Ua tsaug rau koj tuaj xyuas Nature.com.Qhov browser version koj siv tau txwv CSS kev txhawb nqa.Rau qhov kev paub zoo tshaj plaws, peb xav kom koj siv qhov browser tshiab (lossis lov tes taw Compatibility Hom hauv Internet Explorer).Nyob rau lub sijhawm no, txhawm rau ua kom muaj kev txhawb nqa txuas ntxiv, peb yuav ua rau lub xaib tsis muaj qauv thiab JavaScript.
Ib tug carousel uas qhia peb slides nyob rau tib lub sij hawm.Siv cov nyees khawm dhau los thiab Tom ntej kom txav mus los ntawm peb qhov swb ib zaug, lossis siv cov khawm slider thaum kawg kom txav mus los ntawm peb qhov swb ib zaug.
Additive manufacturing yog hloov txoj kev tshawb fawb thiab industrialists tsim thiab tsim cov khoom siv tshuaj lom neeg kom tau raws li lawv cov kev xav tau tshwj xeeb.Nyob rau hauv daim ntawv no, peb qhia thawj piv txwv ntawm ib tug txaus reactor tsim los ntawm ultrasonic additive manufacturing (UAM) lamination ntawm ib tug khoom hlau ntawv nrog ncaj qha integrated catalytic qhov chaw thiab sensing ntsiab.UAM thev naus laus zis tsis tsuas yog kov yeej ntau qhov kev txwv tam sim no cuam tshuam nrog kev tsim khoom ntxiv ntawm cov tshuaj reactors, tab sis kuj nthuav dav lub peev xwm ntawm cov cuab yeej zoo li no.Ib tug xov tooj ntawm cov tshuaj lom neeg tseem ceeb 1,4-disubstituted 1,2,3-triazole tebchaw tau ua tiav zoo thiab ua kom zoo los ntawm Cu-mediated 1,3-dipolar Huisgen cycloaddition cov tshuaj tiv thaiv siv UAM chemistry chaw.Siv cov khoom tshwj xeeb ntawm UAM thiab kev ua haujlwm tsis tu ncua, cov cuab yeej muaj peev xwm ua kom muaj kev cuam tshuam tsis tu ncua nrog rau muab cov lus pom zoo hauv lub sijhawm los saib xyuas thiab ua kom zoo dua cov tshuaj tiv thaiv.
Vim nws cov txiaj ntsig tseem ceeb ntawm nws cov khoom sib koom ua ke, ntws chemistry yog ib qho tseem ceeb thiab loj hlob hauv ob qho tib si kev kawm thiab kev lag luam vim nws muaj peev xwm los ua kom cov kev xaiv thiab kev ua tau zoo ntawm cov tshuaj synthesis.Qhov no txuas ntxiv los ntawm kev tsim cov organic molecules 1 mus rau cov tshuaj sib txuas 2,3 thiab cov khoom ntuj tsim 4,5,6.Tshaj li 50% ntawm cov tshuaj tiv thaiv hauv cov tshuaj lom neeg thiab tshuaj lag luam tuaj yeem tau txais txiaj ntsig los ntawm kev ntws mus tas li 7.
Nyob rau hauv xyoo tas los no, tau muaj kev loj hlob ntawm cov pab pawg nrhiav los hloov cov iav tsoos los yog cov khoom siv hluav taws xob ntws nrog cov tshuaj "reactors" 8.Kev tsim qauv, kev tsim khoom sai, thiab peb-dimensional (3D) muaj peev xwm ntawm cov txheej txheem no yog qhov muaj txiaj ntsig zoo rau cov neeg uas xav hloov kho lawv cov khoom siv rau ib qho kev cuam tshuam, cov khoom siv, lossis cov xwm txheej.Txog rau tam sim no, txoj haujlwm no tau tsom mus rau yuav luag tshwj xeeb ntawm kev siv polymer-based 3D tshuab luam ntawv xws li stereolithography (SL) 9,10,11, Fused Deposition Modeling (FDM)8,12,13,14 thiab inkjet printing7,15., 16. Qhov tsis muaj kev ntseeg siab thiab muaj peev xwm ntawm cov cuab yeej zoo li no los ua ntau yam tshuaj lom neeg / tshuaj ntsuam xyuas17, 18, 19, 20 yog qhov txwv loj rau kev siv dav dav ntawm AM hauv daim teb no17, 18, 19, 20.
Vim muaj kev siv ntau ntxiv ntawm cov tshuaj lom neeg thiab cov khoom muaj txiaj ntsig zoo txuam nrog AM, cov txheej txheem zoo dua yuav tsum tau tshawb xyuas uas yuav tso cai rau cov neeg siv los tsim cov tshuaj tiv thaiv cov hlab ntsha nrog kev txhim kho chemistry thiab analytical peev xwm.Cov txheej txheem no yuav tsum tso cai rau cov neeg siv xaiv los ntawm ntau lub zog siab lossis cov khoom siv ua haujlwm muaj peev xwm ua haujlwm raws li ntau yam ntawm cov tshuaj tiv thaiv, nrog rau pab txhawb ntau hom kev tshuaj ntsuam xyuas tawm los ntawm lub cuab yeej los pab saib xyuas thiab tswj cov tshuaj tiv thaiv.
Ib qho txheej txheem tsim khoom ntxiv uas tuaj yeem siv los tsim cov tshuaj tiv thaiv kev cai yog Ultrasonic Additive Manufacturing (UAM).Qhov txheej txheem txheej txheej txheej txheej txheej txheej no siv ultrasonic vibrations rau nyias hlau foils los khi lawv ua ke txheej los ntawm txheej nrog tsawg kawg nkaus volumetric cua sov thiab qib siab ntawm cov yas ntws 21, 22, 23. Tsis zoo li feem ntau lwm yam AM technologies, UAM tuaj yeem ncaj qha kev koom ua ke nrog cov khoom tsim tawm, hu ua hybrid manufacturing txheej txheem, nyob rau hauv cov txheej txheem ntawm cov txheej txheem NC los yog txiav txim siab cov txheej txheem ntau lawm. bonded khoom 24, 25. Qhov no txhais tau hais tias tus neeg siv tsis txwv rau cov teeb meem cuam tshuam nrog kev tshem tawm cov khoom qub hauv tsev los ntawm cov kua dej me me, uas feem ntau yog cov hmoov av thiab kua tshuab AM26,27,28.Qhov kev ywj pheej tsim no tseem txuas ntxiv mus rau kev xaiv cov ntaub ntawv muaj - UAM tuaj yeem sib txuas ua ke ntawm cov khoom siv thermally zoo sib xws thiab sib txawv hauv ib kauj ruam txheej txheem.Kev xaiv ntawm cov khoom sib xyaw ua ke dhau ntawm cov txheej txheem melting txhais tau hais tias cov khoom siv thiab tshuaj lom neeg ntawm cov ntawv thov tshwj xeeb tuaj yeem ua tau zoo dua.Ntxiv nrog rau kev sib koom ua ke, lwm qhov tshwm sim uas tshwm sim nrog kev sib txuas ntawm ultrasonic yog qhov siab ntawm cov ntaub ntawv yas ntawm qhov kub tsis tshua muaj 29,30,31,32,33.Qhov tshwj xeeb ntawm UAM no tso cai rau cov khoom siv hluav taws xob / thermal muab tso rau ntawm cov txheej hlau yam tsis muaj kev puas tsuaj.Embedded UAM sensors tuaj yeem pab txhawb kev xa cov ntaub ntawv hauv lub sijhawm los ntawm lub cuab yeej mus rau tus neeg siv los ntawm kev sib xyaw ua ke.
Cov hauj lwm yav dhau los los ntawm cov kws sau ntawv32 tau qhia txog lub peev xwm ntawm UAM txheej txheem los tsim cov qauv hlau 3D microfluidic nrog cov peev xwm ua kom pom tseeb.Cov cuab yeej no tsuas yog siv los saib xyuas lub hom phiaj xwb.Kab lus no nthuav tawm thawj qhov piv txwv ntawm microfluidic chemical reactor tsim los ntawm UAM, ib qho khoom siv uas tsis tsuas yog tswj hwm tab sis kuj ua rau cov tshuaj sib xyaw ua ke nrog cov khoom sib xyaw ua ke catalytic.Cov cuab yeej sib txuas ua ke ntau qhov zoo uas cuam tshuam nrog UAM thev naus laus zis hauv kev tsim cov khoom siv tshuaj 3D, xws li: lub peev xwm los hloov ua tiav 3D tsim ncaj qha los ntawm computer-aided design (CAD) qauv rau hauv cov khoom;multi-material fabrication rau ib tug ua ke ntawm high thermal conductivity thiab catalytic cov ntaub ntawv, raws li zoo raws li thermal sensors embedded ncaj qha ntawm cov reactant kwj rau meej tswj thiab tswj cov tshuaj tiv thaiv kub.Txhawm rau ua kom pom kev ua haujlwm ntawm lub tshuab hluav taws xob, lub tsev qiv ntawv ntawm cov tshuaj tseem ceeb 1,4-disubstituted 1,2,3-triazole tebchaw tau tsim los ntawm tooj liab-catalyzed 1,3-dipolar Huisgen cycloaddition.Txoj haujlwm no qhia txog qhov kev siv cov ntaub ntawv tshawb fawb thiab kev tsim kho tshuab computer tuaj yeem qhib tau tshiab thiab muaj cib fim rau chemistry los ntawm kev tshawb fawb kev kawm.
Tag nrho cov kuab tshuaj thiab cov tshuaj reagents tau yuav los ntawm Sigma-Aldrich, Alfa Aesar, TCI, lossis Fischer Scientific thiab siv yam tsis muaj kev ua kom huv ua ntej.1H thiab 13C NMR spectra kaw ntawm 400 thiab 100 MHz, ntsig txog, tau txais ntawm JEOL ECS-400 400 MHz spectrometer lossis Bruker Avance II 400 MHz spectrometer nrog CDCl3 lossis (CD3)2SO ua hnyav.Txhua qhov kev cuam tshuam tau ua tiav siv Uniqsis FlowSyn flow chemistry platform.
UAM tau siv los tsim txhua yam khoom siv hauv txoj kev tshawb no.Cov thev naus laus zis 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 kho tuaj yeem kawm siv cov ntaub ntawv luam tawm hauv qab no34,35,36,37.Cov cuab yeej siv (Daim duab 1) tau siv los ua haujlwm hnyav 9 kW SonicLayer 4000® UAM system (Fabrisonic, Ohio, USA).Cov ntaub ntawv xaiv rau cov khoom ntws 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 tus neeg sib tw zoo rau tooj liab catalyzed cov tshuaj tiv thaiv thiab yog li siv los ua "txheej txheej hauv microreactor.Al 6061 O yog siv los ua "bulk" khoom., nrog rau cov txheej intercalation siv rau kev tsom xam;intercalation ntawm auxiliary alloy Cheebtsam thiab annealed lub xeev ua ke nrog Cu-110 txheej.pom tias muaj tshuaj lom neeg ruaj khov nrog cov reagents siv hauv qhov haujlwm no.Al 6061 O ua ke nrog Cu-110 kuj suav tias yog cov khoom siv sib xyaw ua ke rau UAM thiab yog li cov khoom tsim nyog rau txoj kev tshawb no38,42.Cov khoom siv no tau teev tseg hauv Table 1 hauv qab no.
Reactor fabrication cov kauj ruam (1) 6061 aluminium alloy substrate (2) Fabrication ntawm qis channel los ntawm cov ntawv ci tooj liab (3) Ntxig cov thermocouples ntawm txheej (4) Upper channel (5) Inlet thiab qhov hluav taws xob (6) Monolithic reactor.
Cov kua dej channel tsim lub tswv yim yog siv txoj hauv kev tortuous kom qhov kev ncua deb mus los ntawm cov kua hauv lub nti thaum tuav tswj cov nti loj.Qhov kev nce ntawm qhov kev ncua deb no yog qhov xav tau kom nce catalyst-reactant lub sijhawm sib cuag thiab muab cov khoom lag luam zoo heev.Cov chips siv 90 ° khoov ntawm qhov kawg ntawm txoj kev ncaj los ua kom muaj kev sib xyaw ua ke hauv cov khoom siv 44 thiab ua kom lub sijhawm sib cuag ntawm cov kua nrog rau saum npoo (catalyst).Txhawm rau txhim kho qhov sib xyaw ua ke uas tuaj yeem ua tiav, tus qauv tsim ntawm lub reactor suav nrog ob lub reactant inlets ua ke hauv Y-kev sib txuas ua ntej nkag mus rau qhov sib xyaw coil seem.Qhov thib peb nkag, uas hla qhov ntws ib nrab los ntawm nws qhov chaw nyob, suav nrog hauv txoj kev npaj rau yav tom ntej ntau theem kev sib txuam.
Tag nrho cov channel muaj square profile (tsis muaj taper kaum), uas yog qhov tshwm sim ntawm lub sij hawm CNC milling siv los tsim cov channel geometry.Cov channel qhov ntev yog xaiv los muab lub siab (rau microreactor) volumetric tawm los, tseem me me txaus los pab txhawb kev sib cuam tshuam nrog rau saum npoo (catalysts) rau feem ntau ntawm cov kua nws muaj.Qhov loj me uas tsim nyog yog raws li cov kws sau ntawv cov kev paub dhau los nrog cov khoom siv hlau-kua tshuaj tiv thaiv.Qhov ntev ntawm cov channel kawg yog 750 µm x 750 µm thiab tag nrho cov reactor ntim yog 1 ml.Ib tug built-in connector (1/4 "-28 UNF xov) muaj nyob rau hauv tus tsim kom tso cai yooj yim interfacing ntawm cov cuab yeej nrog coj mus muag chemistry khoom.Channel loj yog txwv los ntawm cov thickness ntawm cov ntawv ci, nws cov khoom siv kho tshuab, thiab kev sib txuas tsis siv nrog ultrasonics.Ntawm qhov dav dav 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, qhov twg qhov dav ntawm 750 µm yuav tsis ua rau sag.
Cov duab (square) ntawm cov channel yog txiav txim siab siv lub square cutter.Cov duab thiab qhov loj ntawm cov channel tuaj yeem hloov pauv 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 channel nkhaus nrog lub cuab yeej 125 µm tuaj yeem pom hauv Monaghan45.Thaum cov ntawv ci txheej yog siv tiaj, daim ntawv thov ntawm cov ntawv ci rau cov channel yuav muaj lub tiaj tus (square) nto.Hauv txoj haujlwm no, ib qho square contour tau siv los khaws cov channel symmetry.
Thaum lub sij hawm ib tug programmed ncua nyob rau hauv ntau lawm, thermocouple kub sensors (hom K) yog ua ncaj qha mus rau hauv lub ntaus ntawv ntawm lub sab sauv thiab qis channel pawg (Fig. 1 - theem 3).Cov thermocouples no tuaj yeem tswj qhov ntsuas kub ntawm -200 txog 1350 ° C.
Cov txheej txheem hlau deposition yog ua los ntawm UAM horn siv hlau ntawv 25.4 hli dav thiab 150 microns tuab.Cov khaubncaws sab nraud povtseg ntawm cov ntawv ci no txuas nrog hauv cov kab uas nyob ib sab kom npog tag nrho thaj chaw tsim;qhov loj ntawm cov khoom tso tawm yog loj dua qhov khoom kawg raws li cov txheej txheem rho tawm tsim cov duab huv huv kawg.CNC machining yog siv los tshuab cov khoom siv sab nraud thiab sab hauv, uas ua rau lub ntsej muag tiav ntawm cov khoom siv thiab cov channel sib xws rau cov cuab yeej xaiv thiab CNC txheej txheem tsis (hauv qhov piv txwv no, txog 1.6 µm Ra).Nruam, nruam ultrasonic cov khoom txau thiab machining cycles yog siv thoob plaws hauv lub cuab yeej tsim cov txheej txheem los xyuas kom meej qhov tseeb qhov tseeb yog tswj thiab qhov tiav tiav raws li CNC nplua milling precision qib.Qhov dav ntawm cov channel siv rau cov cuab yeej no me me kom ntseeg tau tias cov khoom siv ntawv ci tsis "sag" hauv cov kua dej, yog li cov channel muaj ib qho square cross seem.Qhov muaj peev xwm ntawm cov khoom siv foil thiab qhov tsis sib xws ntawm UAM txheej txheem tau txiav txim siab sim los ntawm tus khub tsim khoom (Fabrisonic LLC, USA).
Cov kev tshawb fawb tau pom tias ntawm qhov sib txuas 46, 47 ntawm UAM compound muaj me ntsis diffusion ntawm cov ntsiab lus tsis muaj kev kho cua sov ntxiv, yog li rau cov khoom siv hauv kev ua haujlwm no, Cu-110 txheej tseem txawv ntawm Al 6061 txheej thiab hloov pauv ntau.
Nruab ib lub pre-calibrated back pressure regulator (BPR) ntawm 250 psi (1724 kPa) downstream ntawm lub reactor thiab tso dej los ntawm lub reactor ntawm tus nqi ntawm 0.1 mus rau 1 ml min-1.Lub reactor siab tau saib xyuas siv FlowSyn siab transducer ua rau hauv lub kaw lus kom ntseeg tau tias lub kaw lus tuaj yeem tswj lub siab tsis tu ncua.Muaj peev xwm kub gradients nyob rau hauv lub ndlwg reactor tau sim los ntawm kev nrhiav kev sib txawv ntawm cov thermocouples ua rau hauv lub reactor thiab cov thermocouples ua rau hauv lub tshav kub phaj ntawm FlowSyn nti.Qhov no yog ua tiav los ntawm kev hloov qhov programmed hotplate kub ntawm 100 thiab 150 ° C hauv 25 ° C nce ntxiv thiab saib xyuas qhov sib txawv ntawm qhov programmed thiab kaw qhov kub.Qhov no tau ua tiav siv tc-08 cov ntaub ntawv logger (PicoTech, Cambridge, UK) thiab nrog PicoLog software.
Cov xwm txheej rau cycloaddition cov tshuaj tiv thaiv ntawm phenylacetylene thiab iodoethane yog optimized (Scheme 1-Cycloaddition of phenylacetylene thiab iodoethane, Scheme 1-Cycloaddition of phenylacetylene thiab iodoethane).Qhov kev ua kom zoo dua no tau ua los ntawm kev siv tag nrho cov qauv tsim ntawm kev sim (DOE) mus kom ze, siv qhov kub thiab qhov chaw nyob raws li qhov sib txawv thaum kho cov alkyne: azide piv ntawm 1: 2.
Kev sib cais ntawm sodium azide (0.25 M, 4: 1 DMF: H2O), iodoethane (0.25 M, DMF), thiab phenylacetylene (0.125 M, DMF) tau npaj.Ib 1.5 ml aliquot ntawm txhua qhov kev daws yog tov thiab pumped los ntawm lub reactor ntawm qhov xav tau txaus tus nqi thiab kub.Cov lus teb ntawm tus qauv raug coj los ua qhov sib piv ntawm thaj chaw ncov ntawm cov khoom triazole rau cov khoom pib ntawm phenylacetylene thiab tau txiav txim siab siv cov kua chromatography (HPLC).Rau kev txheeb xyuas qhov sib xws, tag nrho cov tshuaj tiv thaiv tau muab tam sim ntawd tom qab cov tshuaj tiv thaiv sib tov tawm ntawm lub reactor.Cov parameter ranges xaiv rau optimization yog qhia nyob rau hauv Table 2.
Tag nrho cov qauv tau txheeb xyuas siv Chromaster HPLC system (VWR, PA, USA) uas muaj lub twj tso kua mis quaternary, kem qhov cub, qhov sib txawv wavelength UV ntes thiab autosampler.Kem yog Equivalence 5 C18 (VWR, PA, USA), 4.6 x 100 mm, 5 µm particle loj, khaws cia ntawm 40 ° C.Cov kuab tshuaj yog isocratic methanol: dej 50:50 ntawm tus nqi ntws ntawm 1.5 ml·min-1.Kev txhaj tshuaj ntim yog 5 μl thiab lub ntsuas ntsuas wavelength yog 254 nm.Qhov % ncov cheeb tsam rau cov qauv DOE yog xam los ntawm qhov chaw siab tshaj ntawm cov khoom seem alkyne thiab triazole nkaus xwb.Qhov kev taw qhia ntawm cov khoom pib ua rau nws muaj peev xwm txheeb xyuas qhov sib thooj peaks.
Kev sib koom ua ke ntawm cov txiaj ntsig ntawm kev tshuaj ntsuam xyuas lub tshuab hluav taws xob nrog MODDE DOE software (Umetrics, Malmö, Sweden) tso cai rau kev txheeb xyuas qhov tseeb ntawm cov txiaj ntsig thiab kev txiav txim siab ntawm qhov kev pom zoo ntawm cov tshuaj tiv thaiv rau qhov cycloaddition no.Khiav lub built-in optimizer thiab xaiv tag nrho cov qauv tseem ceeb cov ntsiab lus tsim ib txheej ntawm cov tshuaj tiv thaiv tej yam kev mob tsim los ua kom lub ncov cheeb tsam ntawm cov khoom thaum txo lub ncov cheeb tsam rau acetylene feedstock.
Oxidation ntawm tooj liab nyob rau hauv lub catalytic cov tshuaj tiv thaiv chamber tau ua tiav siv cov tshuaj hydrogen peroxide (36%) ntws los ntawm cov tshuaj tiv thaiv chamber (ntws tus nqi = 0.4 ml min-1, lub sij hawm nyob = 2.5 min) ua ntej synthesis ntawm txhua triazole compound.tsev qiv ntawv.
Thaum qhov kev pom zoo ntawm cov xwm txheej tau raug txiav txim siab, lawv tau siv rau ntau yam ntawm acetylene thiab haloalkane derivatives kom tso cai muab tso ua ke ntawm cov tsev qiv ntawv me me, yog li tsim kom muaj peev xwm siv cov xwm txheej no mus 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).Aliquots ntawm 3 ml ntawm txhua qhov kev daws tau sib xyaw thiab tso tawm los ntawm lub reactor ntawm tus nqi ntawm 75 µl / min thiab qhov kub ntawm 150 ° C.Tag nrho cov ntim tau sau rau hauv ib lub vial thiab diluted nrog 10 ml ntawm ethyl acetate.Cov qauv tov yog ntxuav nrog 3 x 10 ml ntawm dej.Cov khaubncaws sab nraud povtseg tau muab tso ua ke thiab muab rho tawm nrog 10 ml ethyl acetate, tom qab ntawd cov txheej txheem organic tau ua ke, ntxuav nrog 3 × 10 ml brine, qhuav dhau MgSO 4 thiab lim, ces cov kuab tshuaj tau muab tshem tawm hauv lub tshuab nqus tsev.Cov qauv raug ntxuav los ntawm silica gel kem chromatography siv ethyl acetate ua ntej kev soj ntsuam los ntawm kev sib xyaw ntawm HPLC, 1H NMR, 13C NMR thiab siab daws teeb meem loj spectrometry (HR-MS).
Tag nrho cov spectra tau txais los ntawm kev siv Thermofischer Precision Orbitrap 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 silica daim hlau nrog aluminium substrate.Cov phiajcim tau pom nrog UV teeb (254 nm) lossis vanillin staining thiab cua sov.
Tag nrho cov qauv tau soj ntsuam siv lub tshuab VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) nruab nrog lub tshuab ntsuas hluav taws xob, lub twj tso kua mis binary nrog lub qhov cub thiab ib lub tshuab ntsuas wavelength.ACE Equivalence 5 C18 kem (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland) tau siv.
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.Kem tau khaws cia ntawm 40 ° C.Lub wavelength ntawm lub ntes yog 254 nm.
Qhov % ncov cheeb tsam ntawm tus qauv yog xam los ntawm lub ncov cheeb tsam ntawm cov residual alkyne, cov khoom triazole nkaus xwb, thiab cov kev taw qhia ntawm cov khoom pib ua rau nws muaj peev xwm txheeb xyuas qhov sib thooj peaks.
Tag nrho cov qauv tau txheeb xyuas siv Thermo iCAP 6000 ICP-OES.Tag nrho cov qauv calibration 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 ib qho kev daws ntawm 5% DMF thiab 2% HNO3, thiab tag nrho cov qauv tau diluted 20 zaug nrog cov qauv tov ntawm DMF-HNO3.
UAM siv ultrasonic hlau vuam raws li ib txoj hauv kev koom nrog cov ntawv hlau siv los tsim kev sib dhos zaum kawg.Ultrasonic hlau vuam siv cov cuab yeej vibrating hlau (hu ua horn lossis ultrasonic horn) siv lub siab rau cov ntawv ci / yav dhau los sib sau ua ke kom sib koom ua ke / yav dhau los sib koom ua ke los ntawm vibrating cov khoom.Rau kev ua haujlwm tas mus li, cov sonotrode muaj cov duab cylindrical thiab yob hla cov khoom siv, gluing tag nrho cheeb tsam.Thaum siv lub siab thiab kev co, cov oxides ntawm cov khoom tuaj yeem tawg.Lub siab tsis tu ncua thiab kev co tuaj yeem ua rau kev puas tsuaj ntawm roughness ntawm cov khoom 36 .Kaw kev sib cuag nrog lub zos tshav kub thiab siab ces ua rau ib tug ruaj theem daim ntawv cog lus ntawm cov khoom interfaces;nws tuaj yeem txhawb kev sib koom ua ke los ntawm kev hloov lub zog saum npoo 48.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 los ntawm lwm yam khoom siv ntxiv.Qhov no tso cai rau kev sib txuas ncaj qha (piv txwv li tsis muaj kev hloov kho saum npoo, cov khoom ntim lossis cov nplaum) ntawm ob peb txheej ntawm cov khoom sib txawv rau hauv ib qho kev sib koom ua ke.
Qhov thib ob qhov txiaj ntsig zoo rau CAM yog qhov siab ntawm cov yas ntws tau pom nyob rau hauv cov ntaub ntawv hlau txawm tias qhov kub thiab txias, piv txwv li zoo hauv qab lub melting point ntawm cov khoom siv hlau.Kev sib xyaw ua ke ntawm ultrasonic vibrations thiab siab ua rau muaj qib siab ntawm cov qoob loo hauv zos ciam teb thiab recrystallization yam tsis muaj qhov kub thiab txias nce ib txwm cuam tshuam nrog cov ntaub ntawv loj.Thaum lub sij hawm tsim ntawm lub rooj sib txoos zaum kawg, qhov tshwm sim no tuaj yeem siv los embed active thiab passive Cheebtsam ntawm cov khaubncaws sab nraud povtseg ntawm hlau ntawv, txheej los ntawm txheej.Cov ntsiab lus xws li optical fiber 49, reinforcement 46, electronics 50 thiab thermocouples (qhov haujlwm no) tau ua tiav zoo rau hauv UAM cov qauv tsim kom muaj kev sib koom ua ke thiab kev sib koom ua ke.
Hauv kev ua haujlwm no, ob qho tib si sib txawv ntawm cov khoom siv sib txawv thiab UAM intercalation peev xwm tau siv los tsim cov microreactor zoo tagnrho rau catalytic kub tswj.
Muab piv rau palladium (Pd) thiab lwm yam siv hlau catalysts, Cu catalysis muaj ntau qhov zoo: (i) Kev lag luam, Cu yog pheej yig dua li ntau lwm cov hlau siv hauv catalysis thiab yog li qhov kev xaiv zoo nkauj rau kev lag luam tshuaj (ii) qhov ntau ntawm Cu-catalyzed cross-coupling cov tshuaj tiv thaiv yog nthuav tawm thiab zoo li me ntsis 515, 3. yzed cov tshuaj tiv thaiv ua haujlwm zoo thaum tsis muaj lwm yam ligands.Cov ligands no feem ntau yooj yim thiab pheej yig.Yog tias xav tau, qhov uas 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, xws li Sonogashira's bimetallic catalyzed coupling thiab cycloaddition nrog azides (nias chemistry) (v) Cu kuj tseem tuaj yeem txhawb cov arylation ntawm qee cov tshuaj tiv thaiv hauv Ullophile.
Tsis ntev los no, piv txwv ntawm heterogenization ntawm tag nrho cov kev tshwm sim no nyob rau hauv lub xub ntiag ntawm Cu(0) tau tshwm sim.Qhov no feem ntau yog los ntawm kev lag luam kws tshuaj thiab kev loj hlob tsom mus rau kev rov qab thiab rov siv cov hlau catalysts55,56.
Qhov 1,3-dipolar cycloaddition cov tshuaj tiv thaiv ntawm acetylene thiab azide rau 1,2,3-triazole, thawj zaug tau npaj los ntawm Huisgen hauv xyoo 1960s57, suav hais tias yog ib qho kev sib tham ua qauv qhia.Qhov tshwm sim 1,2,3 triazole fragments yog qhov tshwj xeeb tshaj yog cov tshuaj pharmacophore hauv kev tshawb nrhiav tshuaj vim lawv cov kev siv tshuaj lom neeg thiab siv ntau yam tshuaj 58 .
Cov tshuaj tiv thaiv no tau txais kev saib xyuas tshiab thaum Sharpless thiab lwm tus tau qhia txog lub tswv yim ntawm "nias chemistry" 59.Lo lus "nias chemistry" yog siv los piav qhia txog cov txheej txheem muaj zog thiab xaiv cov tshuaj tiv thaiv rau kev sib txuas ceev ceev ntawm cov tebchaw tshiab thiab cov tsev qiv ntawv sib txuas siv heteroatomic bonding (CXC) 60.Qhov kev thov hluavtaws ntawm cov tshuaj tiv thaiv no yog vim muaj cov txiaj ntsig siab txuam nrog lawv.Cov xwm txheej yog qhov yooj yim, tiv thaiv oxygen thiab dej, thiab cov khoom sib cais yog yooj yim61.
Classical 1,3-dipole Huisgen cycloaddition tsis poob rau hauv qeb "nias chemistry".Txawm li cas los xij, Medal thiab Sharpless qhia tau hais tias qhov kev tshwm sim azide-alkyne coupling no dhau 107-108 nyob rau hauv lub xub ntiag ntawm Cu(I) piv rau ib qho tseem ceeb acceleration nyob rau hauv tus nqi ntawm non-catalytic 1,3-dipolar cycloaddition 62,63.Cov tshuaj tiv thaiv siab heev no tsis tas yuav muaj kev tiv thaiv cov pab pawg lossis cov tshuaj tiv thaiv hnyav thiab muab kev hloov pauv thiab kev xaiv yuav luag rau 1,4-disubstituted 1,2,3-triazoles (anti-1,2,3-triazoles) dhau sijhawm (Fig. 3).
Isometric cov txiaj ntsig ntawm cov pa thiab tooj liab-catalyzed Huisgen cycloadditions.Cu(I)-catalyzed Huisgen cycloadditions muab 1,4-disubstituted 1,2,3-triazoles, thaum thermally induced Huisgen cycloadditions feem ntau muab 1,4- thiab 1,5-triazoles ib 1: 1 sib tov ntawm azole stereoisomers.
Cov txheej txheem feem ntau cuam tshuam nrog txo qhov chaw ruaj khov ntawm Cu(II), xws li txo CuSO4 lossis Cu(II)/Cu(0) compound nrog sodium ntsev.Piv nrog rau lwm cov hlau catalyzed cov tshuaj tiv thaiv, kev siv Cu(I) muaj qhov zoo ntawm kev pheej yig thiab yooj yim los daws.
Kinetic thiab isotopic kev tshawb fawb los ntawm Worrell et al.65 tau qhia tias nyob rau hauv cov ntaub ntawv ntawm lub davhlau ya nyob twg alkynes, ob qhov sib npaug ntawm tooj liab yog koom tes rau hauv activating reactivity ntawm txhua molecule hais txog azide.Lub tswv yim txheej txheem pib los ntawm ib tug rau-tus tswv cuab tooj liab nplhaib tsim los ntawm kev sib koom tes ntawm azide rau σ-bonded tooj liab acetylide nrog π-bonded tooj liab raws li ib tug ruaj khov pub ligand.Copper triazolyl derivatives yog tsim los ntawm lub nplhaib contraction ua raws li proton decomposition los tsim 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 nrog cov cuab yeej tshuaj ntsuam xyuas rau hauv cov tshuab no rau kev saib xyuas cov txheej txheem ntawm lub sijhawm hauv situ66,67.UAM tau ua pov thawj tias yog ib txoj hauv kev tsim nyog rau kev tsim thiab tsim cov 3D flow reactors los ntawm catalytically active, thermally conductive cov ntaub ntawv nrog ncaj qha embedded sensing ntsiab (Fig. 4).
Aluminium-tooj ​​liab txaus reactor tsim los ntawm ultrasonic additive manufacturing (UAM) nrog ib tug complex internal channel qauv, built-in thermocouples thiab ib tug catalytic tshuaj chamber.Txhawm rau pom cov kua dej sab hauv, cov qauv pob tshab uas siv stereolithography kuj pom.
Txhawm rau kom ntseeg tau tias cov reactors raug tsim rau yav tom ntej cov tshuaj tiv thaiv cov organic, cov kuab tshuaj yuav tsum muaj kev nyab xeeb sov siab tshaj lawv qhov kub kub;lawv raug ntsuas thiab ntsuas kub.Kev ntsuas siab pom tau tias lub kaw lus tswj tau qhov ruaj khov thiab qhov siab tsis tu ncua txawm tias qhov siab siab hauv qhov system (1.7 MPa).Kev ntsuam xyuas hydrostatic tau ua nyob rau hauv chav tsev kub siv H2O ua kua.
Txuas lub built-in (Daim duab 1) thermocouple rau qhov ntsuas kub cov ntaub ntawv logger pom tias qhov ntsuas kub ntawm thermocouple yog 6 ° C (± 1 ° C) qis dua qhov programmed kub hauv FlowSyn system.Feem ntau, 10 ° C nce hauv qhov kub thiab txias ob npaug ntawm cov tshuaj tiv thaiv, yog li qhov kub ntawm qhov sib txawv ntawm ob peb degrees tuaj yeem hloov pauv cov tshuaj tiv thaiv zoo heev.Qhov sib txawv no yog vim qhov kub poob thoob plaws hauv RPV vim qhov siab thermal diffusivity ntawm cov khoom siv hauv kev tsim khoom.Qhov no thermal drift yog tas li thiab yog li ntawd yuav tsum tau coj mus rau hauv tus account thaum teeb tsa cov cuab yeej los xyuas kom meej qhov kub thiab txias tau mus txog thiab ntsuas thaum lub sij hawm cov tshuaj tiv thaiv.Yog li, lub cuab yeej saib xyuas online no ua rau muaj kev tswj xyuas nruj ntawm cov tshuaj tiv thaiv kub thiab ua rau muaj kev ua kom zoo dua qub thiab txhim kho cov kev mob zoo.Cov sensors no tseem tuaj yeem siv los txheeb xyuas cov kev tawm tsam exothermic thiab tiv thaiv kev khiav tawm hauv cov txheej txheem loj.
Lub reactor nthuav tawm hauv daim ntawv 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) Kev kov yeej cov teeb meem sau tseg uas cuam tshuam nrog kev ua cov tooj liab lossis txhuas alloy (ii) txhim kho cov kev daws teeb meem sab hauv piv rau cov hmoov av laser melting (PBF) 5 txoj kev (M 6 kev ntxhib los mos) thiab cov txheej txheem kev ntxhib los mos (PBF) 6. iii) kev ua haujlwm qis dua, uas ua rau muaj kev sib txuas ncaj qha rau 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 rau ntau yam organic solvents17,19.
Lub functionality ntawm lub reactor tau pom los ntawm ib tug series ntawm tooj liab-catalyzed alkinazide cycloaddition tshwm sim nyob rau hauv tas li ntawd mus tej yam kev mob (Fig. 2).Lub ultrasonic luam copper reactor qhia nyob rau hauv daim duab.4 tau koom ua ke nrog kev lag luam khiav lag luam thiab siv los ua ke lub tsev qiv ntawv azide ntawm ntau yam 1,4-disubstituted 1,2,3-triazoles siv cov tshuaj tiv thaiv kub ntawm acetylene thiab alkyl pawg halides nyob rau hauv lub xub ntiag ntawm sodium chloride (Fig. 3).Kev siv txoj hauv kev txuas mus ntxiv kom txo tau cov teeb meem kev nyab xeeb uas tuaj yeem tshwm sim hauv cov txheej txheem batch, txij li cov tshuaj tiv thaiv no ua rau muaj kev cuam tshuam ntau heev thiab muaj kev phom sij azide intermediates [317], [318].Thaum xub thawj, cov tshuaj tiv thaiv tau ua kom zoo rau cycloaddition ntawm phenylacetylene thiab iodoethane (Scheme 1 - Cycloaddition ntawm phenylacetylene thiab iodoethane) (saib daim duab 5).
(Sab laug sab laug) Schematic ntawm kev teeb tsa siv los sib koom ua ke 3DP reactor rau hauv qhov system ntws (sab sauv sab xis) tau los ntawm kev ua kom zoo (qis dua) cov tswv yim ntawm Huisgen 57 cycloaddition scheme ntawm phenylacetylene thiab iodoethane rau optimization thiab qhia qhov optimized conversion tus nqi ntawm cov tshuaj tiv thaiv.
Los ntawm kev tswj lub sij hawm nyob ntawm cov reactants nyob rau hauv lub catalytic seem ntawm lub reactor thiab ua tib zoo saib xyuas cov tshuaj tiv thaiv kub nrog ib tug ncaj qha integrated thermocouple sensor, cov tshuaj tiv thaiv tej yam kev mob yuav ua tau sai thiab meej optimized nrog tsawg kawg ntawm lub sij hawm thiab cov ntaub ntawv.Nws tau pom sai sai tias qhov kev hloov pauv siab tshaj plaws tau ua tiav siv lub sijhawm nyob ntawm 15 feeb thiab qhov ntsuas kub ntawm 150 ° C.Nws tuaj yeem pom los ntawm cov phiaj xwm coefficient ntawm MODDE software uas ob qho tib si lub sijhawm nyob thiab qhov kub thiab txias yog suav tias yog cov xwm txheej tseem ceeb ntawm cov qauv.Khiav lub built-in optimizer siv cov kev xaiv no tsim ib txheej ntawm cov tshuaj tiv thaiv tej yam kev mob tsim los ua kom cov khoom siab tshaj plaws hauv cheeb tsam thaum txo qis pib cov khoom siab tshaj qhov chaw.Qhov kev ua kom zoo no ua rau muaj 53% kev hloov pauv ntawm cov khoom triazole, uas yog raws nraim cov qauv kev kwv yees ntawm 54%.