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Carousel yana nuna nunin faifai guda uku a lokaci guda.Yi amfani da maɓallan da suka gabata da na gaba don matsawa ta cikin nunin faifai guda uku a lokaci ɗaya, ko amfani da maɓallan maɓalli a ƙarshen don matsawa ta cikin nunin faifai uku a lokaci ɗaya.
Ƙarfafa masana'antu yana canza yadda masu bincike da masana'antu ke tsarawa da kera na'urorin sinadarai don biyan takamaiman bukatunsu.A cikin wannan takarda, mun bayar da rahoton misali na farko na kwarara reactor kafa ta ultrasonic ƙari masana'antu (UAM) lamination na wani m karfe takardar tare da kai tsaye hadedde catalytic sassa da ji abubuwa.Fasahar UAM ba wai kawai ta shawo kan yawancin gazawar da ke da alaƙa a halin yanzu tare da haɓaka masana'antar sarrafa sinadarai ba, har ma tana faɗaɗa ƙarfin irin waɗannan na'urori.An sami nasarar haɓaka adadin abubuwan 1,4-dipolar 1,2,3-triazole mahadi da haɓakawa ta hanyar Cu-mediated 1,3-dipolar Huisgen cycloaddition reaction ta amfani da kayan aikin UAM.Yin amfani da keɓaɓɓen kaddarorin UAM da ci gaba da sarrafa kwarara, na'urar tana iya haɓaka halayen da ke gudana tare da samar da martani na ainihi don saka idanu da haɓaka halayen.
Saboda gagarumin fa'idarsa akan takwaransa mai girma, ilimin kimiyyar yawo yana da mahimmanci kuma filin girma a cikin tsarin ilimi da masana'antu saboda ikonsa na haɓaka zaɓi da ingancin haɗin sinadarai.Wannan ya haɓaka daga samuwar ƙwayoyin ƙwayoyin cuta masu sauƙi1 zuwa magungunan magunguna2,3 da samfuran halitta4,5,6.Sama da kashi 50% na halayen a cikin ingantattun sinadarai da masana'antar harhada magunguna na iya amfana daga ci gaba da gudana7.
A cikin 'yan shekarun nan, an sami ci gaba na ƙungiyoyi masu neman maye gurbin gilashin gargajiya ko kayan aikin sinadarai masu gudana tare da "reactors" masu daidaitawa.Ƙirar ƙira, ƙirar ƙira mai sauri, da ikon girma uku (3D) na waɗannan hanyoyin suna da amfani ga waɗanda ke son keɓance na'urorinsu don takamaiman saitin halayen, na'urori, ko yanayi.Har zuwa yau, wannan aikin ya mayar da hankali ne kawai akan amfani da fasaha na bugu na 3D na polymer kamar su stereolithography (SL) 9,10,11, Fused Deposition Modeling (FDM) 8,12,13,14 da inkjet printing7,15., 16. Rashin aminci da iyawar irin waɗannan na'urori don yin nau'ikan halayen halayen / nazari17, 18, 19, 20 shine babban abin iyakancewa ga fa'idar aikace-aikacen AM a cikin wannan filin17, 18, 19, 20.
Saboda karuwar amfani da sinadarai masu gudana da kyawawan kaddarorin da ke da alaƙa da AM, ana buƙatar bincika ingantattun dabaru waɗanda za su ba masu amfani damar ƙirƙira tasoshin amsawar kwarara tare da ingantattun sinadarai da damar nazari.Waɗannan hanyoyin ya kamata su ba masu amfani damar zaɓar daga kewayon ƙarfin ƙarfi ko kayan aiki waɗanda ke iya aiki a ƙarƙashin yanayi mai faɗi da yawa, da kuma sauƙaƙe nau'ikan fitowar nazari daban-daban daga na'urar don ba da damar saka idanu da sarrafa abin da ya faru.
Daya ƙari masana'antu tsari da za a iya amfani da su bunkasa al'ada sinadaran reactors ne Ultrasonic Additive Manufacturing (UAM).Wannan m-jihar takardar lamination hanya shafi ultrasonic vibrations zuwa bakin ciki karfe foils to bond su tare Layer da Layer da kadan volumetric dumama da kuma wani babban mataki na filastik ya kwarara 21, 22, 23. Ba kamar mafi sauran AM fasahar, UAM za a iya kai tsaye hadedde tare da subtractive samar, da aka sani da matasan masana'antu tsari, a cikin abin da lokaci-lokaci a-wuri na lamba iko, da Laser siffar da lokaci-lokaci in-wuri na lamba iko (CNC) 23 Layer na milling 21. yana nufin cewa mai amfani bai iyakance ga matsalolin da ke tattare da cire ragowar kayan gini na asali daga ƙananan tashoshi na ruwa ba, wanda shine sau da yawa a cikin foda da tsarin ruwa AM26,27,28.Wannan 'yancin ƙira kuma ya ƙara zuwa zaɓin kayan da ake samu - UAM na iya haɗa haɗaɗɗun abubuwan da ke kama da yanayin zafi a cikin mataki guda ɗaya.Zaɓin haɗin kayan abu fiye da tsarin narkewa yana nufin cewa buƙatun inji da sinadarai na takamaiman aikace-aikace na iya zama mafi dacewa.Baya ga m bonding, wani sabon abu da ke faruwa tare da ultrasonic bonding ne high fluidity na filastik kayan a in mun gwada da low yanayin zafi29,30,31,32,33.Wannan siffa ta musamman ta UAM tana ba da damar sanya abubuwa na inji / thermal a sanya tsakanin yadudduka na ƙarfe ba tare da lalacewa ba.Abubuwan na'urori masu auna firikwensin UAM na iya sauƙaƙe isar da bayanan ainihin lokaci daga na'urar zuwa mai amfani ta hanyar haɗaɗɗiyar nazari.
Ayyukan da marubuta32 suka yi a baya sun nuna ikon tsarin UAM don ƙirƙirar sifofin microfluidic na 3D na ƙarfe tare da ikon ganewa.Wannan na'urar don dalilai ne na saka idanu kawai.Wannan labarin yana gabatar da misali na farko na reactor sinadarai na microfluidic wanda UAM ke ƙera, na'ura ce mai aiki wacce ba kawai sarrafawa ba amma kuma tana haifar da haɗin sinadarai tare da kayan haɗin kai na tsari.Na'urar ta haɗu da fa'idodi da yawa waɗanda ke da alaƙa da fasahar UAM a cikin kera na'urorin sinadarai na 3D, kamar: ikon juyar da cikakkiyar ƙirar 3D kai tsaye daga ƙirar ƙirar komputa (CAD) mai taimakon kwamfuta zuwa samfur;Ƙirƙirar abubuwa da yawa don haɗuwa da haɓakar haɓakar zafi mai ƙarfi da kayan haɓakawa, kazalika da na'urori masu auna zafin jiki waɗanda ke haɗa kai tsaye tsakanin rafukan masu amsawa don daidaitaccen sarrafawa da sarrafa yanayin zafin jiki.Don nuna aikin reactor, ɗakin karatu na mahimmancin magunguna na 1,4-disustituted 1,2,3-triazole mahadi an haɗa shi ta hanyar jan ƙarfe-catalyzed 1,3-dipolar Huisgen cycloaddition.Wannan aikin yana nuna yadda yin amfani da kimiyyar kayan aiki da ƙira ta hanyar kwamfuta za ta iya buɗe sabbin damammaki da dama ga ilimin sunadarai ta hanyar bincike na tsaka-tsaki.
An sayi duk abubuwan kaushi da reagents daga Sigma-Aldrich, Alfa Aesar, TCI, ko Fischer Scientific kuma an yi amfani da su ba tare da tsarkakewa ba.1H da 13C NMR spectra da aka yi rikodin a 400 da 100 MHz, bi da bi, an samu su a kan spectrometer JEOL ECS-400 400 MHz ko Bruker Avance II 400 MHz spectrometer tare da CDCl3 ko (CD3)2SO a matsayin sauran ƙarfi.An yi duk halayen ta amfani da dandalin Uniqsis FlowSyn.
An yi amfani da UAM don ƙirƙira duk na'urori a cikin wannan binciken.An ƙirƙira fasahar a cikin 1999 kuma cikakkun bayanan fasaha, sigogin aiki da ci gaba tun lokacin da aka ƙirƙira ta ana iya yin nazari ta amfani da waɗannan kayan da aka buga34,35,36,37.An aiwatar da na'urar (Fig. 1) ta amfani da tsarin aiki mai nauyi 9 kW SonicLayer 4000® UAM (Fabrisonic, Ohio, USA).Abubuwan da aka zaɓa don na'urar kwarara sune Cu-110 da Al 6061. Cu-110 yana da babban abun ciki na jan karfe (mafi ƙarancin 99.9% jan ƙarfe), yana mai da shi ɗan takara mai kyau don halayen jan ƙarfe catalyzed kuma saboda haka ana amfani dashi azaman "launi mai aiki a cikin microreactor.Ana amfani da Al 6061 O azaman kayan “kauri”., da kuma tsaka-tsakin tsaka-tsakin da aka yi amfani da shi don bincike;intercalation na karin gami aka gyara da annealed jihar a hade tare da Cu-110 Layer.an gano yana da kwanciyar hankali tare da reagents da aka yi amfani da su a cikin wannan aikin.Al 6061 O a hade tare da Cu-110 kuma ana ɗaukarsa azaman haɗin kayan haɗin gwiwa don UAM kuma saboda haka abu ne mai dacewa don wannan binciken38,42.An jera waɗannan na'urori a cikin Tebur na 1 a ƙasa.
Matakan ƙirƙira Reactor (1) 6061 aluminum alloy substrate (2) Ƙirƙirar ƙananan tashoshi daga foil tagulla (3) Shigar da ma'aunin zafi da sanyio tsakanin yadudduka (4) Tashar ta sama (5) Mai shiga da fitarwa (6) Monolithic reactor.
Falsafar ƙirar tashar ruwa ita ce a yi amfani da tafarki mai banƙyama don ƙara nisan tafiya da ruwan ke cikin guntu yayin da yake riƙe girman guntu mai iya sarrafawa.Wannan haɓakar nisa yana da kyawawa don ƙara lokacin tuntuɓar mai ƙara kuzari da samar da kyakkyawan amfanin samfur.Chips ɗin suna amfani da lanƙwasa 90° a ƙarshen madaidaiciyar hanya don haifar da haɗaɗɗiyar haɗe-haɗe a cikin na'urar44 kuma ƙara lokacin hulɗar ruwan tare da saman (mai kara kuzari).Don ƙara haɓaka haɗakar da za a iya samu, ƙirar reactor ta ƙunshi inlets masu amsawa guda biyu waɗanda aka haɗa a cikin haɗin Y kafin shigar da sashin na'ura mai haɗawa.Ƙofar shiga ta uku, wacce ta ratsa rabin hanyar zama, tana cikin shirin don haɓaka halayen halayen matakai da yawa na gaba.
Duk tashoshi suna da bayanin martaba mai murabba'i (babu madaidaicin kusurwa), wanda shine sakamakon milling na CNC na lokaci-lokaci da ake amfani da shi don ƙirƙirar geometry ta tashar.An zaɓi girman tashoshi don samar da yawan amfanin ƙasa mai girma (na microreactor), duk da haka ƙananan isa don sauƙaƙe hulɗa tare da saman (masu haɓakawa) don yawancin ruwaye da ke ƙunshe.Girman da ya dace ya dogara ne akan ƙwarewar marubutan da suka gabata tare da na'urori masu ɗaukar ruwa na ƙarfe.Girman ciki na tashar ƙarshe sun kasance 750 µm x 750 µm kuma jimillar ƙarar reactor shine 1 ml.An haɗa haɗin haɗin ciki (1/4 ″-28 zaren UNF) a cikin ƙira don ba da damar mu'amala da na'urar cikin sauƙi tare da kayan aikin sinadarai masu gudana na kasuwanci.Girman tashoshi yana iyakance ta kauri na kayan foil, kayan aikin injin sa, da sigogin haɗin kai da aka yi amfani da su tare da ultrasonics.A wani nisa don kayan da aka ba, kayan za su "sag" a cikin tashar da aka halitta.A halin yanzu babu takamaiman samfuri don wannan lissafin, don haka matsakaicin nisa na tashar don kayan da aka ba da ƙira an ƙaddara ta gwaji, a cikin abin da nisa na 750 µm ba zai haifar da sag ba.
An ƙayyade siffar (square) na tashar ta amfani da mai yanke murabba'i.Za'a iya canza siffar da girman tashoshi a kan na'urorin CNC ta yin amfani da kayan aikin yankan daban-daban don samun nau'i daban-daban da halaye.Misali na ƙirƙirar tashar mai lankwasa tare da kayan aikin 125 µm ana iya samun su a Monaghan45.Lokacin da aka yi amfani da shinge mai laushi, aikace-aikacen kayan aiki zuwa tashoshi zai sami shimfidar wuri (square).A cikin wannan aikin, an yi amfani da kwandon murabba'i don adana alamar tasha.
A lokacin da aka tsara shirin dakatarwa a samarwa, ana gina firikwensin zafin jiki na thermocouple (nau'in K) kai tsaye a cikin na'urar tsakanin manyan ƙungiyoyin tashoshi na sama da ƙananan (Fig. 1 - mataki 3).Wadannan thermocouples na iya sarrafa canjin zafin jiki daga -200 zuwa 1350 ° C.
Ƙaho na UAM ne ke aiwatar da tsarin shigar da ƙarfe ta hanyar amfani da foil ɗin ƙarfe mai faɗin 25.4 mm da kauri 150 microns.Wadannan yadudduka na tsare an haɗa su a cikin jerin sassan da ke kusa da su don rufe dukan ginin ginin;Girman kayan da aka ajiye ya fi girma fiye da samfurin ƙarshe yayin da tsarin raguwa ya haifar da siffar tsabta ta ƙarshe.Ana amfani da mashin ɗin CNC don na'ura na waje da na ciki na kayan aiki, yana haifar da ƙarewar kayan aiki da tashoshi masu dacewa da kayan aikin da aka zaɓa da sigogin tsarin CNC (a cikin wannan misali, kusan 1.6 µm Ra).Ci gaba, ci gaba da feshin kayan abu na ultrasonic da machining ana amfani da su a ko'ina cikin tsarin masana'antar na'urar don tabbatar da daidaiton girman girman kuma ɓangaren da ya gama ya haɗu da matakan daidaitaccen milling na CNC.Nisa na tashar da aka yi amfani da shi don wannan na'urar yana da ƙananan isa don tabbatar da cewa kayan da ba a so ba "sag" a cikin tashar ruwa, don haka tashar tana da ɓangaren giciye na murabba'i.Matsaloli masu yiwuwa a cikin kayan foil da ma'auni na tsarin UAM an ƙaddara su ta hanyar gwaji ta abokin aikin masana'anta (Fabrisonic LLC, Amurka).
Nazarin ya nuna cewa a cikin haɗin gwiwar 46, 47 na UAM fili akwai ƙananan yaduwa na abubuwa ba tare da ƙarin maganin zafi ba, don haka ga na'urorin da ke cikin wannan aikin Layer Cu-110 ya kasance daban-daban daga Al 6061 Layer kuma yana canzawa sosai.
Shigar da mai daidaita matsa lamba na baya (BPR) a 250 psi (1724 kPa) a ƙasan magudanar ruwa da kuma zub da ruwa ta cikin reactor a ƙimar 0.1 zuwa 1 ml min-1.An lura da matsa lamba na reactor ta amfani da mai canza matsa lamba na FlowSyn da aka gina a cikin tsarin don tabbatar da cewa tsarin zai iya ci gaba da matsa lamba.An gwada yuwuwar matakan zafin jiki a cikin injin mai gudana ta hanyar nemo kowane bambance-bambance tsakanin thermocouples da aka gina a cikin reactor da thermocouples da aka gina a cikin farantin dumama na FlowSyn guntu.Ana samun wannan ta hanyar canza yanayin zafi mai zafi tsakanin 100 zuwa 150 ° C a cikin 25 ° C da kuma lura da kowane bambance-bambance tsakanin yanayin da aka tsara da rikodin.An cimma wannan ta amfani da tc-08 data logger (PicoTech, Cambridge, UK) da software na rakiyar PicoLog.
An inganta yanayin halayen cycloaddition na phenylacetylene da iodoethane (Tsarin 1-Cycloaddition na phenylacetylene da iodoethane, Tsarin 1-Cycloaddition na phenylacetylene da iodoethane).An yi wannan haɓakawa ta amfani da cikakkiyar ƙirar gwaje-gwajen (DOE), ta yin amfani da zafin jiki da lokacin zama azaman masu canji yayin gyara alkyne: azide rabo a 1: 2.
An shirya mafita daban-daban na sodium azide (0.25 M, 4: 1 DMF: H2O), iodoethane (0.25 M, DMF), da phenylacetylene (0.125 M, DMF).An gauraya aliquot 1.5 ml na kowane bayani kuma an juye shi ta cikin reactor a ƙimar da ake so da zazzabi.An dauki martanin samfurin azaman rabon yanki mafi girma na samfurin triazole zuwa kayan farawa na phenylacetylene kuma an ƙaddara ta amfani da babban aikin ruwa chromatography (HPLC).Don daidaiton bincike, an ɗauki duk halayen nan da nan bayan cakudar da ya bar reactor.Ana nuna kewayon ma'auni da aka zaɓa don haɓakawa a cikin Tebur 2.
An yi nazarin duk samfuran ta amfani da tsarin Chromaster HPLC (VWR, PA, Amurka) wanda ya ƙunshi famfo na quaternary, tanda shafi, mai gano hasken UV mai canzawa da kuma autosampler.Rukunin ya kasance daidai 5 C18 (VWR, PA, Amurka), 4.6 x 100 mm, 5 µm girman barbashi, kiyayewa a 40°C.Mai ƙarfi shine methanol isocratic: ruwa 50:50 a cikin adadin 1.5 ml · min-1.Girman allurar ya kasance 5 μl kuma tsayin mai gano shine 254 nm.An ƙididdige yankin % kololuwar samfurin DOE daga mafi girman wuraren ragowar alkyne da samfuran triazole kawai.Gabatarwar kayan farawa yana ba da damar gano kololuwar da suka dace.
Haɗa sakamakon bincike na reactor tare da software na MODDE DOE (Umetrics, Malmö, Sweden) ya ba da damar cikakken nazarin sakamakon da kuma ƙayyadaddun yanayin da ya dace na wannan cycloaddition.Gudanar da ginanniyar ingantawa da zaɓar duk mahimman sharuɗɗan ƙira suna ƙirƙirar saitin yanayin amsawa da aka tsara don haɓaka kololuwar yankin samfurin yayin rage girman yanki don kayan abinci na acetylene.
Oxidation na jan karfe surface a cikin catalytic dauki dakin da aka samu ta amfani da wani hydrogen peroxide bayani (36%) gudãna ta hanyar dauki dakin (flow rate = 0.4 ml min-1, zama lokaci = 2.5 min) kafin kira na kowane triazole fili.ɗakin karatu.
Da zarar an ƙayyade mafi kyawun yanayin yanayi, an yi amfani da su zuwa kewayon acetylene da abubuwan haloalkane don ba da damar haɗar ƙaramin ɗakin karatu na haɗin gwiwa, ta haka ne ke tabbatar da yiwuwar yin amfani da waɗannan sharuɗɗan zuwa faɗuwar kewayon yuwuwar sakewa (Fig. 1).2).
Shirya mafita daban-daban na sodium azide (0.25 M, 4: 1 DMF: H2O), haloalkanes (0.25 M, DMF), da alkynes (0.125 M, DMF).Aliquots na 3 ml na kowane bayani an gauraye da kuma zub da su ta cikin reactor a wani kudi na 75 µl/min da zafin jiki na 150°C.An tattara dukan ƙarar a cikin vial kuma an diluted da 10 ml na ethyl acetate.An wanke samfurin samfurin tare da 3 x 10 ml na ruwa.An haɗu da yadudduka masu ruwa da ruwa kuma an fitar da su tare da 10 ml ethyl acetate, sa'an nan kuma an haɗa nau'in kwayoyin halitta, a wanke da brine 3 × 10 ml, bushe a kan MgSO 4 kuma a tace, sa'an nan kuma an cire sauran ƙarfi a cikin vacuo.An tsarkake samfurori ta hanyar silica gel shafi chromatography ta amfani da ethyl acetate kafin bincike ta hanyar haɗin HPLC, 1H NMR, 13C NMR da babban ƙuduri na spectrometry (HR-MS).
An samo duk nau'ikan bakan ta amfani da ma'auni na Thermofischer Precision Orbitrap mass spectrometer tare da ESI a matsayin tushen ionization.An shirya duk samfuran ta amfani da acetonitrile azaman ƙarfi.
An gudanar da bincike na TLC akan faranti na silica tare da ƙaramin aluminum.An hango faranti tare da hasken UV (254 nm) ko tabon vanillin da dumama.
An yi nazarin duk samfurori ta amfani da tsarin VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) sanye take da autosampler, famfo na binary tare da tanda ginshiƙi da kuma mai gano tsayin tsayi guda ɗaya.An yi amfani da ginshiƙin ACE Daidaita 5 C18 (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland).
An yi allura (5 µl) kai tsaye daga cakudaccen ɗanyen da aka diluted (1:10 dilution) kuma an bincika tare da ruwa: methanol (50:50 ko 70:30), sai dai wasu samfuran ta amfani da tsarin 70:30 mai ƙarfi (wanda aka nuna azaman lambar tauraro) a ƙimar kwarara na 1.5 ml/min.An adana ginshiƙan a 40 ° C.Tsawon tsayin na'urar ganowa shine 254 nm.
An ƙididdige yanki mafi girman % na samfurin daga mafi girman yanki na ragowar alkyne, samfurin triazole kawai, da gabatarwar kayan farawa ya ba da damar gano kololuwar daidai.
An bincika duk samfuran ta amfani da Thermo iCAP 6000 ICP-OES.An shirya duk matakan daidaitawa ta amfani da daidaitaccen bayani na 1000 ppm Cu a cikin 2% nitric acid (SPEX Certi Prep).An shirya duk matakan a cikin wani bayani na 5% DMF da 2% HNO3, kuma duk samfurori an diluted sau 20 tare da samfurin samfurin DMF-HNO3.
UAM yana amfani da ultrasonic karfe walda a matsayin hanyar shiga da karfe tsare amfani don ƙirƙirar karshe taro.Ultrasonic karfe waldi yana amfani da kayan aiki na ƙarfe mai girgiza (wanda ake kira ƙaho ko ƙaho na ultrasonic) don amfani da matsa lamba zuwa ga tsare / daɗaɗɗen Layer da za a haɗa / a baya ƙarfafa ta hanyar girgiza kayan.Don ci gaba da aiki, sonotrode yana da siffar cylindrical kuma yana jujjuya saman kayan, yana gluing duk yankin.Lokacin da aka yi amfani da matsa lamba da girgiza, oxides a saman kayan zasu iya fashe.Matsi na yau da kullun da rawar jiki na iya haifar da lalata ƙarancin kayan 36.Matsakaicin kusanci tare da yanayin zafi da matsa lamba sannan yana haifar da haɗin gwiwa mai ƙarfi a mahaɗan kayan;Hakanan yana iya haɓaka haɗin kai ta hanyar canza makamashin saman48.Yanayin tsarin haɗin kai yana shawo kan yawancin matsalolin da ke da alaƙa da canjin yanayin narke da tasirin zafin jiki da aka ambata a cikin wasu fasahohin masana'anta.Wannan yana ba da damar haɗin kai tsaye (watau ba tare da gyare-gyaren ƙasa ba, filaye ko adhesives) na yadudduka daban-daban na abubuwa daban-daban zuwa ƙaƙƙarfan tsari guda ɗaya.
Abu mai kyau na biyu ga CAM shine babban matakin kwararar filastik da aka gani a cikin kayan ƙarfe ko da a ƙananan yanayin zafi, watau ƙasa da wurin narkewar kayan ƙarfe.A hade ultrasonic vibrations da matsa lamba yana haifar da wani babban matakin na gida hatsi iyaka hijirarsa da recrystallization ba tare da gagarumin zafin jiki karuwa a al'ada hade da girma kayan.A lokacin ƙirƙirar taro na ƙarshe, ana iya amfani da wannan al'amari don haɗa abubuwa masu aiki da ma'amala tsakanin yadudduka na bangon ƙarfe, Layer ta Layer.Abubuwan da suka haɗa da fiber na gani 49, ƙarfafawa 46, lantarki 50 da thermocouples (wannan aikin) an samu nasarar haɗa su cikin tsarin UAM don ƙirƙirar taruka masu haɗaka masu aiki da m.
A cikin wannan aikin, an yi amfani da damar daurin abu daban-daban da kuma damar haɗin gwiwar UAM don ƙirƙirar microreactor mai kyau don sarrafa zafin jiki na catalytic.
Idan aka kwatanta da palladium (Pd) da sauran abubuwan karafa da aka saba amfani da su, Cu catalysis yana da fa'idodi da yawa: (i) Tattalin arziki, Cu yana da arha fiye da sauran karafa da ake amfani da su a cikin catalysis kuma saboda haka zaɓi ne mai ban sha'awa ga masana'antar sinadarai (ii) kewayon halayen haɗin giciye na Cu-catalyzed yana faɗaɗa kuma ya bayyana ya zama ɗan daidaitawa zuwa hanyar Pd251. s aiki da kyau in babu sauran ligands.Wadannan ligands galibi suna da saukin tsari kuma ba su da tsada.idan ana so, yayin da waɗanda aka yi amfani da su a cikin ilmin sunadarai na Pd sau da yawa suna da rikitarwa, masu tsada, da kuma iska (iv) Cu, musamman da aka sani da ikonsa na haɗin alkynes a cikin kira, irin su Sonogashira's bimetallic catalyzed coupling da cycloaddition tare da azides (danna sunadarai) (v) Cu kuma iya inganta arylation na wasu nucles.type a cikin U.
Kwanan nan, misalan heterogenization na duk waɗannan halayen a gaban Cu (0) an nuna su.Wannan ya samo asali ne saboda masana'antar harhada magunguna da kuma karuwar mayar da hankali kan farfadowa da sake amfani da karafa55,56.
Halin cycloaddition na 1,3-dipolar tsakanin acetylene da azide zuwa 1,2,3-triazole, wanda Huisgen ya fara ba da shawara a cikin 1960s57, ana ɗaukarsa azaman halayen nunin haɗin gwiwa.Sakamakon 1,2,3 triazole gutsuttsura suna da sha'awa na musamman a matsayin pharmacophore a cikin binciken miyagun ƙwayoyi saboda aikace-aikacen nazarin halittu da amfani da su a cikin wasu nau'o'in warkewa 58.
Wannan martanin ya sami sabunta hankali lokacin da Sharpless da wasu suka gabatar da manufar "click chemistry"59.Kalmar “click chemistry” ana amfani da ita don bayyana ƙaƙƙarfan saitin halayen halayen don saurin haɗa sabbin mahadi da ɗakunan karatu ta hanyar amfani da haɗin gwiwar heteroatomic (CXC)60.Roƙon roba na waɗannan halayen shine saboda yawan amfanin ƙasa da ke tattare da su.yanayi yana da sauƙi, juriya ga iskar oxygen da ruwa, kuma rabuwar samfur yana da sauƙi61.
Na gargajiya 1,3-dipole Huisgen cycloaddition baya fada cikin "click chemistry" category.Duk da haka, Medal da Sharpless sun nuna cewa wannan taron haɗin gwiwar azide-alkyne yana fuskantar 107-108 a gaban Cu (I) idan aka kwatanta da wani gagarumin haɓakawa a cikin ƙimar 62,3-dipolar cycloaddition 62,63.Wannan haɓakar haɓakawa na ci gaba baya buƙatar ƙungiyoyin karewa ko yanayin halayen halayen kuma yana ba da kusan cikakkiyar juzu'i da zaɓin zaɓi zuwa 1,4-disubstituted 1,2,3-triazoles (anti-1,2,3-triazoles) a tsawon lokaci (Fig. 3).
Sakamakon isometric na al'ada da jan ƙarfe-catalyzed Huisgen cycloadditions.Cu (I) - catalyzed Huisgen cycloadditions yana ba da 1,4-disustituted 1,2,3-triazoles kawai, yayin da Huisgen cycloadditions da aka haifar da thermally yana ba da 1,4- da 1,5-triazoles a 1: 1 cakuda azole stereoisomers.
Yawancin ka'idoji sun haɗa da rage barga tushen Cu(II), kamar rage CuSO4 ko mahaɗin Cu (II)/Cu (0) a haɗe da gishirin sodium.Idan aka kwatanta da sauran halayen haɓakar ƙarfe na ƙarfe, amfani da Cu(I) yana da babban fa'idar kasancewa mara tsada da sauƙin sarrafawa.
Kinetic da nazarin isotopic na Worrell et al.65 sun nuna cewa a cikin yanayin alkynes na ƙarshe, nau'i biyu na jan karfe suna da hannu wajen kunna sake kunnawa kowane kwayoyin halitta dangane da azide.Tsarin da aka tsara yana gudana ta hanyar zoben ƙarfe na ƙarfe mai mambobi shida da aka kafa ta hanyar daidaitawar azide zuwa σ-bonded jan karfe acetylide tare da jan karfe mai ɗaure da π a matsayin tsayayyen ligand mai bayarwa.Ana samun abubuwan da suka samo asali na triazolyl na jan karfe sakamakon raguwar zobe tare da bazuwar proton don samar da samfuran triazol da rufe zagayowar catalytic.
Yayin da fa'idodin na'urorin sunadarai masu kwarara ke da kyau a rubuce, an yi sha'awar haɗa kayan aikin nazari cikin waɗannan tsarin don sa ido kan tsari na lokaci a cikin situ66,67.UAM ya tabbatar da zama hanyar da ta dace don ƙira da kera masana'anta masu rikiɗar 3D masu gudana daga catalytically aiki, kayan gudanarwar thermal tare da abubuwan ganowa kai tsaye (Fig. 4).
Aluminum-Copper kwarara reactor kerarre ta ultrasonic ƙari masana'antu (UAM) tare da hadaddun ciki tashar tsarin, ginannen thermocouples da catalytic dauki dakin.Don ganin hanyoyin ruwa na ciki, ana kuma nuna samfuri na zahiri da aka yi ta amfani da stereolithography.
Don tabbatar da cewa an yi reactors don halayen kwayoyin halitta na gaba, masu kaushi dole ne a ɗora zafi sama da wurin tafasa;an gwada matsi da zafin jiki.Gwajin gwajin ya nuna cewa tsarin yana kula da kwanciyar hankali da matsa lamba har ma da matsa lamba mai girma a cikin tsarin (1.7 MPa).An gudanar da gwaje-gwajen hydrostatic a zafin jiki ta amfani da H2O azaman ruwa.
Haɗin ginin da aka gina (Hoto 1) thermocouple zuwa ma'aunin bayanan zafin jiki ya nuna cewa zafin jiki na thermocouple ya kasance 6 ° C (± 1 ° C) ƙasa da yanayin da aka tsara a cikin tsarin FlowSyn.Yawanci, haɓakar zafin jiki na 10 ° C yana ninka adadin amsawa, don haka bambancin zafin jiki na 'yan digiri kaɗan na iya canza ƙimar amsawa sosai.Wannan bambance-bambancen shine saboda asarar zafin jiki a ko'ina cikin RPV saboda babban diffusivity na thermal na kayan da aka yi amfani da su a cikin tsarin masana'antu.Wannan motsi na thermal yana dawwama don haka ana iya la'akari da shi lokacin saita kayan aiki don tabbatar da ingantacciyar yanayin zafi da aunawa yayin amsawa.Don haka, wannan kayan aikin sa ido na kan layi yana sauƙaƙe kulawar zafin jiki mai ƙarfi kuma yana ba da gudummawa ga ingantaccen ingantaccen tsari da haɓaka yanayi mafi kyau.Hakanan za'a iya amfani da waɗannan na'urori masu auna firikwensin don gano halayen exothermic da hana halayen gudu a cikin manyan sikelin.
The reactor gabatar a cikin wannan takarda shi ne na farko misali na aikace-aikace na UAM fasahar zuwa ƙirƙira na sinadaran reactors da kuma magance da dama manyan gazawar a halin yanzu hade da AM / 3D bugu na wadannan na'urorin, kamar: (i) Cin nasara da lura matsaloli hade da aiki na jan karfe ko aluminum gami (ii) inganta ciki tashar ƙuduri idan aka kwatanta da foda gado narke (PBF) hanyoyin kamar yadda zaɓaɓɓen Laser narkar da kayan aiki (PBF) da zažužžukan Laser narkar da kayan aiki (PBF2). ƙananan zafin jiki na sarrafawa, wanda ke sauƙaƙe na'urori masu haɗawa kai tsaye, wanda ba zai yiwu ba a fasaha na gado na foda, (v) cin nasara mara kyau na kayan aikin injiniya da hankali na kayan aikin polymer zuwa daban-daban na yau da kullum na kwayoyin halitta17,19.
Ayyukan reactor an nuna su ta hanyar jerin halayen alkinazide cycloaddition na jan ƙarfe-catalyzed a ƙarƙashin yanayin ci gaba da gudana (Fig. 2).The ultrasonic buga jan reactor nuna a fig.4 an haɗa shi tare da tsarin tafiyar da kasuwanci kuma an yi amfani da shi don haɗawa da ɗakin karatu na azide na daban-daban 1,4-disubstituted 1,2,3-triazoles ta amfani da yanayin zafin jiki na acetylene da alkyl halides a gaban sodium chloride (Fig. 3).Yin amfani da tsarin ci gaba da gudana yana rage matsalolin aminci waɗanda zasu iya tasowa a cikin tsarin tsari, tun da wannan amsa yana haifar da matsananciyar azide mai saurin amsawa da haɗari [317], [318].Da farko, an inganta halayen halayen don cycloaddition na phenylacetylene da iodoethane (Tsarin 1 - Cycloaddition na phenylacetylene da iodoethane) (duba siffa 5).
(Hagu na sama) Tsarin saitin da aka yi amfani da shi don shigar da reactor na 3DP a cikin tsarin gudana (babban dama) da aka samu daga ingantacciyar (ƙananan) makirci na Huisgen 57 cycloaddition makirci tsakanin phenylacetylene da iodoethane don ingantawa da kuma nuna ingantattun sigogin juzu'i na amsawa.
Ta hanyar sarrafa lokacin zama na masu amsawa a cikin sashin catalytic na reactor kuma a hankali kula da yanayin zafin jiki tare da firikwensin thermocouple kai tsaye, ana iya inganta yanayin da sauri da daidai tare da ƙaramin lokaci da kayan aiki.An gano da sauri cewa an sami mafi girman juyi ta amfani da lokacin zama na mintuna 15 da zafin jiki na 150 ° C.Ana iya gani daga ƙayyadaddun makirci na software na MODDE cewa duka lokacin wurin zama da zafin jiki ana ɗaukar mahimman yanayi na ƙirar.Gudanar da ginanniyar ingantawa ta amfani da waɗannan zaɓaɓɓun yanayi yana haifar da saitin yanayin amsawa da aka ƙera don haɓaka wuraren kololuwar samfur yayin rage farkon wuraren kololuwar kayan.Wannan ingantawa ya haifar da juzu'in 53% na samfurin triazole, wanda yayi daidai da hasashen samfurin na 54%.