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Wax-soo-saarka wax-soo-saarka wax-soo-saarka ayaa beddelaya habka cilmi-baarayaasha iyo warshad-yaqaannada u qaabeeyaan oo u soo saaraan aaladaha kiimikaad si ay u daboolaan baahiyahooda gaarka ah.Waraaqdan, waxaan ku soo gudbineynaa tusaalaha ugu horreeya ee reactor-ka qulqulka ee ay sameeyeen wax-soo-saarka wax-soo-saarka ultrasonic (UAM) ee xaashida adag ee adag oo leh qaybo toos ah oo isku dhafan iyo walxaha dareenka.Tiknoolajiyada UAM kaliya kama adkaanayso qaar badan oo ka mid ah xaddidaadyada hadda la xidhiidha wax-soo-saarka wax-soo-saarka kiimikada, laakiin sidoo kale waxay si weyn u ballaarisaa awoodda aaladahaas.Tiro ka mid ah nafleyda muhimka ah ee 1,4-lagu khilaafay 1,2,3-triazole xeryahooda ayaa si guul leh loo farsameeyay oo lagu hagaajiyay falcelinta cycloaddition Cu-mediated 1,3-dipolar Huisgen iyadoo la adeegsanayo xarunta kimisteriga UAM.Isticmaalka sifooyinka gaarka ah ee UAM iyo socodsiinta socodka joogtada ah, qalabku wuxuu awoodaa inuu kiciyo falcelinta socda iyo sidoo kale bixinta jawaab celinta waqtiga dhabta ah si loo kormeero loona hagaajiyo falcelinta.
Sababo la xiriira faa'iidooyinka muhiimka ah ee ay ka sarreeyaan dhiggiisa tirada badan, kimisteriga qulqulka ayaa ah mid muhiim ah oo sii kordhaya goobaha tacliinta iyo warshadaha labadaba sababtoo ah awoodda ay u leedahay inay kordhiso xulashada iyo waxtarka isku-dhafka kiimikada.Tani waxay ka bilaabataa samaynta molecules organic fudud1 ilaa xeryahooda dawooyinka2,3 iyo alaabta dabiiciga ah4,5,6.In ka badan 50% falcelinta kiimikada wanaagsan iyo warshadaha dawooyinka ayaa ka faa'iidaysan kara socodka joogtada ah7.
Sanadihii la soo dhaafay, waxaa jiray isbeddello sii kordhaya oo kooxo doonaya in ay ku beddelaan agabka muraayadaha dhaqameed ama qulqulka kimistariga iyagoo isticmaalaya kiimiko la qabsan karo "reactors"8.Naqshadaynta soo noqnoqota, wax soo saarka degdega ah, iyo awoodaha saddex-geesoodka ah (3D) ee hababkan ayaa faa'iido u leh kuwa doonaya inay u habeeyaan qalabkooda qayb gaar ah oo falcelin, qalab, ama xaalado.Ilaa hadda, shaqadani waxay si gaar ah diiradda u saartay isticmaalka farsamooyinka daabacaadda 3D ee polymer-ku-salaysan sida stereolithography (SL) 9,10,11, Fused Deposition Modeling (FDM) 8,12,13,14 iyo daabacaadda khadadka7,15., 16. La'aanta isku halaynta iyo awoodda qalabka noocan oo kale ah si ay u sameeyaan fal-celin kiimiko ah oo kala duwan17, 18, 19, 20 waa arrin xaddidan oo weyn oo loogu talagalay codsiga ballaaran ee AM ee goobtan17, 18, 19, 20.
Sababo la xiriira isticmaalka sii kordhaya ee kimistariga socodka iyo guryaha wanaagsan ee la xiriira AM, farsamooyin ka wanaagsan ayaa loo baahan yahay in la sahamiyo kuwaas oo u oggolaanaya isticmaaleyaasha inay abuuraan weelasha falcelinta qulqulka oo leh kimistari la hagaajiyay iyo awoodaha falanqaynta.Hababkani waa inay u oggolaadaan dadka isticmaala inay ka doortaan noocyo kala duwan oo awood sare leh ama qalab shaqeynaya oo awood u leh inay ku shaqeeyaan xaalado badan oo falcelin ah, iyo sidoo kale inay fududeeyaan noocyada kala duwan ee wax soo saarka falanqaynta ee qalabka si ay awood ugu yeeshaan kormeerka iyo xakamaynta falcelinta.
Mid ka mid ah habka wax soo saarka wax soo saarka ee loo isticmaali karo si loo horumariyo reactors kiimikaad caadadii waa Ultrasonic Additive Manufacturing (UAM).Tani habka lamination sheet adag-state khusaysaa gariirka ultrasonic in foils biraha dhuuban si ay u wada xidhi lakabka by lakabka kulaylka volumetric ugu yar iyo heerka sare ee socodka caag ah 21, 22, 23. Si ka duwan inta badan teknoolajiyada AM kale, UAM si toos ah u dhexgalaan karaa wax soo saarka subtractive, loo yaqaan habka wax soo saarka hybrid ah, taas oo xilliyeed in-meel ku-meel-gaar ah xakamaynta (CNC) 23 wax lagu milling ah ee lakabka 4. macnaheedu waa in isticmaaluhu aanu ku koobnayn dhibaatooyinka la xidhiidha ka saarista alaabta dhismaha ee asalka ah ee ka soo baxa kanaalada dareeraha yar yar, taas oo inta badan ku jirta nidaamka budada iyo dareeraha AM26,27,28.Xorriyadda naqshadayntan waxay sidoo kale ku fidsan tahay doorashada agabyada la heli karo - UAM waxay isku xidhi kartaa isku-darka kulaylka la midka ah iyo kuwa aan la midka ahayn ee hal tallaabo.Doorashada isku-dhafka walxaha ee ka baxsan habka dhalaalka waxay la macno tahay in shuruudaha farsamada iyo kiimikada ee codsiyada gaarka ah si fiican loo dabooli karo.Marka lagu daro isku-xidhka adag, dhacdo kale oo ku dhacda isku-xidhka ultrasonic waa dareeraha sarreeya ee alaabta caaga ah ee heerkul hooseeya29,30,31,32,33.Tilmaamkan gaarka ah ee UAM wuxuu u oggolaanayaa walxaha makaanikada / kulaylka in la dhigo inta u dhaxaysa lakabyada birta iyada oo aan waxyeello lahayn.Dareemayaasha UAM ee ku-xidhan waxay fududayn karaan gaarsiinta macluumaadka waqtiga-dhabta ah ee aaladda ilaa isticmaalaha iyada oo loo marayo falanqayn isku dhafan.
Shaqadii hore ee qorayaashu32 waxay muujiyeen awoodda habka UAM si ay u abuuraan qaab-dhismeedyo microfluidic 3D macdan ah oo leh awood dareen leh.Qalabkan waxa loogu talagalay ujeeddooyin la socodka oo keliya.Maqaalkani waxa uu soo bandhigayaa tusaalaha ugu horreeya ee fal-celiyeyaasha kiimikaad ee microfluidic ay soo saartay UAM, qalab firfircoon oo aan xakamayn oo keliya laakiin sidoo kale kicinaya isku-darka kiimikaad oo leh qalab dhismeed oo isku dhafan.Qalabku wuxuu isku daraa faa'iidooyin dhowr ah oo la xidhiidha tignoolajiyada UAM ee soo saarista aaladaha kiimikaad ee 3D, sida: awoodda loogu beddelo naqshad dhammaystiran oo 3D ah oo si toos ah loogu beddelayo qaabka kombuyuutar-ku-caawinta (CAD) ee badeecad;Wax-soo-saarka maaddooyinka badan ee isku-dhafan ee kulaylka sareeyo iyo walxaha kicinta, iyo sidoo kale dareemayaasha kulaylka ee si toos ah ugu dhexjira durdurrada falcelinta si loo xakameeyo saxda ah iyo maaraynta heerkulka falcelinta.Si loo muujiyo shaqeynta reactor-ka, maktabadda dawooyinka muhiimka ah ee 1,4-lagu khilaafay 1,2,3-triazole xeryahooda waxaa lagu farsameeyay naxaas-catalyzed 1,3-dipolar Huisgen cycloaddition.Shaqadani waxay iftiiminaysaa sida isticmaalka agabka sayniska iyo naqshadaynta kombuyuutarku ay u furi karaan fursado cusub iyo fursado kimistari iyada oo loo marayo cilmi-baadhisyo kala duwan.
Dhammaan dareerayaasha iyo reage-yaasha waxa laga soo iibiyay Sigma-Aldrich, Alfa Aesar, TCI, ama Fischer Scientific waxaana la isticmaalay iyada oo aan la nadiifin ka hor.1H iyo 13C NMR spectra oo lagu duubay 400 iyo 100 MHz, siday u kala horreeyaan, ayaa lagu helay JEOL ECS-400 400 MHz spectrometer ama Bruker Avance II 400 MHz spectrometer oo leh CDCl3 ama (CD3)2SO sida dareere ahaan.Dhammaan falcelinta waxaa la sameeyay iyadoo la adeegsanayo Uniqsis FlowSyn nidaamka kimisteriga.
UAM waxa loo isticmaalay in lagu sameeyo dhammaan aaladaha daraasaddan.Tignoolajiyada waxaa la alifay 1999-kii iyo tafaasiilkeeda farsamo, cabirrada hawlgalka iyo horumarkeeda tan iyo markii la alifay waxaa lagu baran karaa iyadoo la adeegsanayo agabka soo socda ee la daabacay34,35,36,37.Qalabka (Jaantus. 1) waxaa la hirgeliyay iyadoo la adeegsanayo hawl culus oo ah 9 kW SonicLayer 4000® UAM system (Fabrisonic, Ohio, USA).Qalabka loo doortay qalabka socodka waxay ahaayeen Cu-110 iyo Al 6061. Cu-110 waxay leedahay maaddo naxaas ah oo sarreeya (ugu yaraan 99.9% copper), taasoo ka dhigaysa musharax wanaagsan oo loogu talagalay falcelinta naxaasta ee naxaasta ah oo sidaas darteed loo isticmaalo "lakabka firfircoon ee gudaha microreactor.Al 6061 O waxaa loo isticmaalaa sida walxaha "badan"., iyo sidoo kale lakabka isdhexgalka ee loo isticmaalo falanqaynta;isdhexgalka ee qaybaha daawaha kaalmeeya iyo gobolka annealed oo lagu daray Cu-110 lakabka.la ogaaday inay kiimikaad ahaan u deggan tahay reage-yaasha loo isticmaalo shaqadan.Al 6061 O marka lagu daro Cu-110 waxaa sidoo kale loo arkaa inay yihiin walxaha isku dhafan ee UAM sidaas darteedna waa walxo ku habboon daraasaddan38,42.Qalabkani waxa ay ku taxan yihiin shaxda 1 ee hoose.
Tallaabooyinka abuuritaanka reactor (1) 6061 substrate alloy aluminium (2) Samaynta kanaalka hoose ee foornada naxaasta ah (3) Gelida heerkulbeegyada inta u dhaxaysa lakabyada (4) Kanaalka sare (5) Gelida iyo meelaha laga baxo (6) fal-celinta monolithic.
Falsafada naqshadeynta kanaalka dareeraha waa in la isticmaalo waddo togan si loo kordhiyo masaafada uu ku safray dareeraha gudaha chip-ka iyadoo la ilaalinayo cabbirka jajabka la maarayn karo.Korodhkan fogaanta ayaa ah mid la jecel yahay si loo kordhiyo wakhtiga xidhiidhka ka falcelinta kicinta iyo bixinta wax soo saar wanaagsan.Chips-yadu waxay adeegsadaan 90° qaloocyada darafyada dariiqa toosan si ay u dhaliyaan qas qas gudaha aaladda44 oo ay kordhiyaan wakhtiga xidhiidhka dareeraha ee dusha sare (catalyst).Si loo sii wanaajiyo isku dhafka la gaari karo, naqshadeynta reactor-ka waxaa ka mid ah laba ilbiriqsi oo fal-celin ah oo lagu daray isku-xir Y ka hor inta aan la gelin qaybta gariiradda isku dhafka ah.Albaabka saddexaad, kaas oo ka gudba qulqulka kala bar degganaanshihiisa, ayaa lagu daray qorshaha mustaqbalka falcelinta isku-dhafka marxaladaha badan.
Dhammaan kanaalada waxay leeyihiin muuqaal labajibbaaran (malaha xaglo taper), taas oo ah natiijada warshadaynta CNC ee xilliyeed ee loo isticmaalo abuurista joomatari kanaalka.Cabbirrada kanaalka ayaa loo doortaa si ay u bixiyaan wax-soo-saarka mugga sare (microreactor), weli yar oo ku filan si loo fududeeyo isdhexgalka dusha sare (catalysts) ee inta badan dareerayaasha ay ku jirto.Cabbirka ku habboon wuxuu ku salaysan yahay waayo-aragnimadii hore ee qorayaasha ee qalabka falcelinta dareeraha-biraha.Cabbirrada gudaha ee kanaalka ugu dambeeya waxay ahaayeen 750 µm x 750 µm iyo wadarta mugga reactor-ku wuxuu ahaa 1 ml.Xidhiidhiyaha gudaha ku dhex jira (1/4″-28 dun UNF) ayaa lagu soo daray naqshadaynta si loogu oggolaado in si sahlan loo dhexgalo aaladda qalabka kiimiko socodka ganacsiga.Cabbirka kanaalka ayaa xaddidaya dhumucda walxaha foil, sifooyinkeeda farsamaysan, iyo xuduudaha isku xidhka ee loo isticmaalo ultrasonics.Balac gaar ah oo loogu talagalay walxaha la bixiyay, maaddadu waxay "sagi doontaa" kanaalka la sameeyay.Hadda ma jiro nooc gaar ah oo xisaabintan ah, markaa ballaca kanaalka ugu sarreeya ee walxaha iyo nashqadaynta waxaa lagu go'aamiyaa si tijaabo ah, taas oo ballac ah 750 µm aysan keeni doonin sag.
Qaabka (square) ee kanaalka waxaa lagu go'aamiyaa iyadoo la isticmaalayo gooyo labajibbaaran.Qaabka iyo cabbirka kanaalada ayaa lagu beddeli karaa mashiinnada CNC iyadoo la adeegsanayo qalab goyn oo kala duwan si loo helo heerarka socodka iyo sifooyinka kala duwan.Tusaale ahaan abuurista kanaal qaloocan oo leh qalab 125 µm ah ayaa laga heli karaa Monaghan45.Marka lakabka bireedku si siman loo dabaqo, codsiga walxaha bireed ee kanaalada waxay yeelan doonaan dusha siman (square).Shaqadan, koontoor labajibbaaran ayaa loo isticmaalay si loo ilaaliyo summetry kanaalka.
Inta lagu jiro hakadka la qorsheeyay ee wax soo saarka, dareemayaasha heerkulka kuleylaha (nooca K) ayaa si toos ah loogu dhex dhisayaa aaladda u dhexeysa kooxaha kanaalka sare iyo kan hoose (Jaantus. 1 - heerka 3).Heerkulbeegyadan ayaa xakameyn kara isbeddelada heerkulka laga bilaabo -200 ilaa 1350 °C.
Habka dhigista birta waxaa fuliya geeska UAM iyadoo la isticmaalayo birta birta ah ee 25.4 mm ballaaran iyo 150 microns.Lakabyadan bireedku waxay ku xidhan yihiin taxane taxane ah oo isku xiga si ay u daboolaan dhammaan aagga dhismaha;cabbirka alaabta la dhigay ayaa ka weyn alaabta ugu dambeysa maadaama habka kala-goynta uu abuurayo qaabka ugu dambeeya ee nadiifka ah.Mashiinka CNC waxaa loo isticmaalaa in lagu makiinado wareegyada dibadda iyo gudaha ee qalabka, taasoo keentay in qalabka la dhammeeyo iyo kanaalada u dhigma aaladda la xushay iyo cabbirrada habka CNC (tusaale ahaan, qiyaastii 1.6 µm Ra).Joogtaynta, buufinta walxaha ultrasonic oo joogto ah iyo wareegyada mishiinada ayaa loo isticmaalaa inta lagu gudajiro habka wax soo saarka ee aaladda si loo hubiyo saxnaanta cabbirka in la ilaaliyo oo qaybta la dhammeeyey ay la kulanto heerka saxda ah ee wax-shiidka ee CNC.Baaxadda kanaalka loo isticmaalo qalabkani waa mid yar oo ku filan si loo hubiyo in walxaha foilku uusan "sageynin" kanaalka dareeraha, sidaas darteed kanaalka wuxuu leeyahay qayb iskutallaab ah oo labajibbaaran.Nusqaamaha suurtagalka ah ee walxaha foil-ka iyo cabbiraadaha habka UAM waxaa si tijaabo ah u go'aamiyay lammaanaha wax-soo-saarka (Fabrisonic LLC, USA).
Daraasaduhu waxay muujiyeen in interface-ka 46, 47 ee xarunta UAM ay jiraan faafin yar oo curiyeyaasha ah iyada oo aan lahayn daaweyn kuleyl ah oo dheeraad ah, sidaas darteed qalabka ku jira shaqadan lakabka Cu-110 ayaa weli ka duwan lakabka Al 6061 oo isbeddel weyn.
Ku rakib nidaamiyaha cadaadiska dhabarka ee horay loo hagaajiyay (BPR) 250 psi (1724 kPa) ee hoos-tagga reactor-ka oo ku soo shub biyaha iyada oo loo marayo reactor-ka heerka 0.1 ilaa 1 ml min-1.Cadaadiska reactor-ka ayaa la kormeeray iyadoo la adeegsanayo beddelaha cadaadiska FlowSyn ee lagu dhex dhisay nidaamka si loo hubiyo in nidaamku sii wadi karo cadaadis joogto ah.Heerkulbeegyada suurtagalka ah ee ku jira reactor-ka socodka ayaa la tijaabiyay iyada oo la raadinayo farqi kasta oo u dhexeeya heerkulbeegyada lagu dhisay reactor-ka iyo heerkulbeegyada lagu dhex dhisay saxanka kuleylka ee Chip FlowSyn.Tan waxa lagu gaaraa iyada oo la beddelo heerkulka kulaylaha ee barnaamijka ah ee u dhexeeya 100 iyo 150 °C 25 °C kordhinta iyo la socodka wixii farqi ah ee u dhexeeya heerkulka la qorsheeyey iyo kan la duubay.Tan waxaa lagu gaaray iyadoo la adeegsanayo tc-08 xogta logger (PicoTech, Cambridge, UK) iyo software-ka PicoLog ee la socda.
Shuruudaha falcelinta cycloaddition ee phenylacetylene iyo iodoethane ayaa la hagaajiyay (Scheme 1-Cycloaddition of phenylacetylene iyo iodoethane, Scheme 1-Cycloaddition of phenylacetylene iyo iodoethane).Hagaajintan waxaa lagu sameeyay iyadoo la adeegsanayo qaab qaabaysan oo dhamaystiran oo tijaabo ah (DOE), iyadoo la adeegsanayo heerkulka iyo wakhtiga degenaanshaha doorsoomayaal iyadoo la hagaajinayo saamiga alkyne: azide ee 1: 2.
Xalalka kala duwan ee sodium azide (0.25 M, 4: 1 DMF: H2O), iodoethane (0.25 M, DMF), iyo phenylacetylene (0.125 M, DMF) ayaa la diyaariyey.1.5 ml aliquot oo xal kasta ah ayaa la isku qasay waxaana lagu dhex shubay reactor-ka heerka socodka iyo heerkulka la rabo.Jawaabta tusaalaha waxaa loo qaatay saamiga ugu sarreeya ee badeecada triazol iyo walxaha bilawga ah ee phenylacetylene waxaana lagu go'aamiyay iyadoo la adeegsanayo chromatography dareeraha waxqabadka sare (HPLC).Joogitaanka falanqaynta, dhammaan falcelinta ayaa la qaaday isla markiiba ka dib markii isku darka falcelintu ka tagtay reactor-ka.Heerarka cabbirka ee loo xushay tayaynta ayaa lagu muujiyay shaxda 2.
Dhammaan shaybaarada waxaa lagu falanqeeyay iyadoo la isticmaalayo Chromaster HPLC system (VWR, PA, USA) oo ka kooban bam afar geesle ah, foornada tiirka, baddelka mowjadda dhererka UV iyo autosampler.Tiirka ayaa u dhigma 5 C18 (VWR, PA, USA), 4.6 x 100 mm, 5 µm cabbirka walxaha, lagu hayo 40°C.Walxahaasi waxa uu ahaa methanol isocratic:biyo 50:50 xadiga socodka 1.5 ml·min-1.Mugga cirbaddu waxay ahayd 5 μl iyo hirarka dhererka baaraha wuxuu ahaa 254 nm.Aagga % ugu sarreeya ee muunadda DOE waxaa laga soo xisaabiyay meelaha ugu sarreeya ee alkyne iyo triazool oo keliya.Soo bandhigida walxaha bilawga ah ayaa suurtogal ka dhigaya in la aqoonsado meelaha ugu sarreeya.
Isku darka natiijooyinka falanqaynta reactor-ka iyo software-ka MODDE DOE (Umetrics, Malmö, Sweden) waxay oggolaatay falanqaynta isbeddelka saxda ah ee natiijooyinka iyo go'aaminta xaaladaha falcelinta ugu habboon ee duufaantan.Ku socodsiinta hagaajinta gudaha iyo xulashada dhammaan shuruudaha moodeelka ee muhiimka ah waxay abuurtaa shuruudo falcelin ah oo loogu talagalay in lagu kordhiyo aagga ugu sarreeya ee badeecadda iyadoo la dhimayo aagga ugu sarreeya ee quudinta acetylene.
Oxidation ee dusha naxaasta ee qolka falcelinta catalytic ayaa lagu gaadhay iyadoo la isticmaalayo xal hydrogen peroxide (36%) oo ku qulqulaya qolka falcelinta (heerka socodka = 0.4 ml min-1, wakhtiga degenaanshaha = 2.5 min) ka hor inta aan la isku dhejin xarun kasta oo triazole.maktabad.
Marka la go'aamiyo shuruudaha ugu fiican, waxaa lagu dabaqay noocyo kala duwan oo acetylene iyo haloalkane ah si ay u oggolaadaan isku-dubarid maktabad yar oo isku dhafan, taas oo abuuraysa suurtogalnimada in shuruudahan lagu dabaqo tiro balaadhan oo ah reagents suurtagal ah (Jaantus. 1).2).
Diyaarso xalal gaar ah oo sodium azide ah (0.25 M, 4: 1 DMF: H2O), haloalkanes (0.25 M, DMF), iyo alkynes (0.125 M, DMF).Aliquots 3 ml oo xal kasta ah ayaa la isku qasay waxaana lagu dhex shubay reactor-ka heerka 75 µl/min iyo heerkul ah 150°C.Mugga oo dhan waxaa lagu soo ururiyay fiilo waxaana lagu qasi jiray 10 ml oo ah ethyl acetate.Xalka muunada waxaa lagu dhaqay 3 x 10 ml oo biyo ah.Lakabyada aqueous ayaa la isku daray oo laga soo saaray 10 ml ethyl acetate, ka dibna lakabyada organic waa la isku daray, lagu dhaqay 3 × 10 ml brine, la qalajiyey MgSO 4 oo la sifeeyay, ka dibna dareeraha ayaa laga saaray vacuo.Tusaalooyinka waxaa lagu sifeeyay silica gel column chromatography iyadoo la adeegsanayo ethyl acetate ka hor falanqaynta isku darka HPLC, 1H NMR, 13C NMR iyo xallinta sare ee cabbirka cabbirka (HR-MS).
Dhammaan spectra-yada waxa lagu helay iyadoo la isticmaalayo a Thermofischer Precision Orbitrap mass spectrometer oo leh ESI oo ah isha ionization.Dhammaan shaybaarada waxaa lagu diyaariyey acetonitrile sida dareere ahaan.
Falanqaynta TLC waxaa lagu sameeyay taarikada silica leh substrate aluminium ah.Taarikada waxaa lagu sawiray iftiinka UV (254 nm) ama wasakhaynta vanillin iyo kuleylinta.
Dhammaan shaybaarada waxaa lagu falanqeeyay iyadoo la adeegsanayo nidaamka VWR Chromaster (VWR International Ltd., Leighton Buzzard, UK) oo lagu qalabeeyay autosampler, bamka binary oo leh foorno tiir ah iyo hal mawjadaha baaraha.Tiirka ACE Equivalence 5 C18 (150 x 4.6 mm, Advanced Chromatography Technologies Ltd., Aberdeen, Scotland) ayaa la isticmaalay.
Irbadaha (5 µl) ayaa si toos ah looga sameeyay isku darka falcelinta cayriin ee la qasi jiray (1:10 dilution) waxaana lagu falanqeeyay biyo: methanol (50:50 ama 70:30), marka laga reebo muunado qaarkood iyadoo la adeegsanayo 70:30 nidaamka dareeraha (oo lagu tilmaamay lambarka xiddigga) heerka socodka 1.5 ml/min.Tiirka waxaa lagu hayaa heerkul ah 40 ° C.Dhererka mowjadda baarehu waa 254 nm.
Aagga % ugu sarreeya ee muunadda waxaa laga soo xisaabiyay aagga ugu sarreeya ee alkyne haraaga ah, badeecada triazole oo keliya, iyo soo bandhigida walxaha bilawga ah ayaa suurtageliyay in la aqoonsado meelaha ugu sarreeya.
Dhammaan shaybaarada waxaa lagu falanqeeyay iyadoo la isticmaalayo Thermo iCAP 6000 ICP-OES.Dhammaan heerarka cabbiraadda waxaa la diyaariyey iyadoo la adeegsanayo 1000 ppm Cu xal caadi ah oo ah 2% nitric acid (SPEX Certi Prep).Dhammaan heerarka waxaa lagu diyaariyey xal 5% DMF iyo 2% HNO3, iyo dhammaan shaybaarrada waxaa lagu qasi jiray 20 jeer muunad xal DMF-HNO3.
UAM waxay isticmaashaa alxanka birta ultrasonic si ay ugu biirto birta birta ah ee loo isticmaalo in lagu abuuro shirka kama dambaysta ah.Alxanka birta Ultrasonic waxay isticmaashaa qalab bir gariiraya (oo loo yaqaan gees ama gees ultrasonic) si ay cadaadis ugu saarto lakabka birta ah ee hore loo xoojiyay si loogu xidho/hore loo xoojiyay iyadoo la gariirayo walxaha.Hawlgalka joogtada ah, sonotrode wuxuu leeyahay qaab cylindrical ah wuxuuna ku duubaa dusha sare ee alaabta, isagoo ku dhejinaya aagga oo dhan.Marka cadaadiska iyo gariirka la isticmaalo, oksaydhyada dusha sare ee maaddadu way dillaaci kartaa.Cadaadiska joogtada ah iyo gariirku waxay u horseedi karaan burburinta qallafsanaanta walxaha 36.Xidhiidhka dhow ee kulaylka iyo cadaadiska gudaha ayaa markaa keenaya dammaanad adag oo weji ah oo ku saabsan is-dhexgalka walxaha;Waxa kale oo ay kor u qaadi kartaa isku-xidhka iyada oo beddeleysa tamarta dusha sare48.Dabeecadda habka isku xidhka ayaa ka adkaaday qaar badan oo ka mid ah dhibaatooyinka la xidhiidha heerkulka dhalaalka doorsooma iyo saamaynta heerkulka sare ee lagu sheegay tignoolajiyada wax soo saarka dheeraadka ah.Tani waxay u oggolaanaysaa isku xidhka tooska ah (sida iyada oo aan la beddelin dusha sare, buuxinta ama dhejisyada) ee dhowr lakab oo walxo kala duwan ah oo loo sameeyo hal dhisme oo la isku daray.
Qodobka labaad ee ugu wanaagsan CAM waa heerka sare ee qulqulka caagga ah ee lagu arkay walxaha macdan xitaa heerkulka hooseeya, ie si aad uga hooseeya barta dhalaalka ee alaabta macdan.Isku darka gariirada ultrasonic iyo cadaadiska ayaa sababa heer sare oo ah socdaalka xadka hadhuudhka deegaanka iyo recrystalization iyada oo aan korodhka heerkulka muhiimka ah dhaqan ahaan la xidhiidha alaabta bulk.Inta lagu guda jiro abuuritaanka shirka kama dambaysta ah, dhacdadan waxaa loo isticmaali karaa in lagu dhejiyo qaybaha firfircoon ee firfircoon ee u dhexeeya lakabyada birta, lakabka lakabka.Waxyaabaha ay ka midka yihiin fiber optic 49, xoojinta 46, elektaroonigga 50 iyo thermocouples (shaqadan) ayaa si guul leh loogu dhex daray qaababka UAM si loo abuuro ururo isku dhafan oo firfircoon oo firfircoon.
Shaqadan, labadaba awoodaha isku xidhka walxaha kala duwan iyo awoodaha isdhexgalka UAM ayaa loo isticmaalay si loo abuuro microreactor ku habboon xakamaynta heerkulka catalytic.
Marka la barbardhigo palladium (Pd) iyo biraha kale ee sida caadiga ah loo isticmaalo, Cu-catalysis waxay leedahay faa'iidooyin dhowr ah: (i) Dhaqaale ahaan, Cu way ka jaban tahay biraha kale ee badan ee loo isticmaalo catalysis sidaas darteedna waa doorasho soo jiidasho leh ee warshadaha kiimikada s si fiican u shaqeeyaa maqnaanshaha ligands kale.Xadhigyadani inta badan qaab dhismeed ahaan waa kuwo fudud oo aan qaali ahayn.haddii la rabo, halka kuwa loo isticmaalo Pd chemistry ay inta badan yihiin kuwo adag, qaali ah, iyo hawada xasaasiga ah (iv) Cu, gaar ahaan loo yaqaan awoodda ay ku xirto alkynes in synthesis, sida Sonogashira's bimetallic catalyzed coupling iyo cycloaddition with azides (riix chemistry) (v) Cu sidoo kale waxay kor u qaadi kartaa arylation ee qaar ka mid ah falcelinta nuclesmanophiles in U.
Dhawaan, tusaalooyinka heterogenization ee dhammaan falcelintan joogitaanka Cu (0) ayaa la muujiyay.Tani waxay si weyn ugu wacan tahay warshadaha dawooyinka iyo diiradda sii kordheysa ee soo kabashada iyo dib u adeegsiga biraha birta ah55,56.
Dareen-celinta cycloaddition ee 1,3-dipolar ee u dhaxaysa acetylene iyo azide ilaa 1,2,3-triazole, oo markii ugu horreysay ay Huisgen soo jeedisay 1960-kii 57, ayaa loo arkaa inay tahay fal-celin mudaaharaad ah.Natiijooyinka 1,2,3 triazol ee ka soo baxa ayaa xiiso gaar ah u leh sida farmashiyaha ee helitaanka daroogada sababtoo ah codsiyadooda bayoolojiga iyo isticmaalka daawooyinka kala duwan ee daaweynta 58.
Dareen-celintani waxay heshay dareen hor leh markii Sharpless iyo kuwa kale ay soo bandhigeen fikradda "riix kimistari"59.Erayga "click chemistry" waxaa loo isticmaalaa in lagu qeexo falcelin adag oo la xushay oo ah falcelinta degdega ah ee xeryahooda cusub iyo maktabadaha isku dhafka ah iyadoo la isticmaalayo heteroatomic bonding (CXC)60.Soo jiidashada synthetic ee falcelintan waxaa sabab u ah wax-soo-saarka sare ee la xiriira iyaga.xaaladuhu waa sahlan yihiin, iska caabinta ogsijiinta iyo biyaha, kala soocida alaabadu waa mid fudud61.
1,3-dipole Huisgen cycloaddition kuma dhaco qaybta "click chemistry".Si kastaba ha ahaatee, Bilad iyo Sharpless waxay muujiyeen in dhacdadan isku xidhka azide-alkyne ay marayso 107-108 joogitaanka Cu (I) marka la barbar dhigo dardargelinta muhiimka ah ee qiyaasta 1,3-dipolar cycloaddition 62,63.Habkan falcelinta horumarsan uma baahna ilaalinta kooxaha ama xaaladaha falcelinta qallafsan waxayna bixisaa beddelaad dhammaystiran oo dhammaystiran iyo xulashada 1,4-la khilaafay 1,2,3-triazoles (anti-1,2,3-triazoles) waqti ka dib (Jaantus 3).
Natiijooyinka isometric ee cycloadditions Huisgen-katalyzed ee caadiga ah iyo naxaasta.Cu (I) -catalyzed Huisgen cycloadditions ayaa siinaya kaliya 1,4-lagu khilaafay 1,2,3-triazoles, halka kuleylku sababay cycloadditions Huisgen sida caadiga ah waxay bixiyaan 1,4- iyo 1,5-triazoles a 1: 1 isku dar ah azole stereoisomers.
Hab-maamuusyada intooda badani waxay ku lug leeyihiin dhimista ilaha xasilloon ee Cu(II), sida dhimista CuSO4 ama Cu (II)/Cu (0) oo ay weheliso cusbada sodium.Marka la barbar dhigo falcelinta birta ee kale, isticmaalka Cu(I) ayaa leh faa'iidooyinka ugu muhiimsan ee ah inay noqoto mid jaban oo fudud in la maareeyo.
Kinetic iyo daraasadaha isotopic ee Worrell et al.65 waxay muujiyeen in kiiska alkynes terminal, laba u dhigma oo naxaas ah ayaa ku lug leh kicinta falcelinta molecule kasta marka loo eego azide.Habka la soo jeediyay wuxuu ku sii socdaa giraan naxaas ah oo lix xubnood ka kooban oo uu sameeyay iskudubarid azide ilaa σ-ku-xidhan naxaasta acetylide oo leh naxaas-ku-xidhan oo ah ligand deeq-bixiye oo deggan.Copper triazolyl derivatives ayaa la sameeyay iyadoo ay ugu wacan tahay foosha giraanta oo ay raacdo proton-ka qudhunka si loo sameeyo badeecooyinka triazol oo xidho wareegga catalytic.
In kasta oo faa'iidooyinka aaladaha kimisteriga qulqulka si wanaagsan loo diiwaangeliyay, waxaa jiray rabitaan ah in lagu dhex daro aaladaha falanqaynta nidaamyadan loogu talagalay kormeerka habka-waqtiga dhabta ah ee situ66,67.UAM waxay caddaysay inay tahay hab ku habboon naqshadaynta iyo soo saarista reactors qulqulka qulqulka 3D ee aad u adag ee ka soo jeeda walxo kuleyl leh oo si toos ah ugu xidhan walxaha dareenka (Jaantus. 4).
Aluminium-copper reactor-ka ay soo saarto wax soo saarka ultrasonic additive (UAM) oo leh qaab-dhismeedka kanaalka gudaha ee kakan, heerkulbeegyada ku dhex jira iyo qolka falcelinta catalytic.Si loo arko waddooyinka dareeraha gudaha, tusaale hufan oo la sameeyay iyadoo la isticmaalayo stereolithography ayaa sidoo kale la muujiyay.
Si loo hubiyo in reactors loo sameeyo falcelinta dabiiciga ah ee mustaqbalka, dareerayaasha waa in si badbaado leh loogu kululeeyaa meel ka sarraysa barta karkaraya;waa cadaadis iyo heerkul la tijaabiyay.Tijaabada cadaadiska ayaa muujisay in nidaamku uu ilaalinayo cadaadis joogto ah oo joogto ah xitaa cadaadiska sare ee nidaamka (1.7 MPa).Tijaabooyinka Hydrostatic ayaa lagu sameeyay heerkulka qolka iyadoo la isticmaalayo H2O dareere ahaan.
Ku xidhidhiyaha ku dhex jira (Jaantuska 1) heerkulbeegyada kaydiyaha xogta heerkulka ayaa muujisay in heerkulku uu ahaa 6 °C (± 1 °C) oo ka hooseeya heerkulka barnaamijka ee nidaamka FlowSyn.Caadiyan, kororka 10°C ee heerkulku wuxuu labanlaabmaa heerka falcelinta, markaa kala duwanaanshaha heerkulka dhawr darajo ayaa si weyn u bedeli kara heerka falcelinta.Kala duwanaanshiyahan ayaa sabab u ah luminta heerkulka guud ahaan RPV sababtoo ah kala-baxa kulaylka sare ee alaabta loo isticmaalo habka wax soo saarka.Dhaqdhaqaaqa kuleylku waa mid joogto ah sidaas darteed waa la tixgelin karaa marka la dejinayo qalabka si loo hubiyo in heerkul sax ah la gaaro oo la cabbiro inta lagu jiro falcelinta.Sidaa darteed, qalabkan kormeerka ee internetka wuxuu fududeeyaa xakamaynta adag ee heerkulka falcelinta wuxuuna ka qaybqaataa hagaajinta habka saxda ah iyo horumarinta xaaladaha ugu fiican.Dareemayaashan ayaa sidoo kale loo isticmaali karaa in lagu ogaado falcelinta exothermic iyo ka hortagga falcelinta cararka ee nidaamyada cabbirka ballaaran.
Reactor-ka lagu soo bandhigay warqadan waa tusaalaha ugu horreeya ee codsiga tikniyoolajiyada UAM ee soo saarista reactors kiimikaad iyo wax ka qabta dhowr xaddidaad oo waaweyn oo hadda la xidhiidha daabacaadda AM / 3D ee qalabkan, sida: (i) Ka gudubka dhibaatooyinka la xusay ee la xidhiidha farsamaynta naxaasta ama aluminium aluminium ah (ii) hagaajinta xalinta kanaalka gudaha marka la barbardhigo budada dhalaalka sariirta (PBF) hababka sida muraayadda dhalaalaysa 6 (S9 Po) heerkulka processing hoose, taas oo sahlaysa isku xidhka tooska ah dareemayaal, taas oo aan suurto gal in technology sariirta budada, (v) ka adkaanta guryaha farsamo liidata iyo dareenka qaybaha polymer-ku salaysan ee kala duwan ee dareere organic caadiga ah17,19.
Shaqeynta reactor-ka waxaa lagu muujiyay taxane ah naxaas-catalyzed alkinazide cycloaddition reactions hoos xaaladaha socodka joogtada ah (Jaantus. 2).Qalabka naxaasta daabacan ee ultrasonic ee lagu muujiyey berdaha.4 waxaa lagu dhex daray nidaamka socodka ganacsiga waxaana loo isticmaalay in lagu soo saaro maktabad azide ah oo kala duwan 1,4-lagu khilaafay 1,2,3-triazoles iyadoo la adeegsanayo falcelinta heerkulka xakamaynta ee acetylene iyo halides kooxda alkyl ee joogitaanka sodium chloride (Jaantus. 3).Isticmaalka habka socodka joogtada ah wuxuu yareeyaa arrimaha nabdoonaanta ee ka dhalan kara hababka dufcada, maadaama falcelintani ay soo saarto dhexdhexaadin azide ah oo aad u firfircoon oo khatar ah [317], [318].Markii hore, falcelinta ayaa loo hagaajiyay cycloaddition ee phenylacetylene iyo iodoethane (Scheme 1 - Cycloaddition of phenylacetylene iyo iodoethane) (eeg sawirka 5).
(Bidix sare) Jadwalka habaynta loo isticmaalo in lagu daro reactor 3DP nidaamka socodka (midig sare) ee laga helay nidaamka la hagaajiyay (hoose) ee nidaamka cycloaddition Huisgen 57 ee u dhexeeya phenylacetylene iyo iodoethane si kor loogu qaado loona muujiyo cabbiraadaha heerka beddelka ee la hagaajiyay ee falcelinta.
Iyada oo la xakameynayo wakhtiga degenaanshaha reactants ee qaybta kicinta ee reactor-ka oo si taxadar leh loola socdo heerkulka falcelinta oo leh dareeme kuleyl toos ah oo isku dhafan, xaaladaha falcelinta ayaa si dhakhso ah oo sax ah loogu wanaajin karaa ugu yaraan waqti iyo agab.Si dhakhso ah ayaa loo ogaaday in beddelka ugu sarreeya lagu gaadhay iyadoo la adeegsanayo wakhtiga degenaanshaha ee 15 daqiiqo iyo heerkulka falcelinta ee 150 ° C.Waxaa laga arki karaa goobta isku-dhafka ah ee software-ka MODDE in waqtiga joogitaanka iyo heerkulka falcelinta labadaba loo tixgeliyo xaaladaha muhiimka ah ee moodeelka.Ku socodsiinta hagaajinta ku dhex jirta iyadoo la adeegsanayo shuruudahan la doortay waxay abuurtaa shuruudo falcelin ah oo loogu talagalay in lagu kordhiyo aagagga ugu sarreeya ee alaabta iyadoo la dhimayo meelaha ugu sarreeya ee alaabta.Hagaajintan waxay keentay beddelka 53% ee badeecada triazole, taas oo si sax ah u dhiganta saadaasha moodeelka ee 54%.