tshuaj tiv thaiv cov hlab ntsha nrog kev txhim kho tshuaj lom neeg thiab tshuaj ntsuam xyuas muaj peev xwm.Cov tswv yim no yuav tsum ua kom cov neeg siv xaiv los ntawm ntau yam ntawm cov khoom muaj zog lossis cov khoom siv muaj peev xwm tuav tau ntau yam ntawm cov tshuaj tiv thaiv kab mob, thaum tseem ua kom yooj yim rau kev tswj xyuas ntau yam ntawm cov tshuaj tiv thaiv.
Ib qho txheej txheem tsim khoom ntxiv uas muaj peev xwm los tsim cov kev cai tshuaj reactors yog Ultrasonic Additive Manufacturing (UAM).This solid-state sheet lamination txheej txheem siv ultrasonic oscillations rau nyias hlau foils thiaj li mus koom lawv ua ke txheej los ntawm txheej nrog tsawg kawg nkaus cua sov thiab ib tug high degree ntawm yas ntws 21 , 22 , 23 .Unlike technologies feem ntau hu ua sublogive AM. hybrid manufacturing txheej txheem, uas nyob rau hauv-situ periodic computer numerical tswj (CNC) milling los yog laser machining txhais cov net zoo ntawm ib txheej ntawm bonded khoom 24, 25.Qhov no txhais tau hais tias tus neeg siv tsis txwv los ntawm cov teeb meem cuam tshuam nrog tshem tawm cov residual raw khoom los ntawm me me kua raws, uas feem ntau yog cov ntaub ntawv nrog hmoov thiab kua 7, 25 AM system muaj kev ywj pheej. thiab cov khoom sib txawv sib xyaw ua ke hauv cov txheej txheem ib kauj ruam.Qhov kev xaiv ntawm cov khoom sib txuas dhau ntawm cov txheej txheem yaj txhais tau hais tias cov khoom siv thiab tshuaj lom neeg xav tau ntawm cov ntawv thov tshwj xeeb tuaj yeem ua tau zoo dua. Ntxiv nrog rau cov khoom siv hauv lub xeev kev sib raug zoo, lwm qhov tshwm sim tshwm sim thaum lub sij hawm sib txuas ultrasonic yog qhov siab ntawm cov ntaub ntawv yas ntawm qhov kub qis 29, 30, 31, 32, 33.Qhov tshwj xeeb ntawm Ubedding cov ntsiab lus ntawm cov hlau tsis muaj kev puas tsuaj. s tuaj yeem pab txhawb nqa cov ntaub ntawv ntawm lub sijhawm tiag tiag los ntawm lub cuab yeej mus rau tus neeg siv los ntawm kev sib xyaw ua ke.
Cov kws sau ntawv yav dhau los ua haujlwm32 tau qhia txog kev muaj peev xwm ntawm UAM txheej txheem los tsim cov hlau 3D microfluidic cov qauv nrog kev sib xyaw ua kom pom kev muaj peev xwm.Qhov no yog ib qho kev soj ntsuam nkaus xwb.Cov ntawv no nthuav tawm thawj qhov piv txwv ntawm microfluidic tshuaj reactor fabricated los ntawm UAM;ib qho khoom siv nquag uas tsis tsuas yog saib xyuas tab sis kuj txhawb cov tshuaj synthesis los ntawm cov khoom siv catalyst structurally integrated catalyst.Cov cuab yeej sib txuas ntau yam zoo nrog UAM technology hauv 3D chemical device manufacturing, xws li: lub peev xwm los hloov tag nrho 3D designs ncaj qha los ntawm computer-aided design (CAD) qauv rau hauv cov khoom;multi-material fabrication los ua ke siab thermal conductivity thiab catalytic cov ntaub ntawv;thiab embedding thermal sensors ncaj qha nruab nrab ntawm cov reagent kwj rau cov tshuaj tiv thaiv qhov ntsuas kub thiab kev tswj xyuas.Yuav ua kom pom kev ua haujlwm ntawm lub reactor, lub tsev qiv ntawv ntawm cov tshuaj tseem ceeb 1,4-disubstituted 1,2,3-triazole tebchaw tau tsim los ntawm tooj liab-catalyzed Huisgen 1,3-dipolaroilization ntawm lub khoos phis tawj ua haujlwm li cas. nce lub cib fim tshiab thiab muaj peev xwm rau chemistry los ntawm kev tshawb fawb ntau yam.
Tag nrho cov kuab tshuaj thiab cov tshuaj reagents tau yuav los ntawm Sigma-Aldrich, Alfa Aesar, TCI lossis Fischer Scientific thiab tau siv yam tsis muaj kev ua kom huv ua ntej.1H thiab 13C NMR spectra kaw ntawm 400 MHz thiab 100 MHz, raws li, tau txais siv JEOL ECS-400 400 MHz aspectro 400 MHz thiab Bspectro 3. los yog (CD3)2SO raws li hnyav.Tag nrho cov tshuaj tiv thaiv tau ua los ntawm Uniqsis FlowSyn flow chemistry platform.
UAM tau siv los tsim txhua yam khoom siv hauv qhov kev tshawb fawb no.Lub tshuab tau tsim nyob rau xyoo 1999, thiab nws cov ntsiab lus kev ua haujlwm, kev ua haujlwm tsis zoo thiab kev tsim kho txij li nws qhov kev tsim tawm tuaj yeem kawm los ntawm cov ntaub ntawv luam tawm hauv qab no34,35,36,37.Cov cuab yeej (Daim duab 1) tau siv los siv lub zog siab ultra-siab, 9kW SonicLayer 4000, UAM Flow Flow Systems (UAM) . cov cuab yeej yog Cu-110 thiab Al 6061.Cu-110 muaj cov ntsiab lus tooj liab siab (tsawg kawg 99.9% tooj liab), ua rau nws yog ib tus neeg sib tw zoo rau cov tshuaj tiv thaiv tooj liab-catalyzed, thiab yog li siv los ua "txheej txheej hauv microreactor.Al 6061 O yog siv los ua "bulk" cov khoom, kuj Embedding txheej siv rau kev tsom xam;Alloy auxiliary tivthaiv embedding thiab annealed mob ua ke nrog Cu-110 txheej.Al 6061 O yog cov khoom siv uas tau pom tias muaj kev sib raug zoo nrog UAM cov txheej txheem 38, 39, 40, 41 thiab tau sim thiab pom muaj tshuaj lom neeg ruaj khov nrog cov tshuaj reagents siv hauv kev ua haujlwm no.Kev sib xyaw ua ke ntawm Al 6061 O nrog Cu-110 kuj suav hais tias yog cov khoom siv sib xyaw ua ke rau UAM thiab yog li cov ntaub ntawv tsim nyog rau txoj kev tshawb no.38,42 Cov khoom siv no tau teev tseg hauv Table 1 hauv qab no.
Reactor fabrication theem (1) Al 6061 substrate (2) Fabrication ntawm hauv qab channel teem rau tooj liab ntawv ci (3) Embedding ntawm thermocouples ntawm txheej (4) Sab saum toj channel (5) Inlet thiab qhov hluav taws xob (6) Monolithic reactor.
Lub tswv yim tsim ntawm cov kua dej yog siv txoj hauv kev sib txuas kom nce qhov kev ncua deb ntawm cov dej mus rau hauv lub nti, thaum khaws cov nti ntawm qhov loj me.Qhov kev ncua deb yog xav kom nce catalyst / reagent cuam tshuam lub sij hawm thiab muab cov khoom lag luam zoo tshaj plaws. Cov chips siv 90 ° khoov ntawm qhov kawg ntawm txoj kev ncaj mus rau induce fluctuation 4 lub sij hawm sib txuas ntxiv ntawm qhov sib xyaw ua ke. qhov sib tov uas tuaj yeem ua tiav, cov qauv tsim reactor nta ob reagent inlets ua ke ntawm Y-hluav taws xob ua ntej nkag mus rau serpentine mixing section.Qhov thib peb inlet, uas cuam tshuam cov kwj ib nrab los ntawm nws qhov chaw nyob, suav nrog kev tsim ntawm yav tom ntej multistep cov tshuaj tiv thaiv syntheses.
Tag nrho cov channel muaj ib lub square profile (tsis muaj lub kaum sab xis), qhov tshwm sim ntawm lub sij hawm CNC milling siv los tsim cov channel geometry.Cov channel qhov ntev yog xaiv los xyuas kom meej qhov siab (rau microreactor) ntim cov zis, thaum me me txaus los pab txhawb kev sib cuam tshuam ntawm qhov chaw (catalysts) rau feem ntau ntawm cov dej uas muaj.Qhov tsim nyog loj yog raws li tus sau phau ntawv ' 5 qhov ntev dhau los ntawm cov khoom siv nrog hlau-fl. 750 µm thiab tag nrho cov reactor ntim yog 1 ml.Ib qho kev sib txuas (1/4 "-28 UNF xov) suav nrog hauv kev tsim kom tso cai yooj yim cuam tshuam ntawm cov cuab yeej nrog cov khoom lag luam chemistry.Cov channel loj yog txwv los ntawm cov tuab ntawm cov ntawv ci, nws cov khoom siv kho tshuab, thiab kev sib txuas tsis siv nrog ultrasonics.Ntawm qhov dav tshwj xeeb rau cov khoom siv, cov khoom yuav "sag" rau hauv cov channel tsim.Tam sim no tsis muaj cov qauv tshwj xeeb rau qhov kev suav no, yog li qhov siab tshaj plaws channel dav rau cov khoom siv thiab tsim tau txiav txim siab sim;Hauv qhov no, qhov dav ntawm 750 μm yuav tsis ua rau sag.
Cov duab (square) ntawm cov channel yog txiav txim siab los ntawm kev siv lub square cutter.Cov duab thiab qhov loj ntawm cov channel tuaj yeem hloov kho los ntawm CNC tshuab siv cov cuab yeej txiav sib txawv kom tau txais cov nqi sib txawv thiab cov yam ntxwv.Ib qho piv txwv ntawm kev tsim cov duab nkhaus channel siv lub cuab yeej 125 μm tuaj yeem pom nyob rau hauv kev ua haujlwm ntawm Monaghan45.Thaum cov ntawv ci txheej yog muab tso rau hauv ib qho chaw tiaj tus (plan foil) ntawm cov khoom siv no yuav tsum tau ua tiav. ua haujlwm, txhawm rau tswj qhov sib luag ntawm cov channel, siv cov qauv square.
Thaum lub sij hawm ua ntej qhov kev pab cuam nres hauv kev tsim khoom, cov thermocouple kub sojntsuam (Type K) tau kos ncaj qha rau hauv lub cuab yeej ntawm cov pab pawg sab sauv thiab sab qis (Daim duab 1 - Theem 3).Cov thermocouples tuaj yeem saib xyuas qhov kub thiab txias ntawm −200 txog 1350 ° C.
Cov txheej txheem hlau tso tawm yog ua los ntawm UAM horn siv 25.4 hli dav, 150 micron tuab hlau ntawv.Qhov loj ntawm cov khoom tso tawm yog loj dua li cov khoom kawg raws li cov txheej txheem rho tawm ua qhov kawg net zoo li.CNC machining yog siv los tshuab cov khoom siv sab nraud thiab sab hauv, ua rau cov khoom tiav thiab cov kab sib npaug ntawm cov cuab yeej xaiv thiab CNC txheej txheem tsis (kwv yees li 1.6 μm Ra hauv qhov piv txwv no). Kev tswj xyuas thiab qhov ua tiav yuav ua tau raws li CNC tiav milling qhov tseeb theem.Qhov dav dav siv rau cov cuab yeej no yog me me los xyuas kom meej tias cov ntaub ntawv foil tsis "sag" rau hauv cov kua dej channel, yog li cov channel tuav lub square cross-section.Qhov khoob ntawm cov ntawv ci thiab UAM cov txheej txheem tsis tau txiav txim siab los ntawm ib tus neeg tsim khoom (Fabrisonic LLC, USA).
Cov kev tshawb fawb tau pom tias me ntsis kev nthuav dav tshwm sim ntawm UAM kev sib txuas lus interface 46, 47 yam tsis muaj kev kho cua sov ntxiv, yog li rau cov khoom siv hauv txoj haujlwm no, Cu-110 txheej tseem txawv ntawm Al 6061 txheej thiab hloov pauv sai.
Nruab ib lub pre-calibrated 250 psi (1724 kPa) rov qab siab regulator (BPR) mus rau lub qhov hluav taws xob ntawm lub reactor thiab twj tso kua mis dej los ntawm lub reactor ntawm tus nqi ntawm 0.1 mus rau 1 mL min-1.Lub reactor siab tau soj ntsuam siv lub FlowSyn built-in system siab sensor los xyuas kom meej tias lub kaw lus muaj peev xwm tswj tau qhov kub thiab txias reactor. Nyob rau hauv ib qho kev sib txawv ntawm cov thermocouples embedded nyob rau hauv lub reactor thiab cov embedded nyob rau hauv lub FlowSyn nti cua sov phaj.Qhov no yog ua tiav los ntawm kev sib txawv ntawm qhov programmable hotplate kub ntawm 100 thiab 150 ° C nyob rau hauv 25 ° C increments thiab ceeb toom qhov sib txawv ntawm qhov programmed thiab kaw qhov kub thiab txias.Qhov no tau ua tiav los ntawm kev sib txawv ntawm qhov programmable hotplate kub ntawm 100 thiab 150 ° C hauv 25 ° C increments thiab ceeb toom qhov sib txawv ntawm qhov programmed thiab kaw qhov kub. Hauv PicoLog software.
Cov tshuaj tiv thaiv cycloaddition ntawm phenylacetylene thiab iodoethane tau ua kom zoo dua (Tebchaws 1- Cycloaddition ntawm phenylacetylene thiab iodoethane Scheme 1- Cycloaddition ntawm phenylacetylene thiab iodoethane).Qhov kev ua kom zoo dua no tau ua tiav los ntawm kev tsim tag nrho factorial ntawm kev sim ntsuas qhov ntsuas kub, thiab lub sij hawm kho (DOE) ne:azide ratio ntawm 1:2.
Sib cais kev daws teeb meem ntawm sodium azide (0.25 M, 4: 1 DMF: H2O), iodoethane (0.25 M, DMF), thiab phenylacetylene (0.125 M, DMF) tau npaj.A 1.5 mL aliquot ntawm txhua qhov kev daws tau sib xyaw thiab pumped los ntawm lub reactor ntawm qhov xav tau cov khoom lag luam phenyllen yog qhov piv ntawm cov khoom siv phenylene thiab qhov ntsuas kub ntawm qhov pib ntawm cov khoom siv pneumatic. thiab txiav txim siab los ntawm kev ua haujlwm siab ua kua chromatography (HPLC).Rau qhov sib xws ntawm kev soj ntsuam, tag nrho cov tshuaj tiv thaiv tau raug kuaj tom qab cov tshuaj tiv thaiv sib tov tawm ntawm lub reactor.Cov kev txwv ntau yam xaiv rau kev ua kom zoo yog qhia hauv Table 2.
Tag nrho cov qauv raug soj ntsuam siv Chromaster HPLC system (VWR, PA, USA) uas muaj lub twj tso kua mis quaternary, kem qhov cub, qhov sib txawv wavelength UV detector thiab autosampler.Cov kem yog ib qho Equivalence 5 C18 (VWR, PA, USA), 4.6 × 100 mm nyob rau hauv loj, 5 5 µCratic particle loj: 4. methanol: dej ntawm tus nqi ntws ntawm 1.5 mL.min-1.Qhov ntim txhaj tshuaj yog 5 µL thiab lub ntsuas ntsuas lub wavelength yog 254 nm.Cov % ncov cheeb tsam rau cov qauv DOE yog xam los ntawm cov cheeb tsam ncov ntawm cov khoom seem alkyne thiab triazole nkaus xwb.Kev txhaj tshuaj ntawm cov khoom pib tso cai rau kev txheeb xyuas cov peaks.
Coupling lub reactor tsom xam tso zis rau lub MODDE DOE software (Umetrics, Malmö, Sweden) tso cai rau ib tug meej kev soj ntsuam ntawm cov kev tshwm sim tiam sis thiab kev txiav txim siab ntawm kev pom zoo tshuaj tiv thaiv tej yam kev mob rau no cycloaddition.Running lub built-in optimizer thiab xaiv tag nrho cov tseem ceeb qauv nqe lus yields ib tug txheej ntawm cov tshuaj tiv thaiv tej yam kev mob tsim los maximize cov khoom ncov cheeb tsam thaum txo lub ncov cheeb tsam pib acety.
Lub oxidation ntawm tooj liab nto nyob rau hauv lub catalytic cov tshuaj tiv thaiv chamber tau tiav siv ib tug tov ntawm hydrogen peroxide (36%) ntws los ntawm cov tshuaj tiv thaiv chamber (flow rate = 0.4 mL min-1, lub sij hawm nyob = 2.5 min) ua ntej synthesis ntawm txhua lub tsev qiv ntawv triazole compound.
Thaum ib qho kev pom zoo ntawm cov xwm txheej raug txheeb xyuas, lawv tau siv rau ntau yam ntawm acetylene thiab haloalkane derivatives kom tso cai muab tso ua ke ntawm ib lub tsev qiv ntawv me me synthesis, yog li tsim kom muaj peev xwm siv tau cov kev mob no rau ntau yam ntawm cov muaj peev xwm reagents (Daim duab 1).2).
Npaj cov kev daws teeb meem ntawm sodium azide (0.25 M, 4: 1 DMF: H2O), haloalkanes (0.25 M, DMF) thiab alkynes (0.125 M, DMF). acetate.Cov qauv tov yog ntxuav nrog 3 × 10 mL dej.Cov txheej txheej aqueous tau muab tso ua ke thiab muab rho tawm nrog 10 mL ntawm ethyl acetate;Cov txheej txheem organic tau muab tso ua ke, ntxuav nrog 3 x 10 mL ntawm brine, qhuav dhau MgSO4 thiab lim, tom qab ntawd cov kuab tshuaj tau muab tshem tawm hauv vacuo.Cov qauv raug purified los ntawm kem chromatography ntawm silica gel siv ethyl acetate ua ntej kev tshuaj xyuas los ntawm kev sib xyaw ntawm HPLC, 1H NMR, 13C NMS thiab cov kev daws teeb meem siab (HR-HR).
Tag nrho cov spectra tau txais los ntawm kev siv lub Thermofischer precision Orbitrap daws teeb meem huab hwm coj spectrometer nrog ESI ua qhov chaw ionization.Tag nrho cov qauv tau npaj siv acetonitrile ua hnyav.
TLC tsom xam tau ua tiav ntawm cov ntawv txhuas-rov qab silica.Plates tau pom los ntawm UV teeb (254 nm) lossis vanillin staining thiab cua sov.
Tag nrho cov qauv tau soj ntsuam siv lub VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) system nruab nrog ib qho autosampler, kem cub binary twj tso kua mis thiab ib lub wavelength detector.Cov kem siv yog ACE Equivalence 5 C18 (150 × 4.6 mm, Advanced Chromatography Technologies Ltd., Scotde).
Kev txhaj tshuaj (5 µL) tau tsim ncaj qha los ntawm diluted crude tshuaj sib tov (1:10 dilution) thiab soj ntsuam nrog dej: methanol (50:50 lossis 70:30), tshwj tsis yog rau qee cov qauv siv 70:30 hnyav system (tus lej hnub qub) ntawm tus nqi ntws ntawm 1.5 mL / min.Cov kem 5l th.
Qhov % ncov cheeb tsam ntawm cov qauv yog xam los ntawm lub ncov cheeb tsam ntawm cov residual alkyne, tsuas yog cov khoom triazole, thiab txhaj tshuaj ntawm cov khoom pib tso cai rau kev txheeb xyuas ntawm cov peaks cuam tshuam.
Tag nrho cov qauv raug txheeb xyuas siv Thermo iCAP 6000 ICP-OES.Txhua cov qauv ntsuas tau npaj siv 1000 ppm Cu standard tov nyob rau hauv 2% nitric acid (SPEX Certi Prep).Tag nrho cov qauv tau npaj nyob rau hauv 5% DMF thiab 2% HNO3 tov, thiab tag nrho cov qauv tau diluted DMF 20-HNO3 qauv.
UAM siv ultrasonic hlau vuam raws li cov txheej txheem sib txuas rau cov ntawv hlau hlau siv los tsim cov kev sib dhos zaum kawg. Ultrasonic hlau vuam siv cov cuab yeej vibrating hlau (hu ua horn lossis ultrasonic horn) los siv lub siab rau cov ntawv ci txheej / yav dhau los sib sau ua ke rau kev sib koom ua ke thaum vibrating cov khoom siv.Rau kev ua haujlwm tas mus li, tag nrho cov khoom siv hluav taws xob. Lub siab thiab kev vibration yog siv, cov oxides nyob rau saum npoo ntawm cov khoom tuaj yeem tawg.Nruam siab thiab kev vibration tuaj yeem ua rau cov khoom tawg yooj yim 36 .Intimate contact with locally induced heat and pressure then leads to solid-state bonding at material interfaces;Nws kuj tseem tuaj yeem pab adhesion los ntawm kev hloov pauv hauv lub zog saum npoo av48.Qhov xwm txheej ntawm kev sib koom ua ke tau kov yeej ntau yam teeb meem cuam tshuam nrog qhov sib txawv ntawm qhov kub thiab txias tom qab-tshuaj cuam tshuam tau hais hauv lwm cov txheej txheem tsim khoom ntxiv.Qhov no tso cai rau kev sib txuas ncaj qha (xws li, tsis muaj qhov hloov kho qhov chaw, fillers lossis adhesives) ntawm ntau txheej txheej ntawm cov ntaub ntawv sib txawv rau hauv ib qho kev sib koom ua ke.
Qhov thib ob qhov zoo tshaj plaws rau UAM yog qhov siab ntawm cov yas ntws pom hauv cov khoom siv hlau, txawm tias qhov kub thiab txias, piv txwv li zoo hauv qab lub melting point ntawm metallic cov ntaub ntawv.Qhov sib xyaw ntawm ultrasonic oscillation thiab siab induces siab theem ntawm cov nplej ciam teb tsiv teb tsaws thiab recrystallization tsis muaj qhov kub thiab txias nce ib txwm txuam nrog bulk cov ntaub ntawv. Thaum lub sij hawm kev tsim kho ntawm cov txheej txheem zaum kawg ntawm lub rooj sib txoos ua ke tuaj yeem dhau los ntawm cov khoom siv phenomenon. hlau ntawv ci, txheej los ntawm txheej.Elements xws li optical fibers 49, reinforcements 46, electronics 50, thiab thermocouples (qhov no ua hauj lwm) tau tag nrho cov tau ntse embedded rau hauv UAM lug tsim active thiab passive composite cov rooj sib txoos.
Hauv kev ua haujlwm no, ob qho tib si sib txawv ntawm cov khoom sib txuas thiab kev sib cuam tshuam ntawm UAM tau siv los tsim qhov kawg catalytic kub soj ntsuam microreactor.
Piv nrog palladium (Pd) thiab lwm yam siv hlau catalysts, Cu catalysis muaj ntau qhov zoo: (i) Kev lag luam, Cu tsis tshua kim dua li ntau lwm cov hlau siv hauv catalysis thiab yog li qhov kev xaiv zoo rau kev lag luam tshuaj lom neeg (ii) Qhov ntau ntawm Cu-catalyzed cross-coupling cov tshuaj tiv thaiv yog nce ntxiv thiab zoo li me ntsis 5-1, iii. ed cov tshuaj tiv thaiv ua haujlwm tau zoo thaum tsis muaj lwm cov ligands, Cov ligands no feem ntau yooj yim thiab pheej yig yog tias xav tau, whereas cov siv hauv Pd chemistry feem ntau nyuaj, kim, thiab huab cua-rhiab heev (iv) Cu, tshwj xeeb tshaj yog paub txog nws lub peev xwm los khi alkynes hauv kev sib txuas, Piv txwv li, bimetallic-catalyzed nrog Sonogashirade (Cycvashirade). Nws kuj tseem tuaj yeem txhawb nqa lub arylation ntawm ob peb nucleophiles hauv Ullmann-hom tshuaj tiv thaiv.
Piv txwv ntawm heterogenization ntawm tag nrho cov kev cuam tshuam no tsis ntev los no tau tshwm sim nyob rau hauv lub xub ntiag ntawm Cu(0).Qhov no feem ntau yog vim kev lag luam tshuaj thiab kev loj hlob tsom rau cov hlau catalyst rov qab thiab rov siv dua55,56.
Pioneered los ntawm Huisgen nyob rau hauv lub xyoo 1960s57, 1,3-dipolar cycloaddition cov tshuaj tiv thaiv ntawm acetylene thiab azide rau 1,2,3-triazole yog suav hais tias yog ib tug synergistic demonstration cov tshuaj tiv thaiv.Qhov tshwm sim 1,2,3 triazole moieties yog tshwj xeeb yog txaus siab raws li pharmacophore nyob rau hauv lub teb ntawm kev siv tshuaj lom neeg thiab kev siv ntau yam kev siv tshuaj.
Cov tshuaj tiv thaiv no tau los ua kom pom tseeb dua thaum Sharpless thiab lwm tus tau qhia lub tswv yim ntawm "nias chemistry" 59.Lub sij hawm "nias chemistry" yog siv los piav qhia txog cov txheej txheem muaj zog, txhim khu kev qha thiab xaiv cov tshuaj tiv thaiv rau kev sib txuas ceev ceev ntawm cov tebchaw tshiab thiab cov tsev qiv ntawv combinatorial los ntawm heteroatom linkage (CXC) 60 Cov tshuaj tiv thaiv kev sib txuas ntawm cov pa oxygen, thiab cov tshuaj tiv thaiv siab. dej tsis kam, thiab cov khoom sib cais yog yooj yim61.
Lub classical Huisgen 1,3-dipole cycloaddition tsis yog nyob rau hauv qeb ntawm "nias chemistry".Txawm li cas los xij, Medal thiab Sharpless tau pom tias qhov kev tshwm sim azide-alkyne coupling no dhau 107 mus rau 108 nyob rau hauv lub xub ntiag ntawm Cu(I) piv rau cov uncatalyzed 1,3-6-dipole cov tshuaj tiv thaiv. Tsis tas yuav tiv thaiv cov pab pawg lossis cov xwm txheej hnyav thiab cov txiaj ntsig tau los ze rau kev hloov pauv thiab kev xaiv rau 1,4-disubstituted 1,2,3-triazoles (anti- 1,2,3-triazole) ntawm lub sijhawm teev (Daim duab 3).
Isometric cov txiaj ntsig ntawm cov pa thiab tooj liab-catalyzed Huisgen cycloadditions.Cu(I)-catalyzed Huisgen cycloadditions yield tsuas yog 1,4-disubstituted 1,2,3-triazoles, whereas thermally induced Huisgen cycloadditions feem ntau tawm los 1,54-triazoles ntawm 1,54-triazoles.
Cov txheej txheem feem ntau cuam tshuam nrog kev txo qis ntawm Cu(II) ruaj khov, xws li txo CuSO4 lossis Cu(II) / Cu(0) hom kev sib xyaw nrog cov ntsev ntsev.Piv nrog lwm cov tshuaj tiv thaiv hlau-catalyzed, kev siv Cu(I) muaj qhov zoo ntawm kev pheej yig thiab yooj yim los daws.
Kinetic thiab isotopic labeling kev tshawb fawb los ntawm Worrell li al.65 qhia tau hais tias, nyob rau hauv cov ntaub ntawv ntawm davhlau ya nyob twg alkynes, ob qhov sib npaug ntawm tooj liab yog koom tes nyob rau hauv activating lub reactivity ntawm txhua molecule ntawm azide.Lub tswv yim txheej txheem txheej txheem los ntawm ib tug rau-membered tooj liab hlau nplhaib tsim los ntawm kev sib koom tes ntawm azide rau σ-bonded tooj liab dong-acetyl acetyl. per derivatives yog tsim los ntawm lub nplhaib shrinkage, ua raws li proton decomposition los muab cov khoom triazole thiab kaw lub voj voog catalytic.
Thaum cov txiaj ntsig ntawm cov khoom siv hluav taws xob ntws tau raug sau tseg zoo, muaj lub siab xav koom ua ke cov cuab yeej tshuaj ntsuam xyuas rau hauv cov kab ke no rau hauv-kab, hauv-situ, txheej txheem kev soj ntsuam66,67.UAM ua pov thawj tias yog ib txoj hauv kev tsim thiab tsim cov 3D flow reactors uas ua los ntawm catalytically nquag, thermally conductive cov ntaub ntawv nrog ncaj qha 4 Fis embedded).
Aluminium-tooj ​​liab txaus reactor fabricated los ntawm ultrasonic additive manufacturing (UAM) nrog complex sab hauv channel qauv, embedded thermocouples thiab catalytic cov tshuaj tiv thaiv chamber.To pom cov dej nyob rau hauv txoj kev, ib tug pob tshab qauv fabricated siv stereolithography kuj qhia.
Txhawm rau kom cov reactors raug tsim rau yav tom ntej cov tshuaj tiv thaiv organic, cov kuab tshuaj yuav tsum tau ua kom sov zoo tshaj qhov kub kub;lawv yog cov siab thiab ntsuas kub.Qhov kev ntsuas siab pom tau tias lub kaw lus tswj tau qhov ruaj khov thiab qhov siab tsis tu ncua txawm tias muaj qhov system siab (1.7 MPa).Qhov kev ntsuas hydrostatic tau ua nyob rau hauv chav tsev kub uas siv H2O ua cov kua dej.
Txuas cov embedded (Daim duab 1) thermocouple rau qhov ntsuas kub cov ntaub ntawv logger pom tias lub thermocouple yog 6 ° C (± 1 ° C) txias dua li qhov programmed kub ntawm FlowSyn system. Feem ntau, 10 ° C nce hauv qhov kub thiab txias ua rau ob npaug ntawm cov tshuaj tiv thaiv tus nqi, yog li qhov kub ntawm qhov sib txawv tsuas yog ob peb degrees ntawm lub cev tuaj yeem cuam tshuam qhov kub thiab txias. High thermal diffusivity ntawm cov ntaub ntawv siv nyob rau hauv lub manufacturing txheej txheem.Qhov no thermal drift yog zoo ib yam thiab yog li ntawd yuav tsum tau accounted rau hauv cov cuab yeej teeb tsa kom paub tseeb tias qhov kub thiab txias tau mus txog thiab ntsuas thaum lub sij hawm cov tshuaj tiv thaiv.Yog li ntawd, qhov kev soj ntsuam hauv internet no yooj yim tswj nruj ntawm cov tshuaj tiv thaiv kub thiab ua kom yooj yim dua cov txheej txheem optimization thiab kev loj hlob ntawm kev pom tej yam kev mob.Cov sensors no kuj siv tau los txheeb xyuas cov tshuaj tiv thaiv exotherms.
Lub reactor nthuav tawm hauv txoj haujlwm no yog thawj qhov piv txwv ntawm kev siv UAM thev naus laus zis rau kev tsim cov tshuaj reactors thiab hais txog ntau qhov kev txwv tseem ceeb tam sim no cuam tshuam nrog AM / 3D luam ntawv ntawm cov cuab yeej no, xws li: (i) kov yeej cov teeb meem qhia txog tooj liab lossis txhuas alloy ua (ii) txhim kho cov kev daws teeb meem sab hauv piv rau cov hmoov txaj fusion (PBF) cov txheej txheem melting 6 (6 6 s) zoo li cov khoom siv (Miii) kev ntxhib los mos (Miii). ) Txo cov txheej txheem kub, uas ua kom yooj yim sib txuas ncaj qha ntawm cov sensors, uas tsis tuaj yeem ua tau hauv cov hmoov txaj tshuab, (v) kov yeej cov khoom siv tsis zoo thiab rhiab heev ntawm cov khoom siv polymer-raws li cov khoom siv rau ntau hom organic solvents17,19.
Lub functionality ntawm lub reactor tau pom los ntawm ib tug series ntawm tooj liab-catalyzed alkyne azide cycloaddition tshwm sim nyob rau hauv tas li ndlwg tej yam kev mob (Daim duab 2).Lub ultrasonic-luam tooj liab reactor ntxaws nyob rau hauv daim duab 4 yog integrated nrog ib tug coj mus muag khiav system thiab siv los ua ke cov tsev qiv ntawv azides ntawm ntau yam 1,4-1-disubst kub cov tshuaj tiv thaiv, lene thiab alkyl pawg halides nyob rau hauv lub xub ntiag ntawm sodium chloride (Daim duab 3).Kev siv ib tug tas mus li khiav mus kom ze mitigates kev nyab xeeb kev txhawj xeeb uas yuav tshwm sim nyob rau hauv batch txheej txheem, raws li cov tshuaj tiv thaiv no ua rau reactive heev thiab txaus ntshai azide intermediates [317], [318].Thaum pib, cov tshuaj tiv thaiv yog optimized rau cov phenylethylene-Cyclazide (phenylacetate) thiab phenylase. cloaddition ntawm phenylacetylene thiab iodoethane) (saib daim duab 5).
(Sab laug sab laug) Schematic ntawm kev teeb tsa siv los koom nrog 3DP reactor rau hauv cov dej ntws (sab saum toj sab xis) tau txais nyob rau hauv qhov kev ua kom zoo (hauv qab) cov tswv yim ntawm Huisgen cycloaddition 57 cov tswv yim ntawm phenylacetylene thiab iodoethane rau kev ua kom zoo thiab qhia qhov ua kom zoo tshaj qhov tsis zoo ntawm cov tshuaj tiv thaiv kev hloov pauv.
Los ntawm kev tswj lub sij hawm nyob hauv cov reagents nyob rau hauv lub catalytic ib feem ntawm lub reactor thiab saib xyuas cov tshuaj tiv thaiv kub nrog ib tug ncaj qha integrated thermocouple sojntsuam, cov tshuaj tiv thaiv tej yam kev mob yuav optimized sai thiab meej nrog tsawg tsawg lub sij hawm thiab cov khoom noj. Lub sij hawm thiab cov tshuaj tiv thaiv kub yog suav tias yog cov qauv tseem ceeb cov ntsiab lus.Running lub built-in optimizer siv cov lus xaiv no generates ib txheej ntawm cov tshuaj tiv thaiv tej yam kev mob tsim los maximize cov khoom ncov cheeb tsam thaum txo pib cov khoom ncov cheeb tsam.Qhov no optimization yielded ib tug 53% hloov dua siab tshiab ntawm cov khoom triazole, uas zoo sib xws cov qauv kwv yees ntawm 54%.
Raws li cov ntaub ntawv qhia tau hais tias tooj liab (I) oxide (Cu2O) tuaj yeem ua raws li cov kab mob catalytic zoo ntawm xoom-valent tooj liab qhov chaw hauv cov tshuaj tiv thaiv no, lub peev xwm ua ntej oxidize lub reactor nto ua ntej nqa tawm cov tshuaj tiv thaiv nyob rau hauv ntws tau tshawb xyuas 70,71.Cov tshuaj tiv thaiv ntawm phenylacetylene thiab iodoethane tau zoo dua qhov kev npaj tau los ntawm qhov kev npaj no. Nyob rau hauv ib qho kev nce ntxiv hauv kev hloov pauv ntawm cov khoom pib, uas tau suav tias yog> 99%. Txawm li cas los xij, kev soj ntsuam los ntawm HPLC pom tau tias qhov kev hloov pauv no tau txo qis cov tshuaj tiv thaiv ntev heev kom txog rau thaum kwv yees li 90 feeb, whereupon cov dej num tau tshwm sim rau theem tawm thiab ncav cuag "lub xeev khov kho". chav ntsuas kub los ua CuO thiab Cu2O uas tsis yog txheej txheej tiv thaiv tus kheej.Qhov no tshem tawm qhov yuav tsum tau ntxiv cov khoom siv tooj liab (II) qhov chaw rau co-composition71.