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Li-photosensitizer tse sebetsang hantle li bohlokoa haholo ts'ebelisong e atileng ea bongaka ea phototherapy.Leha ho le joalo, li-photosensitizer tse tloaelehileng ka kakaretso li na le bothata ba ho monya nako e khuts'oane ea maqhubu, ho se khonehe ha lifoto, tlhahiso e tlase ea mefuta ea oksijene e sebetsang (ROS), le ho tima ROS ka lebaka la aggregation.Mona re tlaleha hoo e ka bang infrared (NIR) supramolecular photosensitizer (RuDA) mediated by self-assembles of Ru (II) -arene organometallic complexes ka aqueous solution.RuDA e ka hlahisa oksijene e le 'ngoe feela (1O2) sebakeng se kopantsoeng,' me e bontša boitšoaro bo hlakileng ba moloko oa 1O2 ka lebaka la keketseho e kholo ea ts'ebetso ea crossover pakeng tsa tsamaiso ea singlet-triplet.Tlas'a ketso ea 808 nm laser light, RuDA e bonts'a tlhahiso ea 1O2 quantum ea 16.4% (e amohetsoeng ke FDA e tala ea indocyanine: ΦΔ = 0.2%) le katleho e phahameng ea phetoho ea photothermal ea 24.2% (nanorods ea khauta ea khoebo) e nang le lifoto tse ntle haholo.: 21.0%, li-nanoshell tsa khauta: 13.0%).Ho feta moo, li-RuDA-NP tse nang le biocompatibility e ntle li ka bokella ka mokhoa o ikhethileng libakeng tsa hlahala, tsa baka ho fokotseha ho hoholo ha hlahala nakong ea kalafo ea photodynamic ka phokotso ea 95.2% ea molumo oa tumor ho vivo.Phekolo ena e matlafatsang ea ho kopanya photodynamic e fana ka leano la ho nts'etsapele li-photosensitizer tse nang le thepa e ntle ea photophysical le photochemical.
Ha ho bapisoa le phekolo e tloaelehileng, phekolo ea photodynamic (PDT) ke phekolo e khahlehang bakeng sa kankere ka lebaka la melemo ea eona ea bohlokoa e kang taolo e nepahetseng ea sebaka sa marang-rang, ho se hlaselehe, ho hanyetsa lithethefatsi ho sa tsotellehe, le ho fokotsa litla-morao 1,2,3.Tlas'a mahlaseli a khanyang, li-photosensitizers tse sebelisoang li ka sebelisoa ho theha mefuta ea oksijene e sebetsang haholo (ROS), e lebisang ho apoptosis / necrosis kapa likarabo tsa 'mele oa ho itšireletsa mafung4,5. Leha ho le joalo, boholo ba li-photosensitizer tse tloaelehileng, joalo ka chlorine, porphyrins, le anthraquinones, li monya nako e khuts'oane ea wavelength (frequency <680 nm), kahoo e baka ho kenella ha leseli ka lebaka la ho monya ho matla ha limolek'hule tsa tlhaho (mohlala, hemoglobin le melanin). sebaka se bonahalang6,7. Leha ho le joalo, boholo ba li-photosensitizer tse tloaelehileng, joalo ka chlorine, porphyrins, le anthraquinones, li monya nako e khuts'oane ea wavelength (frequency <680 nm), kahoo e baka ho kenella ha leseli ka lebaka la ho monya ho matla ha limolek'hule tsa tlhaho (mohlala, hemoglobin le melanin). sebaka se bonahalang6,7. Однако большинство обычных фотосенсибилизаторов, таких как хлорины, порфирины и антрахиноны, обладают относительно коротковолновым поглощением (частота < 680 нм), что приводит к плохому проникновению света из-за интенсивного поглощения биологических молекул (например, гемоглобина и меланина) в видимая область6,7. Leha ho le joalo, li-photosensitizer tse tloaelehileng tse kang chlorine, porphyrins le anthraquinones li monya nako e khuts'oane ea wavelength (<680 nm) e bakang ho kenella ha leseli ho fokolang ka lebaka la ho monya ho matla ha limolek'hule tsa baeloji (mohlala, hemoglobin le melanin) sebakeng se bonahalang6,7.吸收, 大多数 传统由于 的生物 的 分子分子 的导致光穿透性差.吸收, 大多数大多数 <680 nm) 因此因此 由于较 分子 (血红 蛋白 黑色素 黑色素) 的,吸收 吸收 吸收 吸收 吸收 吸收 HI导致光穿透性差. Однако большинство традиционных фотосенсибилизаторов, таких как хлорины, порфирины и антрахиноны, имеют относительно коротковолновое поглощение (частота < 680 нм) из-за сильного поглощения биомолекул, таких как гемоглобин и меланин, что приводит к плохому проникновению света. Leha ho le joalo, boholo ba li-photosensitizer tsa setso tse kang chlorine, porphyrins le anthraquinones li monya nako e khuts'oane ea wavelength (frequency <680 nm) ka lebaka la ho monya ka matla ha li-biomolecules tse joalo ka hemoglobin le melanin ho baka ho kenella ha leseli.Sebaka se bonahalang 6.7.Ka hona, li-photosensitizer tse haufi le infrared (NIR) tse kentsoeng "fensetereng ea phekolo" ea 700-900 nm li loketse hantle bakeng sa phototherapy.Kaha khanya e haufi le infrared ke eona e fokolang haholo ke lisele tsa likokoana-hloko, e ka lebisa ho kenella ho tebileng le ho fokotseha ha photodamage8,9.
Ka bomalimabe, li-photosensitizer tse ntseng li le teng tsa NIR ka kakaretso li na le photostability e fokolang, matla a tlase a singlet oxygen (1O2) a hlahisang, le ho tima 1O2 e bakoang ke ho kopanya, e fokotsang ts'ebeliso ea bona ea bongaka10,11.Le hoja ho entsoe boiteko bo matla ba ho ntlafatsa thepa ea photophysical le photochemical ea li-photosensitizers tse tloaelehileng, ho fihlela joale litlaleho tse 'maloa li tlalehile hore li-photosensitizer tse nkang NIR li ka rarolla mathata ana kaofela.Ho phaella moo, li-photosensitizer tse 'maloa li bontšitse tšepiso ea tlhahiso e sebetsang ea 1O212,13,14 ha e khantšitsoe ka leseli le ka holimo ho 800 nm, kaha matla a photon a fokotseha ka potlako sebakeng se haufi le IR.Triphenylamine (TFA) joalo ka mofani oa elektrone 'me [1,2,5]thiadiazole-[3,4-i]dipyrido[a,c]phenazine (TDP) e le sehlopha se amohelang elektronike Donor-acceptor (DA) mofuta oa dae sehlopha ea li-dyes, tse monyang haufi le infrared, tse ithutoang haholo bakeng sa li-bioimaging II tse haufi le infrared le photothermal therapy (PTT) ka lebaka la lekhalo la tsona le moqotetsane.Ka hona, lidae tsa mofuta oa DA li ka sebelisoa bakeng sa PDT ka thabo e haufi-ufi ea IR, le hoja li sa ka tsa ithutoa ka seoelo e le li-photosensitizers bakeng sa PDT.
Hoa tsebahala hore katleho e phahameng ea intersystem crossing (ISC) ea li-photosensitizer e khothalletsa ho thehoa ha 1O2.Leano le tlwaelehileng la ho ntshetsapele tshebetso ya ISC ke ho ntlafatsa kgokahano ya spin-orbit coupling (SOC) ya difotosensitizer ka ho hlahisa diathomo tse boima kapa mefuta e kgethehileng ya organic.Leha ho le joalo, mokhoa ona o ntse o na le mefokolo le meeli19,20.Haufinyane tjena, supramolecular self-assembly e fane ka mokhoa o bohlale o ka tlaase ho ea holimo bakeng sa ho etsoa ha lisebelisoa tse sebetsang boemong ba molek'hule, 21,22 e nang le melemo e mengata ea phototherapy: (1) li-photosensitizer tse ikemetseng li ka 'na tsa e-ba le monyetla oa ho etsa mehaho ea li-ribbon.E ts'oana le meaho ea elektroniki e nang le kabo e teteaneng ea maemo a matla ka lebaka la li-orbit tse fetang lipakeng tsa meaho.Ka hona, papali ea matla pakeng tsa boemo bo tlaase ba singlet e thabisang (S1) le naha ea boahelani e thabisang ea triplet (Tn) e tla ntlafatsoa, e leng molemo bakeng sa ts'ebetso ea ISC 23, 24.(2) Kopano ea Supramolecular e tla fokotsa phomolo e se nang mahlaseli e thehiloeng ho intramolecular motion limitation mechanism (RIM), e leng eona e khothalletsang ts'ebetso ea ISC 25, 26.(3) Kopano ea supramolecular e ka sireletsa limolek'hule tse ka hare tsa monoma ho tloha ho oxidation le ho senyeha, kahoo e ntlafatsa haholo photostability ea photosensitizer.Ka lebaka la melemo e kaholimo, re lumela hore litsamaiso tsa supramolecular photosensitizer e ka ba mokhoa o ts'episang ho hlola mefokolo ea PDT.
Li-complexes tse thehiloeng ho Ru(II) ke sethala sa bongaka se ts'episang bakeng sa lits'ebetso tse ka bang teng tlhahlobong le kalafong ea mafu ka lebaka la thepa ea bona e ikhethang le e khahlang ea likokoana-hloko28,29,30,31,32,33,34.Ho phaella moo, bongata ba linaha tse thabisang le thepa ea photophysicochemical e ka sebelisoang ea Ru(II)-based complexes e fana ka melemo e mengata bakeng sa nts'etsopele ea li-photosensitizers tse thehiloeng ho Ru (II)35,36,37,38,39,40.Mohlala o hlokomelehang ke ruthenium(II) polypyridyl complex TLD-1433, eo hajoale e ntseng e le litekong tsa bongaka tsa Phase II e le photosensitizer bakeng sa kalafo ea mofets'e oa senya o se nang mesifa (NMIBC)41.Ho phaella moo, ruthenium (II) arene organometallic complexes e sebelisoa haholo e le li-chemotherapeutic agents bakeng sa phekolo ea kankere ka lebaka la chefo ea tsona e tlaase le boiketlo ba ho fetola42,43,44,45.Thepa ea ionic ea Ru(II) -arene organometallic complexes e ke ke ea ntlafatsa feela ho qhibiliha ho fokolang ha chromophores ea DA ka li-solvents tse tloaelehileng, empa hape ho ntlafatsa kopano ea chromophores ea DA.Ho feta moo, sebopeho sa pseudooctahedral half-sandwich ea organometallic complexes ea Ru (II) -arenes e ka thibela ka thata ho thibela H-aggregation ea mofuta oa chromophores ea mofuta oa DA, ka tsela eo e nolofalletsa ho thehoa ha J-aggregation ka lihlopha tsa ho monya tse khubelu.Leha ho le joalo, mefokolo ea tlhaho ea Ru(II) -arene complexes, joalo ka botsitso bo tlase le / kapa bioavailability e futsanehileng, e ka ama ts'ebetso ea kalafo le ts'ebetso ea vivo ea li-complexes tsa arene-Ru (II).Leha ho le joalo, liphuputso li bonts'itse hore mefokolo ena e ka hlōloa ka ho koahela li-ruthenium complexes tse nang le li-polymers tse lumellanang le bio ka ho kopanya 'mele kapa covalent conjugation.
Mosebetsing ona, re tlaleha li-complexes tsa DA-conjugated tsa Ru (II) -arene (RuDA) tse nang le mokokotlo oa NIR ka tlamahano ea ho hokahanya pakeng tsa DAD chromophore le Ru (II) -arene moiety.Li-complexes tse hlahisoang li ka ikamahanya le li-metallosupramolecular vesicles ka metsing ka lebaka la ho se kopane.Ka ho hlakileng, kopano ea supramolecular e ile ea fa RuDA ka thepa ea ho tšela li-polymerization-induced intersystem crossing-over, e leng se ileng sa eketsa katleho ea ISC, e neng e le molemo haholo bakeng sa PDT (Fig. 1A).Ho eketsa ho bokellana ha hlahala le biocompatibility ea vivo, FDA-approved Pluronic F127 (PEO-PPO-PEO) e ne e sebelisetsoa ho kenyelletsa RuDA47,48,49 ho theha RuDA-NP nanoparticles (Figure 1B) e neng e sebetsa e le PDT / Dual- mokhoa oa PTT proxy.Ka kankere phototherapy (Setšoantšo sa 1C), RuDA-NP e ne e sebelisetsoa ho tšoara litoeba tse hlobotseng ka lihlahala tsa MDA-MB-231 ho ithuta katleho ea PDT le PTT ka vivo.
Setšoantšo sa moralo oa mochine oa photophysical oa RuDA ka mefuta ea monomeric le e kopantsoeng bakeng sa phototherapy ea kankere, motsoako oa B RuDA-NPs le C RuDA-NPs bakeng sa PDT e entsoeng ke NIR le PTT.
RuDA, e nang le ts'ebetso ea TPA le TDP, e lokiselitsoe ho latela mokhoa o bontšitsoeng ho Setšoantšo sa Tlatsetso 1 (Setšoantšo sa 2A), 'me RuDA e ne e khetholloa ke 1H le 13C NMR spectra, electrospray ionization mass spectrometry, le tlhahlobo ea motheo (Figure Supplementary Figures 2-4 ).RuDA electron density difference map of the lowest singlet transition was computed by time-dependent density functional theory (TD-DFT) ho ithuta ts'ebetso ea phetisetso ea tefiso.Joalokaha ho bontšitsoe ho Supplementary Figure 5, electron density drifts haholo-holo ho tloha triphenylamine ho ea yuniti e amohelang TDP ka mor'a photoexcitation, e ka hlahisoang ke phetoho e tloaelehileng ea intramolecular charge transfer (CT).
Sebopeho sa lik'hemik'hale sa Ore B: Ho monya spectra ea Ore ka metsoako ea likarolo tse fapaneng tsa DMF le metsi.C Maemo a tloaelehileng a ho monya a RuDA (800 nm) le ICG (779 nm) khahlano le nako ho 0.5 W cm-2 ea leseli la 808 nm laser.D The photodegradation ea ABDA e bontšoa ke ho thehoa ha RuDA-induced 1O2 ka metsoako ea DMF / H2O e nang le likahare tse fapaneng tsa metsi tlas'a ketso ea mahlaseli a laser a nang le leqhubu la 808 nm le matla a 0.5 W / cm2.
Abstract — UV-bonable absorption spectroscopy e ile ea sebelisoa ho ithuta ka thepa ea ho ipokella ea Ore metsoakong ea DMF le metsi ka likarolelano tse fapaneng.Joalokaha ho bontšitsoe feiga.2B, RuDA e bonts'a lihlopha tsa ho monya ho tloha ho 600 ho isa ho 900 nm ho DMF e nang le sehlopha se phahameng sa ho monya ho 729 nm.Ho eketsa bongata ba metsi ho lebisitse phetohong e khubelu ea butle-butle ea ho monya ha Ore ho fihla ho 800 nm, e leng se bontšang J-aggregation ea Ore tsamaisong e kopaneng.The photoluminescence spectra ea RuDA ka li-solvents tse fapaneng li bontšoa Setšoantšong sa Tlatsetso ea 6. RuDA e bonahala e bonts'a luminescence e tloaelehileng ea NIR-II e nang le boholo bo boholo ba emission wavelength ea ca.1050 nm ho CH2Cl2 le CH3OH, ka ho latellana.Phetoho e kholo ea Stokes (e ka bang 300 nm) ea RuDA e bontša phetoho e kholo ea geometry ea boemo bo thabileng le ho thehoa ha linaha tse nang le matla a tlaase a thabo.Lihlahisoa tsa luminescence quantum tsa Ore ho CH2Cl2 le CH3OH li ne li ikemiselitse ho ba 3.3 le 0.6%, ka ho latellana.Leha ho le joalo, ka har'a motsoako oa methanol le metsi (5/95, v/v), ho ile ha hlokomeloa bofubelu bo fokolang ba tlhahiso le ho fokotseha ha lihlahisoa tsa quantum (0.22%), e ka 'nang eaba ke ka lebaka la ho ipokella ha Ore. .
Ho bona ka mahlo a kelello ho ipokella ha ORE, re sebelisitse metsi a atomic force microscopy (AFM) ho bona ka mahlo a kelello liphetoho tsa morphological ORE tharollong ea methanol kamora ho eketsa metsi.Ha metsi a ne a le ka tlase ho 80%, ha ho na ho bokellana ho hlakileng ho ileng ha hlokomeloa (Supplementary Fig. 7).Leha ho le joalo, ka keketseho e 'ngoe ea metsi ho ea ho 90-95%, li-nanoparticles tse nyenyane li ile tsa hlaha, tse bontšang ho ikemela ha Ore. tharollo (setšoantšo sa 2C le Supplementary Fig. 8).Ka lehlakoreng le leng, ho monya ha indocyanine e tala (ICG e le taolo) e ile ea theoha ka potlako ho 779 nm, e bontšang hore photostability e babatsehang ea RuDA.Ho phaella moo, botsitso ba RuDA-NPs ho PBS (pH = 5.4, 7.4 le 9.0), 10% FBS le DMEM (glucose e phahameng) e ile ea hlahlojoa ke mahlaseli a mahlaseli a kotsi a UV ka nako e sa tšoaneng.Joalokaha ho bontšitsoe ho Supplementary Figure 9, liphetoho tse nyenyane ho lihlopha tsa ho monya tsa RuDA-NP li ile tsa hlokomeloa ho PBS ho pH 7.4 / 9.0, FBS le DMEM, e bontšang botsitso bo babatsehang ba RuDA-NP.Leha ho le joalo, ka mokhoa oa acidic (рН = 5.4) hydrolysis ea Ore e ile ea fumanoa.Re ile ra boela ra hlahloba ho tsitsa ha RuDA le RuDA-NP ho sebelisa mekhoa e phahameng ea metsi ea chromatography (HPLC).Joalokaha ho bontšitsoe ho Supplementary Figure 10, RuDA e ne e tsitsitse ka motsoako oa methanol le metsi (50 / 50, v / v) bakeng sa hora ea pele, 'me hydrolysis e ile ea hlokomeloa ka mor'a lihora tsa 4.Leha ho le joalo, ho ile ha hlokomeloa feela tlhōrō e pharaletseng ea concave-convex bakeng sa RuDA NPs.Ka hona, gel permeation chromatography (GPC) e ne e sebelisetsoa ho hlahloba botsitso ba RuDA NPs ho PBS (pH = 7.4).Joalokaha ho bontšitsoe ho Supplementary Figure 11, ka mor'a lihora tsa 8 tsa ho kenngoa tlas'a maemo a lekiloeng, bophahamo ba tlhōrō, bophara ba tlhōrō le sebaka se phahameng sa NP RuDA ha sea ka sa fetoha haholo, se bontšang botsitso bo babatsehang ba NP RuDA.Ho phaella moo, litšoantšo tsa TEM li bontšitse hore morphology ea RuDA-NP nanoparticles e ile ea lula e sa fetohe ka mor'a lihora tsa 24 ka diluted PBS buffer (pH = 7.4, Supplementary Fig. 12).
Hobane ho itlhophisa ho ka fana ka litšobotsi tse fapaneng tsa ts'ebetso le lik'hemik'hale ho Ore, re hlokometse ho lokolloa ha 9,10-anthracenediylbis(methylene) dimalonic acid (ABDA, indicator 1O2) ka methanol-metsi a metsoako.Ore e nang le metsi a fapaneng50.Joalokaha ho bontšitsoe Setšoantšong sa 2D le Setšoantšo sa Tlatsetso 13, ha ho na ho senyeha ha ABDA ho ileng ha hlokomeloa ha metsi a ne a le ka tlase ho 20%.Ka keketseho ea mongobo ho isa ho 40%, ho senyeha ha ABDA ho etsahetse, joalo ka ha ho pakoa ke ho fokotseha ha matla a ABDA fluorescence.Hape ho 'nile ha hlokomeloa hore metsi a mangata a phahameng a fella ka ho senyeha ka potlako, ho fana ka maikutlo a hore RuDA e ikemetseng e hlokahala ebile e molemo bakeng sa ho senyeha ha ABDA.Ketsahalo ena e fapane haholo le li-chromophores tsa sejoale-joale tsa ACQ (aggregation-induced quenching).Ha e khantšitsoe ka laser e nang le leqhubu la 808 nm, lihlahisoa tsa quantum tsa 1O2 RuDA ka motsoako oa 98% H2O / 2% DMF ke 16.4%, e leng makhetlo a 82 ho feta a ICG (ΦΔ = 0.2%)51, ho bonts'a katleho e tsotehang ea moloko oa 1O2 RuDA boemong ba ho kopanya.
Electron spins e sebelisang 2,2,6,6-tetramethyl-4-piperidinone (TEMP) le 5,5-dimethyl-1-pyrroline N-oxide (DMPO) e le maraba a spin Resonance spectroscopy (ESR) e sebelisitsoe ho khetholla mefuta e hlahisitsoeng. AFK.ka RuDA.Joalokaha ho bontšitsoe ho Setšoantšo sa Tlatsetso ea 14, ho netefalitsoe hore 1O2 e hlahisoa ka linako tsa mahlaseli pakeng tsa 0 le metsotso ea 4.Ho phaella moo, ha RuDA e ne e kenngoa ka DMPO tlas'a mahlaseli, letšoao le tloaelehileng la EPR la mela e mene ea 1: 2: 2: 1 DMPO-OH · adduct e ile ea fumanoa, e bontšang ho thehoa ha hydroxyl radicals (OH ·).Ka kakaretso, liphetho tse ka holimo li bonts'a bokhoni ba RuDA ba ho susumetsa tlhahiso ea ROS ka mekhoa e 'meli ea mofuta oa I/II oa ho etsa lifoto.
Ho utloisisa hamolemo thepa ea elektronike ea RuDA ka mefuta ea monomeric le e kopantsoeng, moeli oa li-molecular orbitals oa RuDA ka mefuta ea monomeric le ea dimeric e ne e baloa ho sebelisoa mokhoa oa DFT.Joalokaha ho bontšitsoe feiga.3A, e phahameng ka ho fetisisa occupied molecular orbital (HOMO) ea monomeric RuDA e delocalized hammoho le ligand backbone le tlaase-tlaase unoccupied molecular orbital (LUMO) e tsepamisitsoe ho TDP amohela yuniti.Ho fapana le hoo, matla a elektronike ho HOMO ea dimeric e tsepamisitsoe holim'a ligand ea molek'hule e le 'ngoe ea RuDA, ha sekhahla sa elektronike se LUMO se tsepamisitsoe haholo-holo karolong e amohelehang ea molek'hule e' ngoe ea RuDA, e bontšang hore RuDA e ka har'a dimer.Litšobotsi tsa CT.
A HOMO le LUMO tsa Ore li baloa ka mefuta ea monomeric le dimeric.B Maemo a matla a 'ngoe le a mararo a Ore ho li-monomers le dimers.C Maemo a lekantsoeng a RuDA le li-channel tse ka khonehang tsa ISC e le monomeric C le dimeric D. Metsu e bonts'a litsela tse ka khonehang tsa ISC.
Ho ajoa ha li-electrone le likoti ka matla a tlaase a singlet e thabisang ea RuDA ka mefuta ea monomeric le ea dimeric e ile ea hlahlojoa ho sebelisoa Multiwfn 3.852.53 software, e neng e baloa ka mokhoa oa TD-DFT.Joalokaha ho bontšitsoe leiboleng e eketsehileng.Joalo ka ha ho bonts'itsoe ho Lipalo 1-2, likoti tsa monomeric RDA hangata li arotsoe ka har'a mokokotlo oa ligand libakeng tsena tse thabileng tsa singlet, athe li-electrone li fumaneha haholo sehlopheng sa TDP, se bonts'ang litšobotsi tsa intramolecular tsa CT.Ho feta moo, bakeng sa linaha tsena tse thabileng tsa singlet, ho na le ho kopana ho hoholo kapa ho fokolang lipakeng tsa masoba le lielektrone, ho fana ka maikutlo a hore linaha tsena tse thabileng tsa singlet li etsa tlatsetso ho tsoa ho excitation ea lehae (LE).Bakeng sa dimers, ntle le likarolo tsa intramolecular CT le LE, karolo e itseng ea likarolo tsa CT tsa intermolecular e ile ea hlokomeloa linaheng tse fapaneng, haholo-holo S3, S4, S7, le S8, ho ipapisitsoe le tlhahlobo ea CT ea intermolecular, le phetoho ea CT intermolecular e le tsona tse ka sehloohong. (Letlapa la Tlatsetso).3).
E le hore re utloisise hantle liphello tsa liteko, re ile ra tsoela pele ho hlahloba thepa ea RuDA e thabisang linaha ho hlahloba phapang pakeng tsa monomers le dimers (Supplementary Tables 4-5).Joalo ka ha ho bonts'itsoe ho Setšoantšo sa 3B, maemo a matla a singlet le makhetlo a mararo a thabo ea dimer a teteane ho feta a monoma, e thusang ho fokotsa lekhalo la matla lipakeng tsa S1 le Tn. Ho tlalehiloe hore liphetoho tsa ISC li ka phethahala ka har'a lekhalo le lenyenyane la matla (ΔES1-Tn <0.3 eV) pakeng tsa S1 le Tn54. Ho tlalehiloe hore liphetoho tsa ISC li ka phethahala ka har'a lekhalo le lenyenyane la matla (ΔES1-Tn <0.3 eV) pakeng tsa S1 le Tn54. Сообщалось, что переходы ISC e ka khona быть реализованы в пределах небольшой энергетической щели (ES1-Tn <0,3 эВ) между S1 и Tn. Ho tlalehiloe hore liphetoho tsa ISC li ka phethahala ka har'a lekhalo le lenyenyane la matla (ΔES1-Tn <0.3 eV) pakeng tsa S1 le Tn54.据报道，ISC 跃迁可以在S1 和Tn54 之间的小能隙（ΔES1-Tn <0.3 eV）内实现.据报道，ISC 跃迁可以在S1 和Tn54 之间的小能隙（ΔES1-Tn <0.3 eV）内实现. Сообщалось, что переход ISC может быть реализован в пределах небольшой энергетической щели (ES1-Tn < 0,3 эВ) между S1 и Tn54. Ho tlalehiloe hore phetoho ea ISC e ka phethahala ka har'a lekhalo le lenyenyane la matla (ΔES1-Tn <0.3 eV) pakeng tsa S1 le Tn54.Ntle le moo, ke sebaka se le seng feela sa orbital, se tšoaretsoeng kapa se sa sebetseng, se tlamehang ho fapana maemong a le mong le a mararo ho fana ka karolo ea SOC e seng zero.Ka hona, ho itšetlehile ka tlhahlobo ea matla a ho hlasimolla le phetoho ea orbital, litsela tsohle tse ka khonehang tsa phetoho ea ISC li bontšoa ho Figs.3C,D.Haholo-holo, ke mocha o le mong feela oa ISC o fumanehang ho monomer, ha foromo ea dimeric e na le liteishene tse 'ne tsa ISC tse ka ntlafatsang phetoho ea ISC.Ka hona, hoa utloahala ho nahana hore limolek'hule tse ngata tsa RuDA li kopantsoe, liteishene tsa ISC li tla fumaneha haholoanyane.Ka hona, lihlopha tsa RuDA li ka theha lihlopha tsa elektronike tsa lihlopha tse peli sebakeng sa singlet le triplet, ho fokotsa lekhalo la matla pakeng tsa S1 le Tn e fumanehang, ka hona ho eketsa katleho ea ISC ho thusa moloko oa 1O2.
E le ho tsoela pele ho hlakisa mokhoa oa motheo, re ile ra kopanya motsoako oa litšupiso oa arene-Ru (II) complex (RuET) ka ho nkela lihlopha tse peli tsa ethyl le lihlopha tse peli tsa triphenylamine phenyl ho RuDA (Fig. 4A, bakeng sa litlhaloso tse feletseng, bona ESI, Supplementary 15). -21 ) Ho tloha ho mofani (diethylamine) ho amohela (TDF), RuET e na le litšobotsi tse tšoanang tsa intramolecular CT joaloka RuDA.Joalokaha ho lebeletsoe, palo ea ho monya ea RuET ho DMF e bontšitse sehlopha sa phetisetso ea matla a fokolang a matla a nang le matla a ho monya sebakeng se haufi sa infrared sebakeng sa 600-1100 nm (setšoantšo sa 4B).Ho phaella moo, ho bokellana ha RuET ho ile ha boela ha hlokomeloa ka metsi a ntseng a eketseha, a neng a bonahatsoa ka bofubelu bo boholo ba ho monya, bo ileng ba tiisoa ka ho eketsehileng ke litšoantšo tsa AFM tsa metsi (Supplementary Fig. 22).Liphetho li bonts'a hore RuET, joalo ka RuDA, e ka theha linaha tsa intramolecular le ho ipokella ka meaho e kopaneng.
Sebopeho sa lik'hemik'hale sa RuET.B: Mokhoa oa ho monya oa RuET ka metsoako ea likarolo tse fapaneng tsa DMF le metsi.Plots C EIS Nyquist bakeng sa RuDA le RuET.Likarabo tsa photocurrent D tsa RuDA le RuET tlas'a ketso ea mahlaseli a laser a nang le leqhubu la 808 nm.
Photodegradation ea ABDA ka pel'a RuET e ile ea hlahlojoa ka ho khantša mahlaseli ka laser e nang le leqhubu la 808 nm.Hoa makatsa hore ebe ha ho na ho senyeha ha ABDA ho ileng ha bonoa likarolong tse sa tšoaneng tsa metsi (Supplementary Fig. 23).Lebaka le ka 'nang la e-ba teng ke hore RuET ha e khone ho theha mohaho oa elektronike o kopantsoeng ka mokhoa o atlehileng hobane ketane ea ethyl ha e khothalletse phetisetso e sebetsang ea li-intermolecular charges.Ka hona, electrochemical impedance spectroscopy (EIS) le litekanyo tsa nakoana tsa photocurrent li ile tsa etsoa ho bapisa thepa ea photoelectrochemical ea RuDA le RuET.Ho ea ka morero oa Nyquist (Setšoantšo sa 4C), RuDA e bontša radius e nyenyane haholo ho feta RuET, e bolelang hore RuDA56 e na le lipalangoang tsa elektronike tsa intermolecular ka potlako le conductivity e ntlafetseng.Ho phaella moo, sekhahla sa photocurrent sa RuDA se phahame haholo ho feta sa RuET (setšoantšo sa 4D), se tiisang katleho e ntle ea ho fetisa tefo ea RuDA57.Kahoo, sehlopha sa phenyl sa triphenylamine ho Ore se phetha karolo ea bohlokoa ho fana ka phetisetso ea tefiso ea intermolecular le ho thehoa ha mohaho oa elektronike o kopantsoeng.
Ho eketsa ho bokellana ha hlahala le biocompatibility ea vivo, re kentse RuDA hape ka F127.Karolelano ea bophara ba hydrodynamic ea RuDA-NPs e ne e ikemiselitse ho ba 123.1 nm e nang le kabo e moqotetsane (PDI = 0.089) e sebelisa mokhoa o matla oa ho hasanya leseli (DLS) (Setšoantšo sa 5A), e leng se ileng sa khothalletsa ho bokella hlahala ka ho eketsa ho khoneha le ho boloka.EPR) phello.Litšoantšo tsa TEM li bonts'itse hore Ore NPs li na le sebopeho se tšoanang sa spherical se nang le bophara ba 86 nm.Ka ho hlakileng, boholo ba ho noa ha RuDA-NPs bo ile ba hlaha ho 800 nm (Supplementary Fig. 24), e bontšang hore RuDA-NPs e ka boloka mesebetsi le thepa ea ho bokella RuDAs.Palo e baloang ea ROS quantum e hlahisoang bakeng sa NP Ore ke 15.9%, e bapisoang le Ore Thepa ea photothermal ea RuDA NPs e ile ea ithutoa tlas'a ketso ea mahlaseli a laser a nang le leqhubu la 808 nm ho sebelisa k'hamera ea infrared.Joalokaha ho bontšitsoe feiga.5B, C, sehlopha sa taolo (PBS feela) se bile le keketseho e fokolang ea mocheso, ha mocheso oa tharollo ea RuDA-NPs o ntse o eketseha ka potlako ka mocheso o ntseng o eketseha (ΔT) ho 15.5, 26.1, le 43.0 ° C.Likarolo tse phahameng li ne li le 25, 50, le 100 µM, ka ho latellana, tse bontšang phello e matla ea photothermal ea RuDA NPs.Ho phaella moo, litekanyo tsa potoloho ea ho futhumatsa / ho pholile li ile tsa nkoa ho hlahloba botsitso ba photothermal ba RuDA-NP le ho bapisa le ICG.Mocheso oa Ore NPs ha oa ka oa fokotseha ka mor'a hore ho be le mekhahlelo e mehlano ea ho futhumatsa / ho pholile (setšoantšo sa 5D), se bontšang botsitso bo botle ba photothermal ba Ore NPs.Ka lehlakoreng le leng, ICG e bonts'a botsitso bo tlaase ba photothermal joalokaha bo bonoa ho tloha ho nyamela ho bonahalang ha mocheso oa mocheso oa photothermal tlas'a maemo a tšoanang.Ho ea ka mokhoa o fetileng58, photothermal conversion performance (PCE) ea RuDA-NP e ne e baloa e le 24.2%, e phahameng ho feta lisebelisoa tse teng tsa photothermal tse kang khauta ea nanorods (21.0%) le li-nanoshell tsa khauta (13.0%)59 .Ka hona, NP Ore e bonts'a thepa e ntle ea photothermal, e etsang hore ba tšepise baemeli ba PTT.
Tlhahlobo ea litšoantšo tsa DLS le TEM tsa RuDA NPs (inset).B Litšoantšo tse futhumetseng tsa mefuta e sa tšoaneng ea RuDA NPs e pepesehetse mahlaseli a laser ka leqhubu la 808 nm (0.5 W cm-2).C Liphetoho tsa photothermal tsa mefuta e fapaneng ea li-NPs, e leng lintlha tsa bongata.B. D Keketseho ea mocheso oa ORE NP le ICG ho feta lipotoloho tse 5 tsa ho futhumatsa-ho futhumatsa.
Photocytotoxicity ea RuDA NPs khahlanong le MDA-MB-231 lisele tsa kankere ea matsoele ea motho e ile ea hlahlojoa ka in vitro.Joalokaha ho bontšitsoe feiga.6A, B, RuDA-NPs le RuDA li bontšitse cytotoxicity e sa utloahaleng ha ho se na mahlaseli, ho bolelang hore chefo e tlaase e lefifi ea RuDA-NPs le RuDA.Leha ho le joalo, ka mor'a ho pepesehela mahlaseli a laser ka bolelele ba 808 nm, RuDA le RuDA NPs li bontšitse photocytotoxicity e matla khahlanong le MDA-MB-231 lisele tsa mofetše tse nang le litekanyetso tsa IC50 (half-maximum inhibitory concentration) tsa 5.4 le 9.4 μM, ka ho latellana, tse bontšang IC50. hore RuDA-NP le RuDA li na le monyetla oa ho etsa phototherapy ea mofetše.Ho phaella moo, photocytotoxicity ea RuDA-NP le RuDA e ile ea tsoela pele ho batlisisoa ka pel'a vithamine C (Vc), moferefere oa ROS, ho hlakisa karolo ea ROS ho cytotoxicity e entsoeng ke leseli.Ho hlakile hore lisele tse sebetsang li ile tsa eketseha ka mor'a ho eketsoa ha Vc, 'me litekanyetso tsa IC50 tsa RuDA le RuDA NPs e ne e le 25.7 le 40.0 μM, ka ho latellana, e leng se pakang karolo ea bohlokoa ea ROS ho photocytotoxicity ea RuDA le RuDA NPs.Cytotoxicity e entsoeng ke khanya ea RuDA-NPs le RuDA ho MDA-MB-231 lisele tsa kankere ka ho silafatsa lisele tse phelang / tse shoeleng ka calcein AM (fluorescence e tala bakeng sa lisele tse phelang) le propidium iodide (PI, fluorescence e khubelu bakeng sa lisele tse shoeleng).e netefalitsoeng ke lisele) joalo ka lisebelisoa tsa fluorescent.Joalokaha ho bontšitsoe setšoantšong sa 6C, lisele tse tšoaroang ka RuDA-NP kapa RuDA li ile tsa lula li sebetsa ntle le mahlaseli, joalokaha ho pakoa ke fluorescence e tala e matla.Ho fapana le hoo, tlas'a mahlaseli a laser, ho ile ha hlokomeloa feela fluorescence e khubelu, e tiisang hore photocytotoxicity e sebetsang ea RuDA kapa RuDA NPs.Hoa hlokomeleha hore fluorescence e tala e hlahile holim'a tlatsetso ea Vc, e bontšang tlōlo ea photocytotoxicity ea RuDA le RuDA NPs.Liphetho tsena li lumellana le liteko tsa in vitro photocytotoxicity.
Ho sebetsa ho itšetlehileng ka tekanyo ea lisele tsa A RuDA- le B RuDA-NP liseleng tsa MDA-MB-231 boteng kapa bo le sieo ba Vc (0.5 mM), ka ho latellana.Li-bars tsa liphoso, li bolela ± ho kheloha ho tloaelehileng (n = 3). Liteko tsa t tse sa sebetseng, tse mahlakore a mabeli *p <0.05, **p <0.01, le ***p <0.001. Liteko tsa t tse sa sebetseng, tse mahlakore a mabeli *p <0.05, **p <0.01, le ***p <0.001. Непарные двусторонние t-критерии *p <0,05, **p <0,01 le ***p <0,001. Liteko tse sa kopanngoeng tsa mehatla e 'meli *p<0.05, **p<0.01, le ***p<0.001.未配对的双边t 检验*p <0.05,**p <0.01 和***p <0.001.未配对的双边t 检验*p <0.05,**p <0.01 和***p <0.001. Непарные двусторонние t-тесты *p <0,05, **p <0,01 le ***p <0,001. Liteko tse sa kopanngoeng tsa mehatla e 'meli *p<0.05, **p<0.01, le ***p<0.001.C Tlhahlobo ea litšila tsa lisele tse phelang/tse shoeleng ka ho sebelisa calcein AM le propidium iodide e le lisebelisoa tsa fluorescent.Scale bar: 30 µm.Litšoantšo tse emelang tse tharo tse pheta-phetoang tsa likokoana-hloko tse tsoang sehlopheng ka seng lia bontšoa.D Litšoantšo tsa Confocal fluorescence tsa tlhahiso ea ROS ka lisele tsa MDA-MB-231 tlas'a maemo a fapaneng a phekolo.Green DCF fluorescence e bontša boteng ba ROS.Irradiate ka laser e nang le leqhubu la 808 nm ka matla a 0.5 W / cm2 ka metsotso e 10 (300 J / cm2).Scale bar: 30 µm.Litšoantšo tse emelang tse tharo tse pheta-phetoang tsa likokoana-hloko tse tsoang sehlopheng ka seng lia bontšoa.E Flow cytometry RuDA-NPs (50 µM) kapa RuDA (50 µM) tlhahlobo ea phekolo ka kapa ntle le 808 nm laser (0.5 W cm-2) ka boteng le ho ba sieo ha Vc (0.5 mM) bakeng sa 10 min.Litšoantšo tse emelang tse tharo tse pheta-phetoang tsa likokoana-hloko tse tsoang sehlopheng ka seng lia bontšoa.F Nrf-2, HSP70 le HO-1 ea MDA-MB-231 lisele tse tšoaroang ka RuDA-NPs (50 µM) kapa ntle le 808 nm laser irradiation (0.5 W cm-2, 10 min, 300 J cm-2) , lisele tse hlalosang 2).Litšoantšo tse emelang tse peli tse pheta-phetoang tsa likokoana-hloko tse tsoang sehlopheng ka seng lia bontšoa.
Tlhahiso ea Intracellular ROS liseleng tsa MDA-MB-231 e ile ea hlahlojoa ho sebelisoa mokhoa oa ho silafatsa oa 2,7-dichlorodihydrofluorescein diacetate (DCFH-DA).Joalokaha ho bontšitsoe feiga.6D, lisele tse tšoaroang ka RuDA-NPs kapa RuDA li bontšitse fluorescence e tala e ikhethang ha e khantšitsoe ka laser 808 nm, e bontšang hore RuDA-NPs le RuDA li na le bokhoni bo sebetsang ba ho hlahisa ROS.Ho e-na le hoo, ha ho se na leseli kapa ha Vc e le teng, ho ile ha hlokomeloa feela letšoao le fokolang la fluorescent la lisele, le bontšang ho thehoa ha ROS hanyenyane.Maemo a Intracellular ROS liseleng tsa RuDA-NP le lisele tsa MDA-MB-231 tse tšoaroang ke RuDA li ile tsa khethoa ka ho eketsehileng ke phallo ea cytometry.Joalokaha ho bontšitsoe ho Supplementary Figure 25, tekanyo ea fluorescence intensity (MFI) e hlahisoang ke RuDA-NPs le RuDA tlas'a 808 nm laser irradiation e ile ea eketseha haholo ka linako tse ka bang 5.1 le 4.8, ka ho latellana, ha e bapisoa le sehlopha sa taolo, ho tiisa sebopeho sa bona se setle sa AFK.bokhoni.Leha ho le joalo, litekanyetso tsa intracellular tsa ROS liseleng tsa RuDA-NP kapa MDA-MB-231 tse tšoaroang ka RuDA li ne li tšoana feela le ho laola ntle le mahlaseli a laser kapa ka pel'a Vc, e tšoanang le liphello tsa tlhahlobo ea confocal fluorescence.
Ho bontšitsoe hore mitochondria ke sepheo se seholo sa Ru(II) -arene complexes60.Ka hona, sebaka sa subcellular sa RuDA le RuDA-NPs se ile sa batlisisoa.Joalokaha ho bontšitsoe ho Supplementary Figure 26, RuDA le RuDA-NP li bonts'a li-profiles tse tšoanang tsa kabo ea lisele tse nang le palo e phahameng ka ho fetisisa ea ho bokella mitochondria (62.5 ± 4.3 le 60.4 ± 3.6 ng / mg protheine, ka ho latellana).Leha ho le joalo, ke chelete e nyenyane feela ea Ru e fumanoeng likarolong tsa nyutlelie tsa Ore le NP Ore (3.5 le 2.1%, ka ho latellana).Karolo e setseng ea sele e ne e e-na le ruthenium e setseng: 31.7% (30.6 ± 3.4 ng / mg protheine) bakeng sa RuDA le 42.9% (47.2 ± 4.5 ng / mg protheine) bakeng sa RuDA-NPs.Ka kakaretso, Ore le NP Ore li bokelloa haholo ho mitochondria.Ho lekola ho se sebetse ha mitochondrial, re sebelisitse JC-1 le MitoSOX Red staining ho lekola bokhoni ba membrane ea mitochondrial le bokhoni ba tlhahiso ea superoxide, ka ho latellana.Joalokaha ho bontšitsoe ho Supplementary Fig. 27, botala bo botala (JC-1) le bofubelu (MitoSOX Red) fluorescence bo ile ba hlokomeloa ka liseleng tse tšoaroang ka bobeli ba RuDA le RuDA-NPs tlas'a 808 nm laser irradiation, e bontšang hore ka bobeli RuDA le RuDA-NPs haholo fluorescent. E ka susumetsa ka katleho membrane ea mitochondrial depolarization le tlhahiso ea superoxide.Ho phaella moo, mochine oa lefu la sele o ile oa khethoa ho sebelisoa tlhahlobo ea phallo ea cytometry ea annexin V-FITC / propidium iodide (PI).Joalokaha ho bontšoa ho Setšoantšo sa 6E, ha e khantšitsoe ka 808 nm laser, RuDA le RuDA-NP li ile tsa etsa hore ho be le keketseho e kholo ea tekanyo ea pele ea apoptosis (quadrant e ka tlaase e nepahetseng) liseleng tsa MDA-MB-231 ha li bapisoa le PBS kapa PBS hammoho le laser.lisele tse sebetsoang.Leha ho le joalo, ha Vc e eketsoa, tekanyo ea apoptosis ea RuDA le RuDA-NP e fokotsehile haholo ho tloha 50.9% le 52.0% ho 15.8% le 17.8%, ka ho latellana, e tiisang karolo ea bohlokoa ea ROS ho photocytotoxicity ea RuDA le RuDA-NP..Ho phaella moo, lisele tse nyenyane tsa necrotic li ile tsa hlokomeloa lihlopheng tsohle tse lekiloeng (quadrant e ka holimo ka ho le letšehali), e fana ka maikutlo a hore apoptosis e ka 'na ea e-ba mofuta o ka sehloohong oa lefu la sele le bakoang ke RuDA le RuDA-NPs.
Kaha ho senyeha ha khatello ea oxidative ke ntho e ka sehloohong e khethollang apoptosis, ntho ea nyutlelie e amanang le erythroid 2, factor 2 (Nrf2) 62, e leng molaoli ea ka sehloohong oa tsamaiso ea antioxidant, e ile ea batlisisoa ho MDA-MB-231 ea RuDA-NPs.Mokhoa oa ts'ebetso oa li-NP tsa RuDA tse bakoang ke mahlaseli.Ka nako e ts'oanang, polelo ea protheine e tlase ea heme oxygenase 1 (HO-1) e ile ea boela ea fumanoa.Joalokaha ho bontšoa ho Setšoantšo sa 6F le Setšoantšo sa Tlatsetso 29, phototherapy ea RuDA-NP-mediated e ile ea eketsa litekanyetso tsa Nrf2 le HO-1 ha li bapisoa le sehlopha sa PBS, e leng se bontšang hore RuDA-NPs e ka 'na ea susumetsa litsela tsa pontšo ea khatello ea kelello ea oxidative.Ho phaella moo, ho ithuta phello ea photothermal ea RuDA-NPs63, polelo ea protheine ea mocheso oa mocheso Hsp70 e ile ea boela ea hlahlojoa.Ho hlakile hore lisele tse tšoaroang ka RuDA-NPs + 808 nm laser irradiation li bontšitse polelo e eketsehileng ea Hsp70 ha e bapisoa le lihlopha tse ling tse peli, tse bontšang karabo ea cellular ho hyperthermia.
Liphetho tse tsotehang tsa in vitro li ile tsa re susumelletsa ho batlisisa ts'ebetso ea in vivo ea RuDA-NP ka litoeba tse hlobotseng tse nang le lihlahala tsa MDA-MB-231.Kabo ea lisele tsa RuDA NPs e ile ea ithutoa ka ho fumana hore na ruthenium e teng sebeteng, pelo, spleen, liphio, matšoafo le lihlahala.Joalokaha ho bontšitsoe feiga.7A, boholo ba litaba tsa Ore NPs lithong tse tloaelehileng li ile tsa hlaha ka nako ea pele ea ho shebella (lihora tse 4), ha boholo ba litaba bo ne bo khethoa ka har'a lisele tsa tumor lihora tse 8 ka mor'a ente, mohlomong ka lebaka la Ore NPs.Phello ea EPR ea LF.Ho latela liphetho tsa kabo, nako e nepahetseng ea kalafo le NP ore e nkuoe lihora tse 8 kamora tsamaiso.Ho bontša mokhoa oa ho bokella RuDA-NPs libakeng tsa tumor, thepa ea photoacoustic (PA) ea RuDA-NPs e ne e hlahlojoa ka ho rekota lipontšo tsa PA tsa RuDA-NPs ka linako tse fapaneng ka mor'a ho kenngoa.Ntlha ea pele, pontšo ea PA ea RuDA-NP in vivo e ile ea hlahlojoa ka ho rekota litšoantšo tsa PA tsa sebaka sa tumor ka mor'a ente ea intratumoral ea RuDA-NP.Joalokaha ho bontšitsoe ho Setšoantšo sa Tlatsetso 30, RuDA-NPs e bontšitse pontšo e matla ea PA, 'me ho ne ho e-na le kamano e ntle pakeng tsa mahloriso a RuDA-NP le matla a pontšo ea PA (Supplementary Figure 30A).Joale, ka vivo PA litšoantšo tsa libaka tsa tumor li ile tsa tlalehoa ka mor'a ente ea methapo ea RuDA le RuDA-NP ka nako e fapaneng ka mor'a ente.Joalokaha ho bontšitsoe Setšoantšong sa 7B, pontšo ea PA ea RuDA-NPs ho tloha sebakeng sa tumor e ile ea eketseha butle-butle ha nako e ntse e ea 'me ea fihla sehlabeng ka lihora tsa 8 ka mor'a ente, e lumellanang le liphello tsa kabo ea lisele tse khethiloeng ke tlhahlobo ea ICP-MS.Mabapi le RuDA (Supplementary Fig. 30B), matla a mangata a pontšo ea PA a ile a hlaha lihora tsa 4 ka mor'a ente, e bontšang lebelo le potlakileng la ho kena ha RuDA ka har'a hlahala.Ho phaella moo, boitšoaro bo botle ba RuDA le RuDA-NPs bo ile ba hlahlojoa ka ho fumana palo ea ruthenium ka har'a moroto le mantle a sebelisa ICP-MS.Tsela e ka sehloohong ea ho felisa RuDA (Supplementary Fig. 31) le RuDA-NPs (Fig. 7C) ke ka mantle, 'me ho tlosoa ka katleho ha RuDA le RuDA-NPs ho ile ha hlokomeloa nakong ea thuto ea matsatsi a 8, e bolelang hore RuDA. le RuDA-NPs e ka 'na ea felisoa ka katleho' meleng ntle le chefo ea nako e telele.
A. Ex vivo kabo ea RuDA-NP ka li-tishu tsa mouse e ile ea khethoa ke litaba tsa Ru (karolo ea tekanyo e laoloang ea Ru (ID) ka gram ea lisele) ka linako tse fapaneng ka mor'a ente.Lintlha li bolela ± ho kheloha ho tloaelehileng (n = 3). Liteko tsa t tse sa sebetseng, tse mahlakore a mabeli *p <0.05, **p <0.01, le ***p <0.001. Liteko tsa t tse sa sebetseng, tse mahlakore a mabeli *p <0.05, **p <0.01, le ***p <0.001. Непарные двусторонние t-критерии *p <0,05, **p <0,01 le ***p <0,001. Liteko tse sa kopanngoeng tsa mehatla e 'meli *p<0.05, **p<0.01, le ***p<0.001.未配对的双边t 检验*p <0.05,**p <0.01 和***p <0.001.未配对的双边t 检验*p <0.05,**p <0.01 和***p <0.001. Непарные двусторонние t-тесты *p <0,05, **p <0,01 le ***p <0,001. Liteko tse sa kopanngoeng tsa mehatla e 'meli *p<0.05, **p<0.01, le ***p<0.001.B PA litšoantšo tsa libaka tsa tumor tsa vivo ka 808 nm excitation ka mor'a tsamaiso ea methapo ea RuDA-NPs (10 µmol kg-1) ka linako tse fapaneng.Ka mor'a tsamaiso ea methapo ea RuDA NPs (10 µmol kg-1), C Ru e ne e ntšoa ho tloha litoeba ka moroto le mantle ka nako e fapaneng.Lintlha li bolela ± ho kheloha ho tloaelehileng (n = 3).
Matla a ho futhumatsa a RuDA-NP ka vivo a ile a ithutoa ka litoeba tse hlobotseng le MDA-MB-231 le li-tumor tsa RuDA bakeng sa ho bapisa.Joalokaha ho bontšitsoe feiga.8A le setšoantšo sa tlatsetso sa 32, sehlopha sa taolo (saline) se bontšitse phetoho e fokolang ea mocheso (ΔT ≈ 3 ° C) ka mor'a metsotso ea 10 ea ho pepeseha ho tsoelang pele.Leha ho le joalo, mocheso oa RuDA-NPs le RuDA o ile oa eketseha ka potlako ka mocheso o phahameng oa 55.2 le 49.9 ° C, ka ho latellana, ho fana ka hyperthermia e lekaneng bakeng sa phekolo ea kankere ea vivo.Keketseho e bonoang ea mocheso o phahameng oa RuDA NPs (ΔT ≈ 24 ° C) ha e bapisoa le RuDA (ΔT ≈ 19 ° C) e ka 'na ea e-ba ka lebaka la ho phunyeha ha eona hantle le ho bokellana ha lisele tsa tumor ka lebaka la phello ea EPR.
Litšoantšo tse futhumetseng tsa infrared tsa litoeba tse nang le lihlahala tsa MDA-MB-231 tse khantšitsoeng ka laser ea 808 nm ka linako tse fapaneng lihora tsa 8 ka mor'a ente.Lits'oants'o tse emelang li pheta tse 'ne tsa baeloji ho tsoa sehlopheng ka seng li bonts'oa.B Bophahamo ba hlahala e amanang le C Karolelano ea boima ba hlahala ba lihlopha tse fapaneng tsa litoeba nakong ea kalafo.D Li-curve tsa boima ba 'mele tsa lihlopha tse fapaneng tsa litoeba.Irradiate ka laser e nang le leqhubu la 808 nm ka matla a 0.5 W / cm2 ka metsotso e 10 (300 J / cm2).Li-bars tsa liphoso, li bolela ± ho kheloha ho tloaelehileng (n = 3). Liteko tsa t tse sa sebetseng, tse mahlakore a mabeli *p <0.05, **p <0.01, le ***p <0.001. Liteko tsa t tse sa sebetseng, tse mahlakore a mabeli *p <0.05, **p <0.01, le ***p <0.001. Непарные двусторонние t-критерии *p <0,05, **p <0,01 le ***p <0,001. Liteko tse sa kopanngoeng tsa mehatla e 'meli *p<0.05, **p<0.01, le ***p<0.001.未配对的双边t 检验*p <0.05,**p <0.01 和***p <0.001.未配对的双边t 检验*p <0.05,**p <0.01 和***p <0.001. Непарные двусторонние t-тесты *p <0,05, **p <0,01 le ***p <0,001. Liteko tse sa kopanngoeng tsa mehatla e 'meli *p<0.05, **p<0.01, le ***p<0.001. E H&E litšoantšo tse silafatsang tsa litho tse kholo le lihlahala tse tsoang lihlopheng tse fapaneng tsa kalafo, ho kenyeletsoa Saline, Saline + Laser, RuDA, RuDA + Laser, RuDA-NPs, le lihlopha tsa RuDA-NPs + Laser. E H&E litšoantšo tse silafatsang tsa litho tse kholo le lihlahala tse tsoang lihlopheng tse fapaneng tsa kalafo, ho kenyeletsoa Saline, Saline + Laser, RuDA, RuDA + Laser, RuDA-NPs, le lihlopha tsa RuDA-NPs + Laser. Изображения окрашивания E H&E основных органов и опухолей из разных групп лечения, включая группы физиологического раствора, физиологического раствора + лазера, RuDA, RuDA + Laser, RuDA-NPs и RuDA-NPs + Laser. E H&E litšoantšo tse silafatsang tsa litho tse kholo le lihlahala tse tsoang lihlopheng tse fapaneng tsa kalafo, ho kenyeletsoa saline, saline + laser, RuDA, RuDA + Laser, RuDA-NPs, le lihlopha tsa RuDA-NPs + Laser.来自不同治疗组的主要器官和肿瘤的E H&E 染色图像，包括盐水、盐水+ 激光、RuDA、RuDA + 和激光 激光、RuDA + 和激光 NPs、RuDA + 和激光 NPs、RuDA来自不同治疗组的主要器官和肿瘤的E H&E Окрашивание E H&E основных органов и опухолей из различных групп лечения, включая физиологический раствор, физир DARUP, + Rula, +DARUDA E H & E staining ea litho tse kholo le lihlahala tse tsoang lihlopheng tse fapaneng tsa phekolo tse akarelletsang saline, saline + laser, RuDA, RuDA + laser, RuDA-NPs, le RuDA-NPs + laser.Scale bar: 60 µm.
Phello ea phototherapy ka vivo le RuDA le RuDA NPs e ile ea hlahlojoa moo litoeba tse hlobotseng tse nang le li-tumor tsa MDA-MB-231 li ne li kenngoa ka har'a methapo ea RuDA kapa RuDA NPs ka tekanyo e le 'ngoe ea 10.0 µmol kg-1 ka mothapo oa mohatla, ebe joale 8 lihora tse ka mor'a ente.mahlaseli a laser a nang le wavelength ea 808 nm.Joalokaha ho bontšitsoe setšoantšong sa 8B, palo ea lihlahala e ile ea eketseha haholo ka har'a lihlopha tsa saline le laser, tse bontšang hore saline kapa laser 808 irradiation e ne e e-na le phello e fokolang ho hola ha hlahala.Joaloka sehlopheng sa saline, ho hōla ha hlahala ka potlako ho ile ha boela ha hlokomeloa ho litoeba tse tšoaroang ka RuDA-NPs kapa RuDA ha ho se na mahlaseli a laser, a bontšang chefo ea bona e tlaase e lefifi.Ka lehlakoreng le leng, ka mor'a mahlaseli a laser, phekolo ea RuDA-NP le RuDA e ile ea etsa hore ho be le ho fokotseha ho hoholo ha tumor ka ho fokotseha ha molumo oa 95.2% le 84.3%, ka ho latellana, ha ho bapisoa le sehlopha se tšoaroang sa saline, se bontšang PDT e babatsehang ea synergistic., e kenngoeng ke phello ea RuDA / CHTV.- NP kapa Ore Ha e bapisoa le RuDA, RuDA NPs e bontšitse phello e ntle ea phototherapeutic, e neng e le haholo-holo ka lebaka la phello ea EPR ea RuDA NPs.Liphetho tsa thibelo ea ho hōla ha hlahala li ile tsa hlahlojoa ka ho eketsehileng ke boima ba hlahala bo hlahisitsoeng ka letsatsi la 15 la phekolo (setšoantšo sa 8C le Supplementary Fig. 33).Boima bo boholo ba hlahala ho RuDA-NP e ile ea tšoara litoeba 'me RuDA e tšoara litoeba e ne e le 0.08 le 0.27 g, ka ho latellana, e neng e le bobebe ho feta sehlopheng sa taolo (1.43 g).
Ho phaella moo, boima ba 'mele oa litoeba bo ne bo ngotsoe ka matsatsi a mararo ho ithuta chefo e lefifi ea RuDA-NPs kapa RuDA in vivo.Joalokaha ho bontšitsoe setšoantšong sa 8D, ha ho phapang e khōlō ea boima ba 'mele e ileng ea hlokomeloa bakeng sa lihlopha tsohle tsa phekolo. Ho feta moo, ho silafala ha hematoxylin le eosin (H&E) ho litho tse kholo (pelo, sebete, spleen, matšoafo le liphio) ho tsoa lihlopheng tse fapaneng tsa kalafo. Ho feta moo, ho silafala ha hematoxylin le eosin (H&E) ho litho tse kholo (pelo, sebete, spleen, matšoafo le liphio) ho tsoa lihlopheng tse fapaneng tsa kalafo. Кроме того, было проведено окрашивание гематоксилином и эозином (H&E) основных органов (сердца, печени, селезенки, легких и позкыпы). Ho phaella moo, ho silafala ha hematoxylin le eosin (H & E) ho litho tse kholo (pelo, sebete, spleen, matšoafo le liphio) ho tsoa lihlopheng tse fapaneng tsa phekolo.此外，对不同治疗组的主要器官（心脏、肝脏、脾脏、肺和肾脏）进行苏木精和伊红(H&E) (H&E) Кроме того, проводили окрашивание гематоксилином и эозином (H&E) основных органов (сердца, печени, селезенки, легких и почерук) в разлихуных и песни. Ho phaella moo, ho silafala ha hematoxylin le eosin (H & E) ho litho tse kholo (pelo, sebete, spleen, matšoafo le liphio) ho ne ho etsoa ka lihlopha tse fapaneng tsa phekolo.Joalokaha ho bontšitsoe ho Feiga.8E, litšoantšo tse silafatsang tsa H & E tsa litho tse hlano tse kholo tse tsoang ho lihlopha tsa RuDA-NPs le RuDA ha li bontše ho se tloaelehe ho totobetseng kapa tšenyo ea litho. 8E, litšoantšo tse silafatsang tsa H & E tsa litho tse hlano tse kholo tse tsoang ho lihlopha tsa RuDA-NPs le RuDA ha li bontše ho se tloaelehe ho totobetseng kapa tšenyo ea litho.Joalokaha ho bontšitsoe feiga.8E, изображения окрашивания H&E пяти основных органов из групп RuDA-NPs le RuDA не демонстрируют явных аномалий или повреждений органий. 8E, H & E litšoantšo tse silafatsang tsa litho tse hlano tse kholo tse tsoang ho lihlopha tsa RuDA-NPs le RuDA ha li bontše ho se tloaelehe ha litho tse hlakileng kapa liso.如图8E 所示，來自RuDA-NPs 和RuDA 组的五个主要器官的H&E 染色图像沒有显示出明显的异常或器官.如图8E 所示，來自RuDA-NPs 和RuDA 组的五个主要器官的H&E 8E, ha e le hantle, H&E e fana ka chelete e ngata ho feta RuDA-NPs le RuDA e se e ntse e tsoela pele ho sebetsa. Joalokaha ho bontšitsoe setšoantšong sa 8E, litšoantšo tse silafatsang tsa H & E tsa litho tse hlano tse kholo tse tsoang ho lihlopha tsa RuDA-NPs le RuDA ha lia ka tsa bontša ho se tloaelehe ho totobetseng kapa tšenyo ea litho.Liphetho tsena li bontšitse hore ha ho RuDA-NP kapa RuDA e bonts'itseng matšoao a chefo ho vivo. Ho feta moo, litšoantšo tse silafatsang tsa H & E tsa lihlahala li bontšitse hore lihlopha tse peli tsa RuDA + Laser le RuDA-NPs + Laser li ka baka tšenyo e matla ea lisele tsa mofetše, tse bontšang katleho e ntle ea vivo phototherapeutic ea RuDA le RuDA-NPs. Ho feta moo, litšoantšo tse silafatsang tsa H & E tsa lihlahala li bontšitse hore lihlopha tse peli tsa RuDA + Laser le RuDA-NPs + Laser li ka baka tšenyo e matla ea lisele tsa mofetše, tse bontšang katleho e ntle ea vivo phototherapeutic ea RuDA le RuDA-NPs.Ho phaella moo, litšoantšo tsa hlahala tsa hematoxylin-eosin li bontšitse hore lihlopha tse peli tsa RuDA + Laser le RuDA-NPs + Laser li ka baka timetso e matla ea lisele tsa mofetše, ho bontša katleho e phahameng ea phototherapeutic ea RuDA le RuDA-NPs ka vivo.此外，肿瘤的H&E 染色图像显示，RuDA + Laser 和RuDA-NPs + Laser 组均可导致严重的癌细胞破坏，说富坏的时坏，话市明给坏公物的时公平坏，话市显公平。此外 , 肿瘤 的 & e 染色 显示 , ruda + laser 和 ruda-nps + laser 组均 导致 的 癌细胞 破坏 , 证明 组 . ...Ho phaella moo, litšoantšo tsa tumor tsa hematoxylin le eosin li bontšitse hore lihlopha tse peli tsa RuDA + Laser le RuDA-NPs + Laser li ile tsa fella ka timetso e matla ea lisele tsa mofetše, tse bontšang katleho e phahameng ea phototherapeutic ea RuDA le RuDA-NPs ka vivo.
Qetellong, Ru (II) -arene (RuDA) organometallic complex le DA-type ligands e ne e etselitsoe ho nolofatsa mokhoa oa ISC ho sebelisa mokhoa oa ho kopanya.Synthesized RuDA e ka ipokella ka litšebelisano tse se nang covalent ho theha litsamaiso tse tsoang ho RuDA-derived supramolecular, kahoo li nolofaletsa ho thehoa ha 1O2 le phetoho e sebetsang ea photothermal bakeng sa phekolo ea kankere e bakoang ke leseli.Hoa hlokomeleha hore RuDA ea monomeric ha ea ka ea hlahisa 1O2 tlas'a laser irradiation ho 808 nm, empa e ka hlahisa palo e kholo ea 1O2 sebakeng se kopantsoeng, e bontšang ho ba le kelello le katleho ea moralo oa rona.Liphuputso tse latelang li bontšitse hore kopano ea supramolecular e fana ka RuDA ka thepa e ntlafetseng ea photophysical le photochemical, e kang redshift absorption le photobleaching resistance, e leng tse lakatsehang haholo bakeng sa ts'ebetso ea PDT le PTT.Ka bobeli liteko tsa in vitro le in vivo li bontšitse hore RuDA NPs tse nang le biocompatibility e ntle le ho bokellana hantle ka har'a hlahala li bonts'a ts'ebetso e ntle ea anticancer e hlahisoang ke khanya holim'a laser irradiation ka leqhubu la 808 nm.Ka hona, RuDA NPs e le li-reagents tse sebetsang tsa bimodal supramolecular PDT/PTW li tla ruisa sete ea li-photosensitizers tse kentsoeng ho wavelengths ka holimo ho 800 nm.Moralo oa mohopolo oa sisteme ea supramolecular e fana ka tsela e nepahetseng bakeng sa li-photosensitizer tse kentsoeng ke NIR tse nang le litlamorao tse ntle tsa ho etsa lifoto.
Lik'hemik'hale tsohle le li-solvents li ile tsa fumanoa ho bafani ba khoebo 'me tsa sebelisoa ntle le ho hloekisoa ho eketsehileng.RuCl3 e ile ea rekoa ho tsoa ho Boren Precious Metals Co., Ltd. (Kunming, Chaena).[(η6-p-cym)Ru(fendio)Cl]Cl (fendio = 1,10-phenanthroline-5,6-dione) le 4,7-bis[4-(N,N-diphenylamino)phenyl]-5 ,6-Diamino-2,1,3-benzothiadiazole e entsoe ho latela lithuto tse fetileng64,65.Lipontšo tsa NMR li ngotsoe ho Bruker Avance III-HD 600 MHz spectrometer Setsing sa Tlhahlobo ea Tlhahlobo ea Univesithi ea Boroa-bochabela ho sebelisa d6-DMSO kapa CDCl3 e le solvent.Liphetoho tsa lik'hemik'hale δ li fanoa ka ppm.mabapi le tetramethylsilane, le li-constants tsa tšebelisano J li fanoa ka boleng bo felletseng ho hertz.High resolution mass spectrometry (HRMS) e entsoe ka sesebelisoa sa Agilent 6224 ESI/TOF MS.Tlhahlobo ea mantlha ea C, H, le N e entsoe ho Vario MICROCHNOS elemental analyzer (Elementar).Lipontšo tse bonahalang tsa UV li ile tsa lekanngoa ho Shimadzu UV3600 spectrophotometer.Lipontšo tsa Fluorescence li ngotsoe ho Shimadzu RF-6000 spectrofluorimeter.Litšoantšo tsa EPR li ngotsoe ho Bruker EMXmicro-6/1 sesebelisoa.Morpholoji le sebopeho sa lisampole tse lokisitsoeng li ile tsa ithutoa ka lisebelisoa tsa FEI Tecnai G20 (TEM) le Bruker Icon (AFM) tse sebetsang ka matla a 200 kV.Ho hasanya ha leseli le matla (DLS) ho entsoe ho Nanobrook Omni analyzer (Brookhaven).Lintho tsa photoelectrochemical li ile tsa lekanyetsoa ho setupong sa electrochemical (CHI-660, Chaena).Litšoantšo tsa photoacoustic li ile tsa fumanoa ho sebelisoa tsamaiso ea FUJIFILM VisualSonics Vevo® LAZR.Litšoantšo tsa confocal li ile tsa fumanoa ho sebelisoa microscope ea Olympus FV3000 confocal.Tlhahlobo ea FACS e entsoe ho BD Calibur flow cytometer.Liteko tse phahameng tsa ts'ebetso ea "liquid chromatography" (HPLC) li entsoe ho sistimi ea Waters Alliance e2695 ho sebelisoa sesebelisoa sa 2489 UV/Vis.Liteko tsa Gel Permeation Chromatography (GPC) li ngotsoe ho sesebelisoa sa Thermo ULTIMATE 3000 se sebelisang ERC RefratoMax520 refractive index detector.
[(η6-p-cym)Ru(fendio)Cl]Cl (fendio = 1,10-phenanthroline-5,6-dione)64 (481.0 mg, 1.0 mmol), 4,7-bis[4 -(N, N-diphenylamino)phenyl]-5,6-diamino-2,1,3-benzothiadiazole 65 (652.0 mg, 1.0 mmol) le glacial acetic acid (30 mL) li ile tsa hlohlelletsoa ka sehatsetsing sa reflux ka lihora tse 12.Joale solvent e ne e ntšoa ka vacuo ho sebelisoa mouoane oa rotary.Sehlahisoa se hlahisitsoeng se ile sa hloekisoa ka flash column chromatography (silica gel, CH2Cl2: MeOH = 20: 1) ho fumana RuDA e le phofo e tala (ka lihlahisoa: 877.5 mg, 80%).anus.E balloa C64H48Cl2N8RuS: C 67.84, H 4.27, N 9.89.Fumana: C 67.92, H 4.26, N 9.82.1H NMR (600 MHz, d6-DMSO) δ 10.04 (s, 2H), 8.98 (s, 2H), 8.15 (s, 2H), 7.79 (s, 4H), 7.44 (s, 8H), 7.21 (d, J = 31.2 Hz, 16H), 6.47 (s, 2H), 6.24 (s, 2H), 2.69 (s, 1H), 2 .25 (s, 3H), 0.99 (s, 6H).138 nmr (150 m6-DCO , 103. , 86.52, 84.75, 63.29, 30.90, 22.29, 18.83.ESI-MS: m/z [M-Cl]+ = 1097.25.
Synthesis ea 4,7-bis [4- (N, N-diethylamino) phenyl-5,6-diamino-2,1,3-benzothiadiazole (L2): L2 e entsoe ka mehato e 'meli.Pd(PPh3)4 (46 mg, 0.040 mmol) e kenyelelitsoe ho N,N-diethyl-4-(tributylstannyl)aniline (1.05 g, 2.4 mmol) le 4,7-dibromo-5,6-dinitro tharollo - 2, 1,3-benzothiadiazole (0.38 g, 1.0 mmol) ka toluene e omileng (100 ml).Motsoako o ile oa tsosoa ka 100 ° C bakeng sa lihora tse 24.Ka mor'a ho tlosa toluene ka vacuo, sephetho se tiileng se ile sa hlatsuoa ka petroleum ether.Joale motsoako oa motsoako ona (234.0 mg, 0.45 mmol) le phofo ea tšepe (0.30 g, 5.4 mmol) ka acetic acid (20 ml) e ile ea tsosoa ka 80 ° C. bakeng sa lihora tse 4.Motsoako oa karabelo o ne o tšeloa ka metsing mme sephetho se sootho se tiileng se ile sa bokelloa ka ho sefa.Sehlahisoa se ile sa hloekisoa habeli ka vacuum sublimation ho fana ka 'mala o motala o tiileng (126.2 mg, 57% chai).anus.E balloa C26H32N6S: C 67.79, H 7.00, N 18.24.E fumanwe: C 67.84, H 6.95, H 18.16.1H NMR (600 MHz, CDCl3), δ (ppm) 7.42 (d, 4H), 6.84 (d, 4H), 4.09 (s, 4H), 3.42 (d, 8H ), 1.22 (s, 12H).13С NMR (150 MHz, CDCl3), δ (ppm) 151.77, 147.39, 138.07, 131.20, 121.09, 113.84, 111.90, 44.34, 12.77.ESI-MS: m/z [M+H]+ = 461.24.
Lik'hemik'hale li ile tsa lokisoa 'me tsa hloekisoa ho latela mekhoa e tšoanang le ea RuDA.anus.E balloa C48H48Cl2N8RuS: C 61.27, H 5.14, N 11.91.E fumanwe: C, 61.32, H, 5.12, N, 11.81,1H NMR (600 MHz, d6-DMSO), δ (ppm) 10.19 (s, 2H), 9.28 (s, 2H), 8.09 (s, 2H), 7.95 (s, 4H), 6.93 (s, 4H), 6.48 (d, 2H), 6.34 (s, 2H) , 3.54 (t, 8H), 2.80 (m, 1H), 2.33 (s, 3H), 1.31 (t, 12H), 1.07 (s, 6H).138 NMR (151 mhz, Cdcl3), Δ (PPM) 158.71, 128.71, 105.07, 105.0, 84.4., 38.06, 31.22, 29.69, 22.29, 19.19, 14.98, 12,93.ESI-MS: m/z [M-Cl]+ = 905.24.
RuDA e ile ea qhibiliha ka MeOH / H2O (5/95, v / v) ka bongata ba 10 μM.Mokhoa oa ho monya oa RuDA o ne o lekantsoe metsotso e meng le e meng ea 5 ho Shimadzu UV-3600 spectrophotometer tlas'a mahlaseli a nang le khanya ea laser e nang le leqhubu la 808 nm (0.5 W / cm2).ICG spectra e ngotsoe tlas'a maemo a tšoanang le a tloaelehileng.
Litšoantšo tsa EPR li ngotsoe ho Bruker EMXmicro-6/1 spectrometer e nang le matla a microwave a 20 mW, mefuta e mengata ea ho hlahloba 100 G, le modulation ea tšimo ea 1 G. 2,2,6,6-tetramethyl-4-piperidone. (TEMP) le 5,5-dimethyl-1-pyrroline N-oxide (DMPO) li ne li sebelisoa e le maraba a spin.Electron spin resonance spectra e ngotsoe bakeng sa tharollo e tsoakiloeng ea RuDA (50 µM) le TEMF (20 mM) kapa DMPO (20 mM) tlas'a ketso ea mahlaseli a laser a nang le leqhubu la 808 nm (0.5 W / cm2).
Lipalo tsa DFT le TD-DFT bakeng sa RuDA li entsoe maemong a PBE1PBE/6–31 G*//LanL2DZ ka tharollo e nang le metsi a sebelisang lenaneo la Gaussian 1666,67,68.Ho aroloa ha HOMO-LUMO, lesoba le elektronike tsa boemo bo tlaase bo thabileng ba singlet RuDA li ne li reretsoe ho sebelisa lenaneo la GaussView (phetolelo ea 5.0).
Re ile ra qala ka ho leka ho lekanya katleho ea moloko oa 1O2 RuDA ho sebelisa mahlaseli a tloaelehileng a UV-a bonahalang a nang le ICG (ΦΔ = 0.002) e le mokhoa o tloaelehileng, empa photodegradation ea ICG e ile ea ama liphello haholo.Ka hona, tlhahiso ea quantum ea 1O2 RuDA e lekantsoe ka ho lemoha phetoho ea matla a ABDA fluorescence hoo e ka bang 428 nm ha e khantša ka laser e nang le leqhubu la 808 nm (0.5 W / cm2).Liteko li ile tsa etsoa ho RuDA le RuDA NPs (20 μM) metsing / DMF (98/2, v / v) e nang le ABDA (50 μM).Palo ea lihlahisoa tsa 1O2 e baloa ho sebelisoa mokhoa o latelang: ΦΔ (PS) = ΦΔ (ICG) × (rFS/APS)/(rICG/AICG).rPS le rICG ke litekanyetso tsa karabelo tsa ABDA le 1O2 tse fumanoang ho photosensitizer le ICG, ka ho latellana.APS le AICG ke ho monya ha photosensitizer le ICG ho 808 nm, ka ho latellana.
Litekanyo tsa AFM li ne li etsoa maemong a mokelikeli ho sebelisoa mokhoa oa ho hlahloba ho Bruker Dimension Icon AFM system.Ho sebelisa mohaho o bulehileng o nang le lisele tsa metsi, lisele li ne li hlatsuoa habeli ka ethanol 'me li omisoa ka molapo oa naetrojene.Kenya lisele tse omisitsoeng hloohong ea optical ea microscope.Hang-hang beha lerotholi la sampole ka har'a letamo la mokelikeli 'me u le behe holim'a cantilever u sebelisa serinji ea polasetiki e sa hloekang le nale e hloekisitsoeng.Lerotholi le leng le behiloe ka ho toba sampuling, 'me ha hlooho ea optical e theoha, marotholi a mabeli a kopana, a etsa meniscus pakeng tsa sampuli le letamo la metsi.Litekanyo tsa AFM li ne li etsoa ho sebelisoa SCANASYST-FLUID V-shaped nitride cantilever (Bruker, hardness k = 0.7 N m-1, f0 = 120–180 kHz).
Li-chromatogram tsa HPLC li ile tsa fumanoa tsamaisong ea Metsi e2695 e nang le kholumo ea phoenix C18 (250 × 4.6 mm, 5 µm) ho sebelisoa mochine oa 2489 UV / Vis.Bolelele ba maqhubu a detector ke 650 nm.Mehato ea selefouno A le B e ne e le metsi le methanol, ka ho latellana, 'me sekhahla sa phallo ea phallo ea selefouno e ne e le 1.0 ml·min-1.The gradient (solvent B) e ne e le ka tsela e latelang: 100% ho tloha metsotso e 0 ho isa ho e 4, 100% ho 50% ho tloha metsotso e 5 ho isa ho e 30, le ho khutlela ho 100% ho tloha metsotso e 31 ho isa ho e 40.Ore e ile ea qhibiliha ka tharollo e tsoakiloeng ea methanol le metsi (50/50, ka molumo) ka har'a motsoako oa 50 μM.Bophahamo ba ente e ne e le 20 μl.
Litlhahlobo tsa GPC li tlalehiloe ho sesebelisoa sa Thermo ULTIMATE 3000 se nang le litšiea tse peli tsa PL aquagel-OH MIXED-H (2×300×7.5 mm, 8 µm) le ERC RefratoMax520 refractive index detector.Kholomo ea GPC e ile ea hlakoloa ka metsi ka sekhahla sa phallo ea 1 ml / min ho 30 ° C.Li-NPs tsa Ore li ile tsa qhibiliha ka tharollo ea PBS (pH = 7.4, 50 μM), molumo oa ente e ne e le 20 μL.
Li-photocurrents li ile tsa lekanyetsoa ho setupong sa electrochemical (CHI-660B, Chaena).Likarabo tsa optoelectronic ha laser e buloa le ho tima (808 nm, 0.5 W / cm2) e ile ea lekanyetsoa ka matla a 0.5 V ka lebokose le letšo, ka ho latellana.Sele e tloaelehileng ea li-electrode tse tharo e ne e sebelisoa ka khalase ea carbon electrode (GCE) e nang le sebōpeho sa L e le electrode e sebetsang, electrode e tloaelehileng ea calomel (SCE) e le electrode ea boitsebiso, le disk ea platinum e le electrode ea counter.Tharollo ea 0.1 M Na2SO4 e ne e sebelisoa e le electrolyte.
Mohala oa sele ea mofetše oa matsoele oa motho MDA-MB-231 o ile oa rekoa ho KeyGEN Biotec Co., LTD (Nanjing, China, lethathamo la nomoro: KG033).Lisele li ne li lengoa ka li-monolayers ho Dulbecco's Modified Eagle's Medium (DMEM, tsoekere e phahameng) e tlatsitsoeng ka tharollo ea 10% fetal bovine serum (FBS), penicillin (100 μg/ml) le streptomycin (100 μg/ml).Lisele tsohle li entsoe ka 37 ° C sebakeng se mongobo se nang le 5% CO2.
Tlhahlobo ea MTT e ne e sebelisetsoa ho fumana hore na cytotoxicity ea RuDA le RuDA-NPs ha e le teng le ho ba sieo ha mahlaseli a khanyang, a nang le Vc (0.5 mM) kapa ntle le eona.Lisele tsa mofets'e tsa MDA-MB-231 li ne li holisitsoe ka lipoleiti tsa seliba tse 96 ka har'a sele e ka bang 1 x 105 lisele / ml / seliba mme li kenngoa lihora tse 12 ho 37.0 ° C sepakapakeng sa 5% CO2 le 95% ea moea.RuDA le RuDA NPs tse qhibilihisitsoeng ka metsing li ile tsa kenngoa liseleng.Ka mor'a lihora tse 12 tsa incubation, lisele li ile tsa pepesehela mahlaseli a laser a 0.5 W cm -2 ka leqhubu la 808 nm ka metsotso e 10 (300 J cm -2) ebe li kenngoa lefifing ka lihora tse 24.Joale lisele li ne li kenngoa ka MTT (5 mg / ml) bakeng sa lihora tse ling tsa 5.Qetellong, fetola seaplane ho DMSO (200 µl) ho qhala likristale tse pherese tsa formazan.Litekanyetso tsa OD li ne li lekantsoe ho sebelisoa sebali sa microplate se nang le leqhubu la 570/630 nm.Boleng ba IC50 bakeng sa sampole ka 'ngoe bo ile ba baloa ho sebelisoa software ea SPSS ho tsoa ho li-curve tsa karabelo ea litekanyetso tse fumanoeng bonyane litekong tse tharo tse ikemetseng.
Lisele tsa MDA-MB-231 li ne li tšoaroa ka RuDA le RuDA-NP ka har'a mahloriso a 50 μM.Ka mor'a lihora tse 12 tsa ho kenngoa, lisele li ne li khabisoa ka laser e nang le leqhubu la 808 nm le matla a 0.5 W / cm2 bakeng sa 10 min (300 J / cm2).Sehlopheng sa vithamine C (Vc), lisele li ne li phekoloa ka 0.5 mM Vc pele ho mahlaseli a laser.Joale lisele li ne li kenngoa lefifing ka lihora tse ling tse 24, ebe li silafatsoa ka calcein AM le propidium iodide (20 μg/ml, 5 μl) metsotso e 30, ebe li hlatsuoa ka PBS (10 μl, pH 7.4).litšoantšo tsa lisele tse silafetseng.
Nako ea poso: Sep-23-2022
