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Masana'antar ƙari tana canza yadda masu bincike da masana masana'antu ke tsarawa da ƙera na'urorin sinadarai don biyan buƙatunsu na musamman. A cikin wannan takarda, mun bayar da rahoton misali na farko na wani reactor mai kwarara wanda aka ƙirƙira ta hanyar amfani da na'urar ƙara ultrasonic (UAM) na takardar ƙarfe mai ƙarfi tare da sassan catalytic da abubuwan ji. Fasahar UAM ba wai kawai ta shawo kan yawancin ƙuntatawa da ke da alaƙa da kera ƙarin reactors na sinadarai ba, har ma tana faɗaɗa ƙarfin irin waɗannan na'urori sosai. An haɗa wasu mahaɗan 1,2,3-triazole masu mahimmanci 1,4-disposals waɗanda aka cire su daga sinadarai ta hanyar amfani da sinadaran Huisgen cycloaddition na 1,3-dipolar Cu ta amfani da kayan aikin sunadarai na UAM. Ta amfani da kaddarorin musamman na UAM da ci gaba da sarrafa kwarara, na'urar tana iya haɓaka halayen da ke gudana tare da samar da ra'ayoyi na ainihi don sa ido da inganta halayen.
Saboda fa'idodin da yake da su fiye da takwarorinsa na babban yanki, ilimin sunadarai na kwarara muhimmin fanni ne kuma mai girma a fannoni na ilimi da na masana'antu saboda ikonsa na ƙara zaɓi da ingancin haɗakar sinadarai. Wannan ya fara ne daga samuwar ƙwayoyin halitta masu sauƙi1 zuwa mahaɗan magunguna2,3 da samfuran halitta4,5,6. Sama da kashi 50% na halayen da ke cikin masana'antar sinadarai masu kyau da magunguna za su iya amfana daga ci gaba da kwarara7.
A cikin 'yan shekarun nan, akwai karuwar ƙungiyoyi da ke neman maye gurbin kayan aikin gilashi na gargajiya ko na sinadarai masu gudana da "masu haɗa sinadarai" masu daidaitawa 8. Tsarin maimaitawa, kera abubuwa cikin sauri, da kuma ƙarfin girma uku (3D) na waɗannan hanyoyin suna da amfani ga waɗanda ke son keɓance na'urorinsu don takamaiman saitin amsawa, na'urori, ko yanayi. Zuwa yanzu, wannan aikin ya mayar da hankali ne kawai kan amfani da dabarun buga 3D na polymer kamar stereolithography (SL)9,10,11, Fused Deposition Modeling (FDM)8,12,13,14 da bugawa ta inkjet7,15. , 16. Rashin aminci da ikon irin waɗannan na'urori don yin nau'ikan halayen sinadarai/nazari iri-iri17, 18, 19, 20 babban abin da ke iyakance amfani da AM a wannan fanni17, 18, 19, 20.
Saboda ƙaruwar amfani da sinadarai masu kwarara da kuma kyawawan halaye da ke da alaƙa da AM, ana buƙatar a bincika ingantattun dabaru waɗanda za su ba masu amfani damar ƙera tasoshin amsawar kwarara tare da ingantattun ƙwarewar sinadarai da nazari. Waɗannan hanyoyin ya kamata su ba masu amfani damar zaɓar daga cikin nau'ikan kayan aiki masu ƙarfi ko masu aiki waɗanda za su iya aiki a ƙarƙashin yanayi daban-daban na amsawa, da kuma sauƙaƙe nau'ikan fitarwa na nazari daga na'urar don ba da damar sa ido da sarrafa amsawar.
Ɗaya daga cikin hanyoyin ƙera ƙarin sinadarai da za a iya amfani da su don haɓaka na'urorin haɗa sinadarai na musamman shine Manufacturing Ultrasonic Additive Manufacturing (UAM). Wannan hanyar lamination ɗin takarda mai ƙarfi tana amfani da rawar jiki na ultrasonic zuwa ƙananan ƙarfe don haɗa su tare da Layer-by Layer tare da ƙaramin dumama mai girma da babban matakin kwararar filastik 21, 22, 23. Ba kamar yawancin sauran fasahohin AM ba, ana iya haɗa UAM kai tsaye tare da samar da abubuwa masu rarrafe, wanda aka sani da tsarin masana'antu na haɗin gwiwa, wanda niƙa ko sarrafa laser na lokaci-lokaci a cikin in-situ control (CNC) ke ƙayyade siffar net na Layer na kayan da aka haɗa 24, 25. Wannan yana nufin cewa mai amfani ba'a iyakance ga matsalolin da ke da alaƙa da cire kayan gini na asali daga ƙananan tashoshi na ruwa ba, wanda galibi haka yake a cikin tsarin foda da ruwa AM26, 27, 28. Wannan 'yancin ƙira kuma ya haɗu zuwa zaɓin kayan da ake da su - UAM na iya haɗa haɗakar kayan da suka yi kama da na zafi da waɗanda ba su da kama da juna a cikin mataki ɗaya na tsari. Zaɓin haɗakar kayan da suka wuce tsarin narkewa yana nufin cewa ana iya biyan buƙatun injiniya da sinadarai na takamaiman aikace-aikace. Baya ga haɗin gwiwa mai ƙarfi, wani abin da ke faruwa tare da haɗin ultrasonic shine yawan ruwan da kayan filastik ke fitarwa a yanayin zafi mai ƙarancin zafi29,30,31,32,33. Wannan fasalin na musamman na UAM yana ba da damar sanya abubuwan injiniya/zafi tsakanin yadudduka na ƙarfe ba tare da lalacewa ba. Na'urori masu auna UAM da aka haɗa za su iya sauƙaƙe isar da bayanai na ainihin lokaci daga na'urar zuwa ga mai amfani ta hanyar nazarin da aka haɗa.
Aikin da marubuta32 suka yi a baya ya nuna ikon tsarin UAM na ƙirƙirar tsarin microfluidic na ƙarfe na 3D tare da ƙarfin ji da aka haɗa. Wannan na'urar don dalilai na sa ido ne kawai. Wannan labarin ya gabatar da misali na farko na wani reactor na sinadarai mai ƙwayoyin cuta wanda UAM ta ƙera, na'ura mai aiki wadda ba wai kawai ke sarrafawa ba har ma tana haifar da haɗakar sinadarai tare da kayan catalytic da aka haɗa a cikin tsari. Na'urar ta haɗa fa'idodi da dama da ke da alaƙa da fasahar UAM wajen ƙera na'urorin sinadarai na 3D, kamar: ikon canza cikakken ƙirar 3D kai tsaye daga samfurin ƙira mai taimakon kwamfuta (CAD) zuwa samfuri; ƙera kayan aiki da yawa don haɗakar babban ƙarfin lantarki da kayan catalytic, da kuma na'urori masu auna zafi da aka saka kai tsaye tsakanin rafukan reactant don sarrafawa da sarrafa zafin jiki na amsawa. Don nuna aikin reactor, an haɗa ɗakin karatu na mahaɗan 1,2,3-triazole masu mahimmanci na magunguna 1,4-dispolar ta hanyar cycloaddition na Huisgen 1,3-dipolar. Wannan aikin ya nuna yadda amfani da kimiyyar kayan aiki da ƙirar kwamfuta za su iya buɗe sabbin damammaki da damammaki ga ilmin sunadarai ta hanyar bincike tsakanin fannoni daban-daban.
An sayi dukkan sinadaran da ke narkewa da kuma sinadaran da ke cikin sinadaran daga Sigma-Aldrich, Alfa Aesar, TCI, ko Fischer Scientific kuma an yi amfani da su ba tare da an riga an tsarkake su ba. An samo nau'ikan 1H da 13C NMR da aka rubuta a 400 da 100 MHz, bi da bi, a kan na'urar JEOL ECS-400 400 MHz ko na'urar spectrometer ta Bruker Avance II 400 MHz tare da CDCl3 ko (CD3)2SO a matsayin sinadaran da ke narkewa. An yi dukkan halayen ta amfani da dandamalin sinadaran Uniqsis FlowSyn.
An yi amfani da UAM don ƙera dukkan na'urori a cikin wannan binciken. An ƙirƙiro fasahar a shekarar 1999 kuma ana iya yin nazarin bayanan fasaha, sigogin aiki da ci gabanta tun lokacin ƙirƙirar ta ta amfani da waɗannan kayan da aka buga34,35,36,37. An aiwatar da na'urar (Hoto na 1) ta amfani da tsarin SonicLayer 4000® UAM mai nauyin 9 kW (Fabrisonic, Ohio, Amurka). Kayan da aka zaɓa don na'urar kwarara sune Cu-110 da Al 6061. Cu-110 yana da babban abun ciki na jan ƙarfe (mafi ƙarancin 99.9% jan ƙarfe), wanda hakan ya sa ya zama kyakkyawan zaɓi ga halayen jan ƙarfe masu haɓakawa kuma saboda haka ana amfani da shi azaman "layi mai aiki a cikin microreactor. Ana amfani da Al 6061 O azaman kayan "babban". , da kuma layin haɗin gwiwa da ake amfani da shi don bincike; haɗa abubuwan haɗin ƙarfe masu taimako da yanayin annealed tare da layin Cu-110. An gano cewa yana da karko ta hanyar sinadarai tare da abubuwan haɗin gwiwa da aka yi amfani da su a cikin wannan aikin. Hakanan ana ɗaukar Al 6061 O tare da Cu-110 a matsayin haɗin kayan da ya dace da UAM kuma saboda haka abu ne mai dacewa don wannan binciken38,42. Waɗannan na'urori an jera su a cikin Tebur 1 a ƙasa.
Matakan ƙera reactor (1) 6061 substrate aluminum alloy substrate (2) Ƙirƙirar tashar ƙasa daga foil na jan ƙarfe (3) Shigar da thermocouples tsakanin yadudduka (4) Tashar sama (5) Shiga da fita (6) Reactor mai monolithic.
Falsafar ƙirar tashar ruwa ita ce amfani da hanya mai tsauri don ƙara nisan da ruwan ke tafiya a cikin guntu yayin da yake kiyaye girman guntu mai sarrafawa. Wannan ƙaruwar nisa ana so ta ƙara lokacin hulɗa da mai amsawa da mai amsawa da kyau da kuma samar da kyakkyawan yawan samfuri. Kwakwalwan suna amfani da lanƙwasa 90° a ƙarshen hanya madaidaiciya don haifar da haɗuwa mai rikitarwa a cikin na'urar44 da kuma ƙara lokacin haɗuwa da ruwan tare da saman (mai ƙarfafawa). Don ƙara haɓaka haɗuwa da za a iya cimmawa, ƙirar mai amsawa ya haɗa da mashigar amsawa guda biyu da aka haɗa a cikin haɗin Y kafin shiga sashin haɗa na'urar. Shiga ta uku, wacce ke ratsa kwararar a tsakiyar wurin zama, an haɗa ta cikin shirin halayen haɗa matakai da yawa na gaba.
Duk tashoshi suna da siffar murabba'i (babu kusurwoyi masu tauri), wanda shine sakamakon niƙa na CNC na lokaci-lokaci da ake amfani da shi don ƙirƙirar yanayin tashar. An zaɓi girman tashar don samar da babban yawan amfanin ƙasa (ga microreactor), duk da haka ƙarami ne don sauƙaƙe hulɗa da saman (masu haɓaka) ga yawancin ruwan da ke cikinta. Girman da ya dace ya dogara ne akan ƙwarewar marubutan da suka gabata tare da na'urorin amsawar ruwa-ƙarfe. Girman ciki na tashar ƙarshe shine 750 µm x 750 µm kuma jimlar girman reactor shine 1 ml. An haɗa haɗin da aka gina a ciki (zaren UNF 1/4″-28) a cikin ƙirar don ba da damar sauƙin haɗawa na'urar tare da kayan aikin sinadarai na kwararar kasuwanci. Girman tashar yana iyakance ne ta hanyar kauri na kayan foil, halayen injina, da sigogin haɗin da aka yi amfani da su tare da ultrasonics. A wani faɗi na kayan da aka bayar, kayan zai "ruɓe" cikin tashar da aka ƙirƙira. A halin yanzu babu wani takamaiman tsari don wannan lissafi, don haka ana ƙayyade matsakaicin faɗin tashar don wani abu da ƙira da aka bayar ta hanyar gwaji, wanda a wannan yanayin faɗin 750 µm ba zai haifar da raguwa ba.
Ana tantance siffar (murabba'i) ta hanyar amfani da abin yanka murabba'i. Ana iya canza siffar da girman tashoshin a kan injunan CNC ta amfani da kayan aikin yankewa daban-daban don samun saurin kwarara da halaye daban-daban. Misali na ƙirƙirar tashar mai lanƙwasa tare da kayan aiki na 125 µm za a iya samu a Monaghan45. Lokacin da aka shafa layin foil ɗin a lebur, amfani da kayan foil ɗin a tashoshin zai sami saman lebur (murabba'i). A cikin wannan aikin, an yi amfani da siffar murabba'i don kiyaye daidaiton tashar.
A lokacin da aka dakatar da samarwa, ana gina na'urori masu auna zafin jiki na thermocouple (nau'in K) kai tsaye a cikin na'urar tsakanin rukunin tashoshi na sama da na ƙasa (Hoto na 1 - mataki na 3). Waɗannan na'urorin thermocouple na iya sarrafa canje-canjen zafin jiki daga -200 zuwa 1350 °C.
Ana gudanar da aikin adana ƙarfe ta hanyar amfani da ƙaho na UAM ta amfani da foil ɗin ƙarfe mai faɗin mm 25.4 da kauri microns 150. Waɗannan layukan foil ɗin an haɗa su a cikin jerin layukan da ke maƙwabtaka don rufe dukkan yankin ginin; girman kayan da aka ajiye ya fi girma fiye da samfurin ƙarshe yayin da tsarin cirewa ke haifar da siffa ta ƙarshe mai tsabta. Ana amfani da injin CNC don injinan kwane-kwane na waje da na ciki na kayan aiki, wanda ke haifar da ƙarewar saman kayan aiki da tashoshi daidai da kayan aikin da aka zaɓa da sigogin aikin CNC (a cikin wannan misalin, kimanin 1.6 µm Ra). Ana amfani da feshi da zagayowar injinan ultrasonic masu ci gaba da ci gaba a duk tsawon tsarin ƙera na'urar don tabbatar da daidaiton girma kuma ɓangaren da aka gama ya cika matakan daidaiton niƙa na CNC. Faɗin tashar da aka yi amfani da ita don wannan na'urar ƙarami ne don tabbatar da cewa kayan foil ɗin ba su "ruɓe" a cikin tashar ruwa ba, don haka tashar tana da sashin giciye mai murabba'i. Abokan hulɗar masana'anta ne suka ƙayyade gibin da zai yiwu a cikin kayan foil ɗin da sigogin tsarin UAM ta hanyar gwaji (Fabrisonic LLC, Amurka).
Bincike ya nuna cewa a mahaɗin 46, 47 na mahaɗin UAM akwai ƙarancin yaɗuwar abubuwa ba tare da ƙarin maganin zafi ba, don haka ga na'urorin da ke cikin wannan aikin, layin Cu-110 ya bambanta da layin Al 6061 kuma yana canzawa sosai.
Shigar da na'urar daidaita matsin lamba ta baya (BPR) a 250 psi (1724 kPa) a ƙasan reactor ɗin sannan a yi famfo da ruwa ta cikin reactor ɗin a cikin ƙimar 0.1 zuwa 1 ml min-1. An sa ido kan matsin lambar reactor ɗin ta amfani da na'urar canza matsin lamba ta FlowSyn da aka gina a cikin tsarin don tabbatar da cewa tsarin zai iya ci gaba da riƙe matsin lamba mai ɗorewa. An gwada yiwuwar canjin zafin jiki a cikin reactor ɗin ta hanyar neman duk wani bambanci tsakanin thermocouples da aka gina a cikin reactor ɗin da thermocouples da aka gina a cikin farantin dumama na guntuwar FlowSyn. Ana samun wannan ta hanyar canza zafin farantin zafi da aka tsara tsakanin 100 zuwa 150 °C a cikin ƙaruwar 25 °C da kuma sa ido kan duk wani bambanci tsakanin yanayin zafi da aka tsara da wanda aka yi rikodin. An cimma wannan ta amfani da mai rikodin bayanai na tc-08 (PicoTech, Cambridge, UK) da software na PicoLog da ke tare da shi.
An inganta yanayin da ake buƙata don amsawar cycloaddition na phenylacetylene da iodoethane (Shiri na 1-Cycloaddition na phenylacetylene da iodoethane, Shiri na 1-Cycloaddition na phenylacetylene da iodoethane). An yi wannan ingantawa ta amfani da cikakken tsarin gwaji na factorial (DOE), ta amfani da zafin jiki da lokacin zama a matsayin masu canji yayin da ake daidaita rabon alkyne:azide 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 haɗa rabon 1.5 ml na kowane maganin kuma an tura shi ta cikin reactor a daidai lokacin da ake buƙata da zafin jiki. An ɗauki martanin samfurin a matsayin rabon yankin kololuwar samfurin triazole zuwa kayan farawa na phenylacetylene kuma an tantance shi ta amfani da babban aikin ruwa chromatography (HPLC). Don daidaiton bincike, an ɗauki duk halayen nan da nan bayan cakuda amsawar ya bar reactor. Jerin sigogin da aka zaɓa don ingantawa an nuna su a cikin Jadawali na 2.
An yi nazarin dukkan samfuran ta amfani da tsarin Chromaster HPLC (VWR, PA, Amurka) wanda ya ƙunshi famfo na quaternary, tanda mai shafi, na'urar gano UV mai canzawa da kuma na'urar sampler mai aiki. Ginshiƙin ya kasance Daidaito 5 C18 (VWR, PA, Amurka), girman barbashi 4.6 x 100 mm, girman barbashi 5 µm, wanda aka kiyaye a 40°C. Maganin mai narkewa shine methanol:water isocratic 50:50 a ƙimar kwararar 1.5 ml·min-1. Girman allurar shine 5 μl kuma tsawon na'urar ganowa shine 254 nm. An ƙididdige yankin % na samfurin DOE daga yankunan ƙololuwar samfuran alkyne da triazole da suka rage kawai. Gabatar da kayan farawa yana ba da damar gano kololuwar da suka dace.
Haɗa sakamakon binciken reactor tare da software na MODDE DOE (Umetrics, Malmö, Sweden) ya ba da damar yin cikakken nazarin yanayin sakamako da kuma tantance mafi kyawun yanayin amsawa don wannan cycloaddition. Gudanar da ingantaccen kayan aiki da zaɓar duk mahimman sharuɗɗan samfuri yana ƙirƙirar saitin yanayin amsawa wanda aka tsara don haɓaka yankin kololuwar samfurin yayin da rage yankin kololuwar abincin acetylene.
An cimma nasarar haɗakar saman jan ƙarfe a cikin ɗakin amsawar catalytic ta amfani da maganin hydrogen peroxide (36%) wanda ke gudana ta cikin ɗakin amsawa (yawan kwarara = 0.4 ml min-1, lokacin zama = minti 2.5) kafin a haɗa kowane mahaɗin triazole. ɗakin karatu.
Da zarar an tantance mafi kyawun yanayin, an shafa su a kan nau'ikan acetylene da haloalkane don ba da damar haɗa ƙaramin ɗakin karatu na haɗa sinadarai, ta haka ne aka tabbatar da yuwuwar amfani da waɗannan yanayi ga nau'ikan abubuwan da ke haifar da sinadarai (Hoto na 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). An haɗa ma'aunin 3 ml na kowane maganin kuma an tura shi ta cikin reactor a cikin ƙimar 75 µl/min da zafin jiki na 150°C. An tattara dukkan adadin a cikin kwalba sannan aka narkar da shi da 10 ml na ethyl acetate. An wanke samfurin maganin da ruwa 3 x 10 ml. An haɗa yadudduka masu ruwa kuma an cire su da ethyl acetate 10 ml, sannan aka haɗa yadudduka na halitta, aka wanke da ruwan gishiri 3 × 10 ml, aka busar da su akan MgSO4 kuma aka tace, sannan aka cire sinadarin a cikin vacuo. An tsarkake samfuran ta hanyar amfani da chromatography na column gel na silica ta amfani da ethyl acetate kafin a yi nazari ta hanyar haɗa HPLC, 1H NMR, 13C NMR da spectrometry na mass resolution high definition (HR-MS).
An samo dukkan spectra ta amfani da na'urar auna ma'aunin Thermofischer Precision Orbitrap tare da ESI a matsayin tushen ionization. An shirya dukkan samfuran ta amfani da acetonitrile a matsayin mai narkewa.
An gudanar da binciken TLC akan faranti na silica tare da wani abu mai kama da aluminum. An yi amfani da hasken UV (254 nm) ko fenti da dumama vanillin a jikin faranti.
An yi nazarin dukkan samfuran ta amfani da tsarin VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) wanda aka sanye shi da na'urar sampler ta atomatik, famfon binary mai murhun ginshiƙi da na'urar gano tsawon rai guda ɗaya. An yi amfani da ginshiƙin ACE Equivalence 5 C18 (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland).
An yi allurai (5 µl) kai tsaye daga cakudawar da aka narkar da ɗanyen abu (narkewar 1:10) kuma an yi nazari da ruwa: methanol (50:50 ko 70:30), sai dai wasu samfuran da aka yi amfani da tsarin narkewar 70:30 (wanda aka nuna a matsayin lambar tauraro) a ƙimar kwararar 1.5 ml/min. An ajiye ginshiƙin a 40°C. Tsawon zangon na'urar ganowa shine 254 nm.
An ƙididdige yankin % na samfurin daga yankin top na sauran alkyne, samfurin triazole kawai, kuma gabatar da kayan farawa ya ba da damar gano top ɗin da suka dace.
An yi nazarin dukkan samfuran ta amfani da Thermo iCAP 6000 ICP-OES. An shirya duk matakan daidaitawa ta amfani da maganin Cu na 1000 ppm a cikin 2% nitric acid (SPEX Certi Prep). An shirya dukkan ka'idoji a cikin maganin 5% DMF da 2% HNO3, kuma an narkar da duk samfuran sau 20 tare da samfurin maganin DMF-HNO3.
UAM yana amfani da walda na ƙarfe na ultrasonic a matsayin hanyar haɗa murfin ƙarfe da aka yi amfani da shi don ƙirƙirar haɗuwa ta ƙarshe. Walda na ƙarfe na Ultrasonic yana amfani da kayan aikin ƙarfe mai girgiza (wanda ake kira ƙaho ko ƙaho na ultrasonic) don shafa matsi a kan foil/wanda aka haɗa a baya don a haɗa shi/wanda aka haɗa a baya ta hanyar girgiza kayan. Don ci gaba da aiki, sonotrode yana da siffar silinda kuma yana birgima a saman kayan, yana manne dukkan yankin. Lokacin da aka yi amfani da matsin lamba da girgiza, oxides a saman kayan na iya fashewa. Matsi da girgiza akai-akai na iya haifar da lalata ƙaiƙayin kayan 36. Kusa da kusanci da zafi da matsin lamba na gida sannan yana haifar da haɗin lokaci mai ƙarfi a mahaɗin kayan; yana kuma iya haɓaka haɗin kai ta hanyar canza kuzarin saman48. Yanayin hanyar haɗin yana shawo kan matsalolin da yawa da ke da alaƙa da yanayin zafi mai canzawa da tasirin zafin jiki mai yawa da aka ambata a cikin wasu fasahar kera ƙari. Wannan yana ba da damar haɗi kai tsaye (watau ba tare da gyaran saman ba, cikawa ko mannewa) na yadudduka da yawa na kayan daban-daban zuwa cikin tsari ɗaya mai haɗaka.
Abu na biyu mai kyau ga CAM shine babban matakin kwararar filastik da ake gani a cikin kayan ƙarfe ko da a yanayin zafi mai ƙasa, watau ƙasa da wurin narkewar kayan ƙarfe. Haɗin girgizar ultrasonic da matsin lamba yana haifar da babban matakin ƙaura na iyakoki na hatsi na gida da sake sake haɗawa ba tare da babban ƙaruwar zafin jiki da aka saba da shi da kayan girma ba. A lokacin ƙirƙirar haɗuwa ta ƙarshe, ana iya amfani da wannan lamari don saka abubuwan aiki da masu wucewa tsakanin yadudduka na foil ɗin ƙarfe, layi-layi. An haɗa abubuwa kamar fiber na gani 49, ƙarfafawa 46, lantarki 50 da thermocouples (wannan aikin) cikin nasarar haɗa su cikin tsarin UAM don ƙirƙirar ƙungiyoyi masu aiki da masu wucewa.
A cikin wannan aikin, an yi amfani da ƙarfin ɗaure kayan aiki daban-daban da kuma ƙarfin haɗin UAM don ƙirƙirar microreactor mai kyau don sarrafa zafin jiki mai catalytic.
Idan aka kwatanta da palladium (Pd) da sauran abubuwan kara kuzari na ƙarfe da aka saba amfani da su, Cu catalysis yana da fa'idodi da yawa: (i) A fannin tattalin arziki, Cu ya fi sauran ƙarfe da yawa da ake amfani da su a catalysis kuma saboda haka zaɓi ne mai kyau ga masana'antar sinadarai (ii) kewayon halayen haɗin gwiwa na Cu-catalyzed yana faɗaɗa kuma da alama yana da ɗan dacewa da hanyoyin Pd51, 52, 53 (iii) Halayen Cu-catalyzed suna aiki da kyau idan babu wasu ligands. Waɗannan ligands galibi suna da sauƙi a tsarin kuma suna da araha. idan ana so, yayin da waɗanda ake amfani da su a cikin sunadarai na Pd galibi suna da rikitarwa, tsada, kuma suna da saurin amsawa ga iska (iv) Cu, musamman sananne saboda ikonsa na haɗa alkynes a cikin haɗin, kamar haɗin bimetallic catalyzed Sonogashira da cycloaddition tare da azides (click chemistry) (v) Cu kuma na iya haɓaka arylation na wasu nucleophiles a cikin halayen Ullmann.
Kwanan nan, an nuna misalan bambance-bambancen dukkan waɗannan halayen a gaban Cu(0). Wannan ya faru ne saboda masana'antar magunguna da kuma ƙaruwar mai da hankali kan dawo da amfani da abubuwan kara kuzari na ƙarfe55,56.
Ana ɗaukar martanin cycloaddition na 1,3-dipolar tsakanin acetylene da azide zuwa 1,2,3-triazole, wanda Huisgen ya fara gabatar da shi a shekarun 1960s57, a matsayin martanin nuna haɗin gwiwa. Sakamakon gutsuttsuran triazole 1,2,3 da suka haifar suna da matuƙar muhimmanci a matsayin maganin magunguna a binciken magunguna saboda amfaninsu na halitta da kuma amfani da su a cikin magunguna daban-daban na magani 58.
Wannan martanin ya sami sabon hankali lokacin da Sharpless da wasu suka gabatar da manufar "click chemistry"59. Kalmar "click chemistry" ana amfani da ita don bayyana wani tsari mai ƙarfi da zaɓi na halayen da ake buƙata don haɗa sabbin mahadi da ɗakunan karatu masu haɗin gwiwa cikin sauri ta amfani da haɗin heteroatomic (CXC)60. Shahararren waɗannan halayen ya faru ne saboda yawan amfanin da ake samu da su. Yanayi suna da sauƙi, juriya ga iskar oxygen da ruwa, kuma rabuwar samfura abu ne mai sauƙi61.
Tsarin cycloaddition na gargajiya na 1,3-dipole Huisgen bai faɗi cikin rukunin "click chemistry" ba. Duk da haka, Medal da Sharpless sun nuna cewa wannan taron haɗin azide-alkyne yana faruwa 107-108 a gaban Cu(I) idan aka kwatanta da gagarumin hanzari a cikin ƙimar cycloaddition 1,3-dipolar wanda ba shi da catalytic 62,63. Wannan tsarin amsawar da aka ci gaba ba ya buƙatar kare ƙungiyoyi ko yanayin amsawar da ba ta da tsauri kuma yana ba da kusan cikakkiyar juyawa da zaɓi zuwa 1,2,3-triazoles (anti-1,2,3-triazoles) 1,4-dissublited (Hoto na 3).
Sakamakon isometric na cycloadditions na Huisgen na gargajiya da na jan ƙarfe. Cycloadditions na Huisgen da aka yi wa katalyz na Cu(I) suna ba da triazoles 1,2,3 kawai da aka yi wa katalyz na 1,4, yayin da cycloadditions na Huisgen da aka yi wa katalyz na zafi yawanci suna ba da 1,4 da 1,5-triazoles cakuda 1:1 na azole stereoisomers.
Yawancin ka'idoji sun haɗa da rage tushen tushen Cu(II), kamar rage CuSO4 ko mahaɗin Cu(II)/Cu(0) tare da gishirin sodium. Idan aka kwatanta da sauran halayen ƙarfe da aka haɗa, amfani da Cu(I) yana da manyan fa'idodi na kasancewa mai araha kuma mai sauƙin sarrafawa.
Nazarin kinetic da isotopic na Worrell et al. 65 sun nuna cewa a yanayin terminal alkynes, daidaikun jan ƙarfe guda biyu suna da hannu wajen kunna amsawar kowace kwayar halitta dangane da azide. Tsarin da aka gabatar yana gudana ta hanyar zoben ƙarfe na jan ƙarfe mai membobi shida wanda aka samar ta hanyar haɗa azide zuwa acetylide na jan ƙarfe mai haɗin σ tare da jan ƙarfe mai haɗin π azaman ligand mai ba da gudummawa mai ƙarfi. Ana samar da abubuwan da suka samo asali na jan ƙarfe triazolyl sakamakon matsewar zobe sannan a biyo baya da rushewar proton don samar da samfuran triazole da rufe zagayowar catalytic.
Duk da cewa an rubuta fa'idodin na'urorin sinadarai masu kwarara, akwai sha'awar haɗa kayan aikin nazari a cikin waɗannan tsarin don sa ido kan tsari na ainihin lokaci a situ66,67. UAM ta tabbatar da cewa hanya ce mai dacewa don tsarawa da ƙera masu samar da wutar lantarki masu rikitarwa na 3D daga kayan aiki masu aiki da zafi masu aiki tare da abubuwan da ke haifar da ji (Hoto na 4).
Na'urar samar da wutar lantarki ta aluminum da jan ƙarfe wadda aka ƙera ta hanyar kera ƙarin na'urori masu amfani da ultrasonic (UAM) tare da tsarin tashoshi na ciki mai rikitarwa, na'urorin thermocouples da aka gina a ciki da kuma ɗakin amsawar catalytic. Don ganin hanyoyin ruwa na ciki, an kuma nuna samfurin haske da aka yi ta amfani da stereolithography.
Domin tabbatar da cewa an ƙera reactors don halayen halitta na gaba, dole ne a dumama daskararrun abubuwa lafiya sama da wurin tafasa; an gwada su da matsin lamba da zafin jiki. Gwajin matsin lamba ya nuna cewa tsarin yana riƙe da matsin lamba mai ɗorewa ko da a matsin lamba mai yawa a cikin tsarin (1.7 MPa). An gudanar da gwaje-gwajen hydrostatic a zafin ɗaki ta amfani da H2O a matsayin ruwa.
Haɗa thermocouple ɗin da aka gina a ciki (Hoto na 1) da mai rikodin bayanan zafin jiki ya nuna cewa zafin thermocouple ya kasance 6 °C (± 1 °C) ƙasa da zafin da aka tsara a cikin tsarin FlowSyn. Yawanci, ƙaruwar zafin jiki na 10 °C yana ninka saurin amsawa, don haka bambancin zafin jiki na digiri kaɗan na iya canza ƙimar amsawa sosai. Wannan bambanci ya faru ne saboda asarar zafin jiki a duk faɗin RPV saboda yawan yaduwar zafi na kayan da ake amfani da su a cikin tsarin kera. Wannan jujjuyawar zafi koyaushe yana da tabbas kuma ana iya la'akari da shi lokacin saita kayan aiki don tabbatar da cewa an isa da auna daidai yanayin zafi yayin amsawar. Don haka, wannan kayan aikin sa ido kan layi yana sauƙaƙe sarrafa zafin amsawar sosai kuma yana ba da gudummawa ga ingantaccen inganta tsari da haɓaka yanayi mafi kyau. Hakanan ana iya amfani da waɗannan na'urori masu auna zafin jiki don gano halayen exothermic da hana halayen gudu a cikin manyan tsarin.
Reactor ɗin da aka gabatar a cikin wannan takarda shine misali na farko na amfani da fasahar UAM wajen ƙera reactors masu sinadarai kuma yana magance wasu manyan ƙuntatawa da ke da alaƙa da buga AM/3D na waɗannan na'urori, kamar: (i) Shawo kan matsalolin da aka lura da ke tattare da sarrafa ƙarfe na tagulla ko aluminum (ii) inganta ƙudurin tashar ciki idan aka kwatanta da hanyoyin narkewar foda (PBF) kamar narkewar laser mai zaɓi (SLM)25,69 Rashin kwararar abu da yanayin saman da ke da tsauri26 (iii) ƙarancin zafin aiki, wanda ke sauƙaƙa na'urori masu haɗa kai tsaye, wanda ba zai yiwu ba a fasahar gadon foda, (v) shawo kan ƙarancin halayen injiniya da kuma jin daɗin abubuwan da aka gina bisa polymer zuwa ga wasu abubuwan narkewa na halitta iri-iri17,19.
An nuna aikin mai karɓar wutar lantarki ta hanyar jerin halayen cycloaddition na alkinazide da aka yi wa jan ƙarfe a ƙarƙashin yanayin kwarara mai ci gaba (Hoto na 2). An haɗa mai karɓar wutar lantarki da aka buga ta hanyar ultrasonic da aka nuna a cikin hoto na 4 tare da tsarin kwararar kasuwanci kuma an yi amfani da shi don haɗa ɗakin karatu na azide na nau'ikan 1,2,3-triazoles daban-daban waɗanda aka cire 1,4-substituted ta amfani da amsawar zafin jiki na acetylene da halides na ƙungiyar alkyl a gaban sodium chloride (Hoto na 3). Amfani da hanyar kwarara mai ci gaba yana rage matsalolin aminci da ka iya tasowa a cikin tsarin tsari, tunda wannan amsawar yana samar da tsaka-tsakin azide mai amsawa da haɗari [317], [318]. Da farko, an inganta amsawar don cycloaddition na phenylacetylene da iodoethane (Shiri na 1 - Cycloaddition na phenylacetylene da iodoethane) (duba Hoto na 5).
(Sama hagu) Tsarin saitin da aka yi amfani da shi don haɗa na'urar 3DP cikin tsarin kwarara (sama dama) da aka samo daga tsarin da aka inganta (ƙasa) na tsarin cycloaddition na Huisgen 57 tsakanin phenylacetylene da iodoethane don ingantawa da nuna sigogin canjin da aka inganta na amsawar.
Ta hanyar sarrafa lokacin zama na masu amsawa a cikin sashin catalytic na reactor da kuma lura da zafin amsawa a hankali tare da na'urar firikwensin thermocouple kai tsaye, yanayin amsawa za a iya inganta shi cikin sauri da daidai tare da mafi ƙarancin lokaci da kayan aiki. An gano da sauri cewa an sami mafi girman juyawa ta amfani da lokacin zama na mintuna 15 da zafin amsawa na 150°C. Ana iya gani daga tsarin coefficient na software na MODDE cewa duka lokacin zama da zafin amsawa ana ɗaukar su a matsayin muhimman yanayi na samfurin. Gudanar da ingantaccen mai gyara da aka gina ta amfani da waɗannan yanayi da aka zaɓa yana ƙirƙirar saitin yanayin amsawa wanda aka tsara don haɓaka yankunan kololuwar samfura yayin da rage yankunan kololuwar kayan farawa. Wannan haɓakawa ya haifar da juyi na 53% na samfurin triazole, wanda ya yi daidai da hasashen samfurin na 54%.