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Photosensitizers dị irè dị mkpa karịsịa maka iji ọgwụ phototherapy eme ihe n'ụlọ ọgwụ.Otú ọ dị, fotosentizer ndị a na-emekarị na-enwekarị nhụjuanya site na mmịnye ogologo ogologo ogologo, enweghị ike ịhụ foto nke ọma, obere mkpụrụ nke ụdị oxygen na-emeghachi omume (ROS), na nchịkọta ROS na-akpata.N'ebe a, anyị na-akọ ihe dị nso-infrared (NIR) supramolecular photosensitizer (RuDA) onye ogbugbo site n'onwe ya mgbakọ nke Ru(II) -arene organometallic complexes na aqueous ngwọta.RuDA nwere ike ịmepụta nanị oxygen singlet (1O2) na steeti a na-achịkọta, ọ na-egosipụtakwa omume 1O2 na-eme ka nchịkọta doro anya n'ihi mmụba dị ukwuu na usoro ntụgharị n'etiti usoro singlet-triplet.N'okpuru ọrụ nke ọkụ laser 808 nm, RuDA na-egosipụta mkpụrụ nke 1O2 quantum nke 16.4% (FDA-akwadoro indocyanine green: ΦΔ = 0.2%) na nrụpụta fotothermal dị elu nke 24.2% (nanorods ọla edo azụmahịa) nwere ezigbo fototability.: 21.0%, ọla edo nanoshells: 13.0%).Na mgbakwunye, RuDA-NP nwere ezigbo bioacompatibility nwere ike ịgbakọta na saịtị etuto ahụ, na-eme ka ọzịza akpụ dị ukwuu n'oge ọgwụgwọ photodynamic yana mbelata 95.2% na olu tumor na vivo.Usoro ọgwụgwọ fotodynamic na-eme ka nchịkọta a na-enye atụmatụ maka ịmepụta fotosentizers nwere ezigbo fotophysical na fotochemical.
E jiri ya tụnyere usoro ọgwụgwọ a na-ahụkarị, ọgwụgwọ photodynamic (PDT) bụ ọgwụgwọ na-adọrọ adọrọ maka ọrịa cancer n'ihi uru ya dị ịrịba ama dị ka njikwa spatiotemporal ziri ezi, adịghị emerụ ahụ, nkwụsị ọgwụ na-abaghị uru, na ibelata mmetụta 1,2,3.N'okpuru irradiation ọkụ, fotosensitizers ejiri nwere ike rụọ ọrụ iji mepụta ụdị oxygen na-emeghachi omume nke ukwuu (ROS), na-eduga na apoptosis / necrosis ma ọ bụ nzaghachi mgbochi4,5. Otú ọ dị, ọtụtụ fotosensitizers ndị a na-emekarị, dị ka chlorin, porphyrins, na anthraquinones, na-enwe mmịnye ogologo oge dị mkpirikpi (ugboro <680 nm), si otú a na-ebute ntinye ọkụ na-adịghị mma n'ihi mmịnye siri ike nke ụmụ irighiri ihe ndị dị ndụ (dịka, hemoglobin na melanin) n'ime ya. mpaghara a na-ahụ anya6,7. Otú ọ dị, ọtụtụ fotosensitizers ndị a na-emekarị, dị ka chlorin, porphyrins, na anthraquinones, na-enwe mmịnye ogologo oge dị mkpirikpi (ugboro <680 nm), si otú a na-ebute ntinye ọkụ na-adịghị mma n'ihi mmịnye siri ike nke ụmụ irighiri ihe ndị dị ndụ (dịka, hemoglobin na melanin) n'ime ya. mpaghara a na-ahụ anya6,7. 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. Otú ọ dị, ọtụtụ fotosensitizers dị ka chlorins, porphyrins na anthraquinones na-enwe mmetụta dị mkpụmkpụ ogologo ogologo mmịfe (<680 nm) nke na-ebute ntinye ọkụ na-adịghị mma n'ihi mmịnye siri ike nke ụmụ irighiri ihe ndị dị ndụ (dịka hemoglobin na melanin) n'ime mpaghara a na-ahụ anya6,7., 大多数 大多数 传统 传统 和 和 和 和 和 和 和 相对 和 的 (频率 <680 nm), 因此 血红 血红 和 和 强烈 强烈 吸收 吸收 吸收导致光穿透性差., 大多数 大多数 大多数 大多数 传统 传统 传统 氢 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 蒽醌 频率 (频率 频率 <680 nm) 因此 蛋白 和 的 ,,, 吸收吸收 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. Agbanyeghị, ọtụtụ fotosensitizer ọdịnala dị ka chlorins, porphyrins na anthraquinones nwere nnabata ogologo ogologo ogologo ogologo (ugboro <680 nm) n'ihi nnabata siri ike nke biomolecules dị ka hemoglobin na melanin na-ebute ntinye ọkụ adịghị mma.Mpaghara a na-ahụ anya 6.7.Ya mere, infrared nso (NIR) na-amịkọrọ fotosensitizers nke na-arụ ọrụ na 700-900 nm "window ọgwụgwọ" dabara nke ọma maka phototherapy.Ebe ọ bụ na ọkụ infrared dị nso bụ nke anụ ahụ dị ndụ na-anabata ya, ọ nwere ike ibute ntinye miri emi yana obere mmebi foto8,9.
N'ụzọ dị mwute, fotosensitizers NIR dị ugbu a na-enwekarị fotostability na-adịghị mma, obere ikuku oxygen (1O2) na-emepụta ike, na nchịkọta 1O2 quenching, nke na-egbochi ngwa ahụike ha10,11.Ọ bụ ezie na agbala mbọ dị ukwuu iji melite njirimara fotophysical na fotochemical nke ndị na-ese foto, ruo ugbu a ọtụtụ akụkọ na-akọ na NIR na-etinye fotosensitizers nwere ike dozie nsogbu ndị a niile.Na mgbakwunye, ọtụtụ fotosensitizers egosila nkwa maka ọgbọ nke ọma nke 1O212,13,14 mgbe ejiri ọkụ dị elu karịa 800 nm, ebe ọ bụ na ike photon na-ebelata ngwa ngwa na mpaghara IR dị nso.Triphenylamine (TFA) dị ka onye na-enye elektrọn na [1,2,5] thiadiazole-[3,4-i] dipyrido[a,c] phenazine (TDP) dị ka ndị na-anabata eletrọn Donor-acceptor (DA) ụdị agba agba otu klas. nke agba agba, na-amịkọrọ infrared nso, bụ nke a mụọla nke ọma maka infrared bioimaging II na photothermal therapy (PTT) n'ihi na ha dị warara bandgap.Ya mere, enwere ike iji akwa ụdị DA maka PDT nwere mkpali dị nso-IR, n'agbanyeghị na adịkarịghị amụ ha dị ka fotosensitizers maka PDT.
A maara nke ọma na oke arụmọrụ nke intersystem crossing (ISC) nke photosensitizers na-akwalite nhazi nke 1O2.Usoro a na-ahụkarị maka ịkwalite usoro ISC bụ ịkwalite njikọ nke spin-orbit (SOC) nke fotosensitizers site na iwebata atom dị arọ ma ọ bụ ihe ọkụkụ pụrụ iche.Agbanyeghị, ụzọ a ka nwere ụfọdụ ọghọm na oke19,20.N'oge na-adịbeghị anya, nchịkọta onwe onye supramolecular enyela ụzọ ọgụgụ isi dị elu maka ịmepụta ihe ndị na-arụ ọrụ na ọkwa molecular, 21,22 nwere ọtụtụ uru na phototherapy: (1) fotosensitizers na-ejikọta onwe ya nwere ike nwee ike ịmepụta ihe owuwu ribbon.Yiri ihe owuwu eletrọnịkị nwere oke ike nkesa ike n'ihi mkpirisi okirikiri n'etiti ngọngọ ụlọ.Ya mere, a ga-emeziwanye egwuregwu ike dị n'etiti ala singlet excited state (S1) na agbata obi triplet excited state (Tn), nke bara uru maka usoro ISC 23, 24 .(2) Mgbakọ Supramolecular ga-ebelata ntụrụndụ na-abụghị nke na-egbuke egbuke dabere na usoro nkwụsị nke intramolecular (RIM), nke na-akwalitekwa usoro ISC 25, 26.(3) Mgbakọ supramolecular nwere ike ichebe ụmụ irighiri ihe dị n'ime nke monomer site na oxidation na mmebi, si otú ahụ na-eme ka fotositizer dịkwuo mma.Nyere uru ndị a dị n'elu, anyị kwenyere na sistemu fotosentizer supramolecular nwere ike ịbụ ihe ọzọ na-ekwe nkwa imeri adịghị ike nke PDT.
Ụlọ ndị ru (II) dabeere na ya bụ ikpo okwu ahụike na-ekwe nkwa maka ngwa nwere ike na nyocha na ọgwụgwọ nke ọrịa n'ihi ọdịdị ndụ ha pụrụ iche ma mara mma28,29,30,31,32,33,34.Na mgbakwunye, ụbara steeti nwere obi ụtọ na akụrụngwa photophysicochemical nke nwere ike ịgbanwe nke ụlọ ru(II) na-enye nnukwu uru maka mmepe nke fotosensitizers dabere na Ru (II)35,36,37,38,39,40.Ihe atụ a ma ama bụ ruthenium (II) polypyridyl complex TLD-1433, nke dị ugbu a na ule ụlọ ọgwụ nke Abụọ dị ka fotosentizer maka ọgwụgwọ ọrịa cancer na-adịghị emerụ ahụ na-adịghị ahụ ike (NMIBC) 41.Na mgbakwunye, ruthenium (II) arene organometallic complexes na-eji ọtụtụ ebe dị ka chemotherapeutic ọgwụ maka ọgwụgwọ ọrịa cancer n'ihi na ha dị ala toxicity na mfe nke mgbanwe42,43,44,45.Njirimara ionic nke Ru (II) -arene organometallic complexes nwere ike ọ bụghị naanị melite adịghị mma solubility nke DA chromophores na ihe mgbaze nkịtị, kamakwa melite mgbakọ DA chromophores.Na mgbakwunye, pseudooctahedral ọkara-sandwich Ọdịdị nke organometallic complexes nke Ru (II) -arenes nwere ike igbochi H-aggregation nke DA-ụdị chromophores, si otú na-eme ka e guzobe J-nchịkọta na redshifted absorption bands.Otú ọ dị, ihe ọghọm dị na ya nke Ru (II) -arene complexes, dị ka nkwụsi ike dị ala na / ma ọ bụ adịghị mma bioavailability, nwere ike imetụta ọgwụgwọ ọgwụgwọ yana ọrụ vivo nke ogige arene-Ru (II).Otú ọ dị, ọmụmụ egosila na enwere ike imeri adịghị ike ndị a site n'itinye ogige ruthenium na polymers biocompatible site na ntinye anụ ahụ ma ọ bụ njikọ njikọ.
N'ime ọrụ a, anyị na-akọ DA-conjugated complexes nke Ru(II) -arene (RuDA) nwere NIR na-akpalite site na njikọ nhazi n'etiti DAD chromophore na Ru (II) -arene moiety.Ihe mgbagwoju anya nwere ike ịgbakọta onwe ya n'ime vesicles metalosupramolecular n'ime mmiri n'ihi mmekọrịta ndị na-abụghị covalent.N'ụzọ dị ịrịba ama, mgbakọ supramolecular nyere RuDA na polymerization-induced intersystem crossing properties, bụ nke mụbara arụmọrụ ISC nke ukwuu, bụ nke dị mma maka PDT (Fig 1A).Iji mee ka mkpokọta tumor na na vivo biocompatibility, FDA-approved Pluronic F127 (PEO-PPO-PEO) ejiri mee ka RuDA47,48,49 mepụta RuDA-NP nanoparticles (Ọnọdụ 1B) nke rụrụ ọrụ dị ka PDT / Dual-arụ ọrụ nke ọma. ọnọdụ PTT proxy.Na ọrịa cancer phototherapy (Ọnụ ọgụgụ 1C), RuDA-NP na-eji na-emeso ụmụ oke gba ọtọ na ụbụrụ MDA-MB-231 iji mụọ irè PDT na PTT na vivo.
Ihe atụ nke usoro fotophysical nke RuDA na monomeric na ụdị nchịkọta maka ọrịa cancer phototherapy, njikọ nke B RuDA-NPs na C RuDA-NP maka NIR-arụ ọrụ PDT na PTT.
RuDA, nke nwere ọrụ TPA na TDP, kwadebere dị ka usoro egosiri na Ntụle 1 (Nyocha 2A), na RuDA ji 1H na 13C NMR spectra, electrospray ionization mass spectrometry, na nyocha elemental (Ngbakwunye 2-4). ).Map dị iche iche nke njupụta eletrọn nke RuDA nke mgbanwe singlet kacha ala ka agbakọrọ site na usoro njiri arụ ọrụ dabere na oge (TD-DFT) iji mụọ usoro mbufe ụgwọ.Dịka egosiri na eserese 5 nke mgbakwunye, njupụta elektrọn na-esi na triphenylamine na-aga na ngalaba nnabata TDP mgbe fotoexcitation gasịrị, nke enwere ike ịsị na mgbanwe mgbanwe ụgwọ intramolecular (CT).
Ọdịdị kemịkalụ nke ore B Absorption ụdịdị ọla na ngwakọta nke oke dị iche iche nke DMF na mmiri.C ụkpụrụ nnabata nke RuDA (800 nm) na ICG (779 nm) na oge na 0.5 W cm-2 nke ọkụ laser 808 nm.D A na-egosipụta fotodegradation nke ABDA site na nhazi nke RuDA nke 1O2 na DMF/H2O nwere ihe dị iche iche nke mmiri dị n'okpuru ọrụ nke radieshon laser na ogologo nke 808 nm na ike nke 0.5 W / cm2.
Abstract-UV-visible absorption spectroscopy ejiri mee ihe iji mụọ ihe gbasara onwe nke Ore na ngwakọta nke DMF na mmiri na oke dị iche iche.Dị ka e gosiri na fig.2B, RuDA na-egosiputa ụdọ absorption sitere na 600 ruo 900 nm na DMF yana eriri absorption kacha na 729 nm.Ịba ụba nke mmiri na-eduga n'ịgbanwe na-acha uhie uhie nke nta nke nta nke ntanye nke Ore kacha ruo 800 nm, nke na-egosi J-nchịkọta Ore na usoro mgbakọ.Eserese fotoluminescence nke RuDA n'ime ihe mgbaze dị iche iche ka egosiri na foto mgbakwunye 6. RuDA na-egosi na ọ na-egosipụta ụdị luminescence NIR-II nwere oke ikuku ikuku nke ca.1050 nm na CH2Cl2 na CH3OH, n'otu n'otu.Nnukwu mgbanwe Stokes (ihe dị ka 300 nm) nke RuDA na-egosi mgbanwe dị ịrịba ama na geometry nke steeti obi ụtọ na nhazi nke steeti obi ụtọ dị ala.Achọpụtara ọnụ ọgụgụ luminescence nke ore na CH2Cl2 na CH3OH ka ọ bụrụ 3.3 na 0.6%, n'otu n'otu.Otú ọ dị, na ngwakọta nke methanol na mmiri (5/95, v / v), a na-ahụ ntakịrị ihe na-acha uhie uhie nke ikuku na mbelata mkpụrụ nke quantum (0.22%), nke nwere ike ịbụ n'ihi nchịkọta onwe nke Ore. .
Iji jiri anya nke uche hụ nchikota onwe nke ORE, anyị na-eji mmiri mmiri atomic Force microscopy (AFM) iji hụ mgbanwe mgbanwe morphological na ORE na ngwọta methanol mgbe agbakwunyere mmiri.Mgbe ọdịnaya mmiri dị n'okpuru 80%, ọ dịghị nchịkọta doro anya a hụrụ (Mgbakwunye 7).Otú ọ dị, site n'ịbawanye ụba nke mmiri na 90-95%, obere nanoparticles pụtara, nke na-egosi nchịkọta onwe nke Ore. Tụkwasị na nke ahụ, irradiation laser na ogologo ogologo nke 808 nm emetụtaghị ike absorption nke RuDA na aqueous. ngwọta (Fig. 2C na mgbakwunye Fig. 8).N'ụzọ dị iche, nnabata nke indocyanine green (ICG dị ka njikwa) dara ngwa ngwa na 779 nm, na-egosi ọmarịcha fotostability nke RuDA.Tụkwasị na nke ahụ, nkwụsi ike nke RuDA-NPs na PBS (pH = 5.4, 7.4 na 9.0), 10% FBS na DMEM (glucose dị elu) na-enyocha site na UV-visible absorption spectroscopy na oge dị iche iche.Dị ka egosiri na foto 9 mgbakwunye, a hụrụ ntakịrị mgbanwe na ruDA-NP absorption bands na PBS na pH 7.4/9.0, FBS na DMEM, na-egosi nkwụsi ike dị mma nke RuDA-NP.Otú ọ dị, na usoro acidic (рН = 5.4) a chọtara hydrolysis nke Ore.Anyị tụlekwara nkwụsi ike nke RuDA na RuDA-NP site na iji usoro chromatography mmiri dị elu (HPLC).Dị ka e gosiri na Mgbakwunye 10, RuDA kwụsiri ike na ngwakọta nke methanol na mmiri (50/50, v / v) maka elekere mbụ, na hydrolysis na-ahụ mgbe awa 4 gasịrị.Otú ọ dị, ọ bụ nanị ọnụ ọgụgụ kasị elu concave-convex ka a hụrụ maka ndị RuDA NP.Ya mere, a na-eji gel permeation chromatography (GPC) chọpụta nkwụsi ike nke RuDA NP na PBS (pH = 7.4).Dị ka egosiri na foto mgbakwunye 11, mgbe awa 8 nke incubation gasịrị n'okpuru ọnọdụ a nwalere, ọnụ ọgụgụ kasị elu, obosara kachasị elu na mpaghara elu nke NP RuDA agbanweghị nke ọma, na-egosi nkwụsi ike nke NP RuDA.Tụkwasị na nke ahụ, ihe oyiyi TEM gosiri na morphology nke RuDA-NP nanoparticles nọgidere na-agbanwe agbanwe mgbe awa 24 gasịrị na ihe nchekwa PBS diluted (pH = 7.4, Fig. 12).
N'ihi na mgbakọ onwe onye nwere ike inye ụdị ọrụ dị iche iche na kemịkal dị iche iche na Ore, anyị hụrụ ntọhapụ nke 9,10-anthracenediylbis (methylene) dimalonic acid (ABDA, egosi 1O2) na ngwakọta mmiri methanol.Ore nwere mmiri dị iche iche50.Dị ka e gosiri na foto 2D na ihe mgbakwunye 13, ọ dịghị mmebi nke ABDA a hụrụ mgbe ọdịnaya mmiri dị n'okpuru 20%.Site na mmụba nke iru mmiri ruo 40%, mmebi ABDA mere, dị ka egosipụtara site na mbelata ike nke fluorescence ABDA.A chọpụtakwara na mmiri dị elu na-ebute mmebi ngwa ngwa, na-atụ aro na RuDA onwe ya dị mkpa na uru maka mmebi ABDA.Ihe omume a dị nnọọ iche na chromophores ACQ ọgbara ọhụrụ.Mgbe a na-eji laser na-agbapụta ìhè nke 808 nm, mkpụrụ nke quantum nke 1O2 RuDA na ngwakọta nke 98% H2O / 2% DMF bụ 16.4%, nke bụ 82 ugboro dị elu karịa nke ICG (ΦΔ = 0.2%)51, na-egosipụta arụmọrụ dị ịrịba ama ọgbọ 1O2 RuDA na steeti mkpokọta.
Electron na-agbagharị na-eji 2,2,6,6-tetramethyl-4-piperidinone (TEMP) na 5,5-dimethyl-1-pyrroline N-oxide (DMPO) dị ka ọnyà ọnyà Resonance spectroscopy (ESR) iji chọpụta ụdị ndị na-esi na ya pụta. AFK.nke RuDA.Dịka egosiri na foto mgbakwunye 14, ekwenyela na 1O2 na-emepụta n'oge irradiation n'etiti nkeji 0 na 4.Tụkwasị na nke ahụ, mgbe a na-etinye RuDA na DMPO n'okpuru irradiation, a na-achọpụta akara ngosi EPR anọ nke 1: 2: 2: 1 DMPO-OH · adduct, na-egosi nhazi nke hydroxyl radicals (OH ·).N'ozuzu, nsonaazụ ndị a dị n'elu na-egosi ikike nke RuDA iji kpalie mmepụta ROS site na usoro nhazi foto nke abụọ I / II.
Iji ghọta nke ọma njirimara eletrọnịkị nke RuDA na ụdị monomeric na agbakọta ọnụ, a na-agbakọ akụkụ molecular orbitals nke RuDA na ụdị monomeric na dimeric site na iji usoro DFT.Dị ka e gosiri na fig.3A, orbital molecular kachasị elu (HOMO) nke monomeric RuDA na-emezigharị n'akụkụ ọkpụkpụ azụ ligand na orbital molecular kachasị dị ala (LUMO) dabere na ngalaba nnabata TDP.N'ụzọ megidere nke ahụ, njupụta elektrọn dị na dimeric HOMO na-etinye uche na ligand nke otu molecule RuDA, ebe njupụta elektrọn na LUMO na-elekwasị anya na ngalaba nnabata nke molecule RuDA ọzọ, nke na-egosi na RuDA dị na dimer.Atụmatụ nke CT.
A na-agbakọ HOMO na LUMO nke ore n'ụdị monomeric na dimeric.B Singlet na triplet ume ọkwa nke ore na monomers na dimers.C echere ọkwa nke RuDA na ọwa ISC nwere ike dị ka monomeric C na dimeric D. Arrow na-egosi ọwa ISC nwere ike.
A na-enyocha nkesa nke electrons na oghere na obere ume singlet nwere obi ụtọ nke RuDA na ụdị monomeric na dimeric site na iji software Multiwfn 3.852.53, nke a gbakọrọ site na iji usoro TD-DFT.Dị ka egosiri na labelụ agbakwunyere.Dị ka e gosiri na Figure 1-2, monomeric RDA oghere na-akasị delocalized n'akụkụ ligand azụ ọkpụkpụ na ndị a singlet obi ụtọ na-ekwu, ebe electrons na-akasị dị na TDP otu, na-egosipụta intramolecular àgwà nke CT.Na mgbakwunye, maka steeti ndị a nwere obi ụtọ, enwere mbelata ma ọ bụ karịa n'etiti oghere na eletrọn, na-atụ aro na steeti ndị a nwere obi ụtọ na-enye ụfọdụ onyinye sitere na mkpali mpaghara (LE).Maka dimers, na mgbakwunye na njirimara CT intramolecular CT na LE, a na-ahụ ụfọdụ akụkụ nke njirimara intermolecular CT na steeti ndị dị iche iche, karịsịa S3, S4, S7, na S8, dabere na nyocha CT intermolecular, yana ntụgharị CT intermolecular dị ka ndị bụ isi. (Okpokoro Mgbakwụnye).3).
Iji ghọta nsonaazụ nnwale nke ọma, anyị nyochakwara ihe onwunwe nke steeti RuDA nwere obi ụtọ iji chọpụta ọdịiche dị n'etiti monomers na dimers (Tables 4-5 mgbakwunye).Dị ka e gosiri na foto 3B, ike ike nke singlet na triplet nwere obi ụtọ na steeti dimer dị nnọọ njọ karịa nke monomer, nke na-enyere aka belata ohere ike dị n'etiti S1 na Tn. A kọwo na mgbanwe ISC nwere ike ime n'ime obere oghere ike (ΔES1-Tn <0.3 eV) n'etiti S1 na Tn54. A kọwo na mgbanwe ISC nwere ike ime n'ime obere oghere ike (ΔES1-Tn <0.3 eV) n'etiti S1 na Tn54. Собщалось, что переходы ISC nwere ike ime ka rеalizovanы na ndị na-emepụta ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-eme ka ọ bụrụ ihe na-adịghị mma. A kọwo na mgbanwe ISC nwere ike ime n'ime obere oghere ike (ΔES1-Tn <0.3 eV) n'etiti S1 na 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 перехоd ISC может быть relylizovan в предлах мольший Боговой ческий Мели (ΔES04-T. A kọwo na mgbanwe ISC nwere ike ime n'ime obere oghere ike (ΔES1-Tn <0.3 eV) n'etiti S1 na Tn54.Na mgbakwunye, naanị otu orbital, nke nwere ma ọ bụ onye na-enweghị, ga-adị iche na steeti singlet na triplet iji nye ngwa SOC na-abụghị efu.Ya mere, dabere na nyocha nke ike mkpali na ntụgharị orbital, a na-egosipụta ọwa niile nwere ike ime mgbanwe ISC na fig.3C,D.N'ụzọ doro anya, ọ bụ naanị otu ọwa ISC dị na monomer, ebe ụdị dimeric nwere ọwa ISC anọ nwere ike ịkwalite mgbanwe ISC.Ya mere, ọ bụ ihe ezi uche dị na ya iche na ka a na-ejikọta ọnụ ọgụgụ ndị RuDA, otú ahụ ka ọwa ISC ga-enwetakwu ohere.Ya mere, mkpokọta RuDA nwere ike ịmepụta ihe owuwu eletrọnịkị abụọ na steeti singlet na triplet, na-ebelata ohere ike dị n'etiti S1 na Tn dịnụ, si otú ahụ na-abawanye arụmọrụ nke ISC iji kwado ọgbọ 1O2.
Iji kọwakwuo usoro dị n'okpuru, anyị na-emepụta ihe ntinye aka nke arene-Ru(II) complex (RuET) site n'iji dochie otu ethyl abụọ na otu triphenylamine phenyl dị na RuDA (Fig 4A, maka nkọwa zuru ezu, lee ESI, mgbakwunye 15). -21) Site na onye nyere onyinye (diethylamine) na-anabata (TDF), RuET nwere otu njirimara CT intramolecular dị ka RuDA.Dị ka a na-atụ anya ya, ihe nrịbama nke RuET na DMF gosipụtara obere nnyefe ike ike na ntinye siri ike na mpaghara infrared dị nso na mpaghara 600-1100 nm (Fig. 4B).Tụkwasị na nke ahụ, a na-ahụkwa nchịkọta RuET na-abawanye ụba nke mmiri, bụ nke gosipụtara na redshift nke absorption kacha, bụ nke a kwadoro site na mmiri mmiri AFM imaging (Mgbakwunye 22).Nsonaazụ na-egosi na RuET, dị ka RuDA, nwere ike ịmepụta steeti intramolecular na-agbakọta onwe ya n'ime ụlọ chịkọtara.
Usoro Chemical nke RuET.B ụdịdị absorption nke RuET na ngwakọta nke oke dị iche iche nke DMF na mmiri.Atụmatụ C EIS Nyquist maka RuDA na RuET.Nzaghachi foto ugbu a D nke RuDA na RuET n'okpuru ọrụ nke radieshon laser nwere ogologo ogologo nke 808 nm.
A na-enyocha fotodegradation nke ABDA n'ihu RuET site na irradiation na laser nwere ogologo ogologo nke 808 nm.N'ụzọ dị ịtụnanya, ọ dịghị mmebi nke ABDA a hụrụ na akụkụ mmiri dị iche iche (Mgbakwunye 23).Ihe nwere ike ime bụ na RuET enweghị ike ịmepụta usoro eletrọnịkị nke ọma n'ihi na yinye ethyl anaghị akwalite nnyefe ego intermolecular dị mma.Ya mere, e mere electrochemical impedance spectroscopy (EIS) na ihe nleba anya foto nke oge iji tụnyere njirimara fotoelectrochemical nke RuDA na RuET.Dabere na atụmatụ Nyquist (Ọnyonyo 4C), RuDA na-egosi radius pere mpe karịa RuET, nke pụtara na RuDA56 nwere ụgbọ njem elektrọnik intermolecular ngwa ngwa yana arụmọrụ ka mma.Tụkwasị na nke ahụ, njupụta foto nke RuDA dị elu karịa nke RuET (Fig 4D), na-akwado ọrụ nnyefe kacha mma nke RuDA57.Ya mere, otu phenyl nke triphenylamine dị na Ore na-arụ ọrụ dị mkpa n'inyefe nnyefe intermolecular na nhazi nke usoro eletrọnịkị banded.
Iji mee ka mkpokọta tumor na in vivo biocompatibility, anyị kpuchiri RuDA na F127.Nkezi dayameta hydrodynamic nke RuDA-NP bụ 123.1 nm nwere nkesa dị warara (PDI = 0.089) site na iji usoro ịgbasa ọkụ ọkụ (DLS) (Njirimara 5A), nke kwalitere mkpokọta tumo site na ịba ụba permeability na njide.EPR) mmetụta.Onyonyo TEM gosiri na Ore NP nwere ụdị okirikiri nwere otu dayameta nke 86 nm.N'ụzọ doro anya, ihe kachasị nke RuDA-NP pụtara na 800 nm (Fig 24).Ọnụ ọgụgụ nke ROS quantum mkpụrụ maka NP Ore bụ 15.9%, nke a na-atụnyere Ore. Achọpụtara njirimara fotothermal nke RuDA NP n'okpuru ọrụ nke radieshon laser na ogologo ogologo nke 808 nm site na iji igwefoto infrared.Dị ka e gosiri na fig.5B,C, otu njikwa (PBS naanị) nwetara ntakịrị mmụba na okpomọkụ, ebe okpomọkụ nke ngwọta RuDA-NP mụbara ngwa ngwa na okpomọkụ na-arịwanye elu (ΔT) ruo 15.5, 26.1, na 43.0 ° C.Ọnụ ọgụgụ dị elu bụ 25, 50, na 100 µM, n'otu n'otu, nke na-egosi mmetụta siri ike nke photothermal nke RuDA NP.Na mgbakwunye, a na-ewere nha okirikiri kpo oku / oyi iji nyochaa nkwụsi ike nke fotothermal nke RuDA-NP ma jiri ya tụnyere ICG.Okpomọkụ nke Ore NP adịghị ebelata mgbe usoro ọkụ ọkụ / oyi na-atụ ise (Fig 5D), nke na-egosi nkwụsi ike nke photothermal nke Ore NP.N'ụzọ dị iche, ICG na-egosipụta nkwụsi ike nke photothermal dị ala dị ka a na-ahụ site na mwepu nke elu ugwu photothermal okpomọkụ n'okpuru otu ọnọdụ ahụ.Dị ka usoro gara aga58 si kwuo, a na-agbakọ ọrụ ntụgharị fotothermal (PCE) nke RuDA-NP dị ka 24.2%, nke dị elu karịa ihe ndị dị na fotothermal dị ka gold nanorods (21.0%) na gold nanoshells (13.0%) 59 .Ya mere, NP Ore na-egosipụta ọmarịcha fotothermal, nke na-eme ka ha bụrụ ndị ọrụ PTT na-ekwe nkwa.
Nyocha nke onyonyo DLS na TEM nke RuDA NP (ntinye).B onyoonyo thermal nke mkpokọta dị iche iche nke RuDA NP ekpughere na radieshon laser na ogologo nke 808 nm (0.5 W cm-2).C ntụgharị ntụgharị fotothermal dị iche iche nke NP ore, nke bụ data ọnụọgụ.B. D Mmụba okpomoku nke ORE NP na ICG n'elu okirikiri ikpo ọkụ 5.
A na-enyocha fotocytotoxicity nke RuDA NPs megide mkpụrụ ndụ cancer ara mmadụ MDA-MB-231 na vitro.Dị ka e gosiri na fig.6A, B, RuDA-NPs na RuDA gosipụtara cytotoxicity na-adịghị ahụkebe na enweghị irradiation, na-egosi obere nsi ọchịchịrị nke RuDA-NPs na RuDA.Otú ọ dị, mgbe ekpughere radieshon laser na ogologo nke 808 nm, RuDA na RuDA NPs gosipụtara fotocytotoxicity siri ike megide mkpụrụ ndụ cancer MDA-MB-231 nwere ụkpụrụ IC50 (ọkara ihe mgbochi inhibitory) nke 5.4 na 9.4 μM, n'otu n'otu, na-egosipụta. na RuDA-NP na RuDA nwere ikike maka phototherapy cancer.Tụkwasị na nke ahụ, a na-enyocha fotocytotoxicity nke RuDA-NP na RuDA n'ihu vitamin C (Vc), onye na-ekpochapụ ROS, iji kọwaa ọrụ ROS na cytotoxicity nke ìhè.N'ụzọ doro anya, viability cell mụbara mgbe mgbakwunye Vc, na ụkpụrụ IC50 nke RuDA na RuDA NP bụ 25.7 na 40.0 μM, n'otu n'otu, nke na-egosi ọrụ dị mkpa nke ROS na photocytotoxicity nke RuDA na RuDA NP.Cytotoxicity nke RuDA-NP na RuDA na-ebute ọkụ na mkpụrụ ndụ cancer MDA-MB-231 site na ndụ ndụ / nwụrụ anwụ site na iji calcein AM (green fluorescence maka mkpụrụ ndụ ndụ) na propidium iodide (PI, fluorescence na-acha uhie uhie maka mkpụrụ ndụ nwụrụ anwụ).kwadoro site na mkpụrụ ndụ) dị ka nyocha fluorescent.Dị ka egosiri na eserese 6C, mkpụrụ ndụ ejiri RuDA-NP ma ọ bụ RuDA emeso ya nọgidere na-adị mma na-enweghị irradiation, dị ka ọ na-egosi site na nnukwu ọkụ ọkụ akwụkwọ ndụ akwụkwọ ndụ.N'ụzọ megidere nke ahụ, n'okpuru irradiation laser, a na-ahụ naanị fluorescence na-acha uhie uhie, nke na-akwado fotocytotoxicity dị irè nke RuDA ma ọ bụ RuDA NP.Ọ bụ ihe kwesịrị ịrịba ama na akwụkwọ ndụ akwụkwọ ndụ fluorescence pụtara na mgbakwunye nke Vc, nke na-egosi mmebi nke photocytotoxicity nke RuDA na RuDA NP.Nsonaazụ ndị a dabara na in vitro photocytotoxicity assays.
Ndabere dabere na dose nke mkpụrụ ndụ A RuDA- na B RuDA-NP na sel MDA-MB-231 na ọnụnọ ma ọ bụ enweghị Vc (0.5 mM), n'otu n'otu.Mpempe mpe mpe mpe mpe mpe mpe mpe akwa, pụtara ± ọkọlọtọ ọkọlọtọ (n = 3). Nnwale t na-ejikọtaghị ọnụ, akụkụ abụọ * p <0.05, **p <0.01, na ***p <0.001. Nnwale t na-ejikọtaghị ọnụ, akụkụ abụọ * p <0.05, **p <0.01, na ***p <0.001. Ụdị ihe eji eme ihe t-критерии * p <0,05, **p <0,01 na *** p <0,001. T-ule ọdụdụ abụọ anaghị ejikọ * p<0.05, **p<0.01, na ***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 na *** p <0,001. T-ule ọdụdụ abụọ anaghị ejikọ * p<0.05, **p<0.01, na ***p<0.001.Nyocha ntụpọ mkpụrụ ndụ ndụ / nwụrụ anwụ site na iji calcein AM na propidium iodide dị ka nyocha fluorescent.Ogwe ọnụ ọgụgụ: 30µm.E gosiputara onyonyo nnochite anya nke nkwugharị ndu atọ sitere na otu ọ bụla.D Confocal fluorescence oyiyi nke mmepụta ROS na sel MDA-MB-231 n'okpuru ọnọdụ ọgwụgwọ dị iche iche.Green DCF fluorescence na-egosi ọnụnọ nke ROS.Irradiate na a laser na a wavelength nke 808 nm na ike nke 0.5 W / cm2 maka 10 nkeji (300 J / cm2).Ogwe ọnụ ọgụgụ: 30µm.E gosiputara onyonyo nnochite anya nke nkwugharị ndu atọ sitere na otu ọ bụla.E Flow cytometry RuDA-NPs (50 µM) ma ọ bụ RuDA (50 µM) nyocha ọgwụgwọ na ma ọ bụ na-enweghị 808 nm laser (0.5 W cm-2) na ọnụnọ na enweghị Vc (0.5 mM) maka 10 min.E gosiputara onyonyo nnochite anya nke nkwugharị ndu atọ sitere na otu ọ bụla.F Nrf-2, HSP70 na HO-1 nke mkpụrụ ndụ MDA-MB-231 na-emeso ya na RuDA-NPs (50 µM) na ma ọ bụ na-enweghị 808 nm irradiation laser (0.5 W cm-2, 10 min, 300 J cm-2), sel kwupụta 2).E gosiputara onyonyo nnochite anya nke nkwugharị ndu abụọ sitere na otu ọ bụla.
A na-enyocha mmepụta ROS intracellular na sel MDA-MB-231 site na iji usoro ntụpọ 2,7-dichlorodihydrofluorescein diacetate (DCFH-DA).Dị ka e gosiri na fig.6D, mkpụrụ ndụ ejiri RuDA-NPs ma ọ bụ RuDA gosipụtara ọkụ ọkụ dị iche iche na-acha akwụkwọ ndụ akwụkwọ ndụ mgbe ejiri 808 nm laser mee ihe, na-egosi na RuDA-NPs na RuDA nwere ikike ịrụ ọrụ nke ọma iji mepụta ROS.N'ụzọ megidere nke ahụ, na enweghị ìhè ma ọ bụ na ọnụnọ Vc, ọ bụ naanị akara ngosi fluorescent na-adịghị ike nke sel ka a hụrụ, nke gosipụtara ntakịrị nhazi nke ROS.Ọkwa ROS intracellular dị na sel RuDA-NP na sel MDA-MB-231 a na-agwọ RuDA ka ekpebisikwara ike site na cytometry eruba.Dị ka e gosiri na Mgbakwunye Figure 25, pụtara fluorescence intensity (MFI) eme site RuDA-NPs na RuDA n'okpuru 808 nm laser irradiation abawanyela nke ukwuu site n'ihe dị ka 5.1 na 4.8 ugboro, n'otu n'otu, ma e jiri ya tụnyere otu njikwa, na-akwado AFK ha dị mma.ikike.Otú ọ dị, ọkwa ROS intracellular dị na mkpụrụ ndụ RuDA-NP ma ọ bụ MDA-MB-231 a na-emeso ya na RuDA bụ nanị iji tụnyere njikwa na-enweghị irradiation laser ma ọ bụ na ọnụnọ nke Vc, dị ka nsonaazụ nke nyocha confocal fluorescence.
E gosiputara na mitochondria bụ isi ebumnuche nke Ru(II) -arene complexes60.Ya mere, a nyochara mpaghara subcellular nke RuDA na RuDA-NP.Dị ka egosiri na eserese 26 nke mgbakwunye, RuDA na RuDA-NP na-egosi profaịlụ nkesa cellular yiri nkesa na mkpokọta kachasị elu na mitochondria (62.5 ± 4.3 na 60.4 ± 3.6 ng/mg protein, n'otu n'otu).Otú ọ dị, ọ bụ nanị ntakịrị ego Ru ka a chọtara n'ime akụkụ nuklia nke Ore na NP Ore (3.5 na 2.1%, n'otu n'otu).Akụkụ mkpụrụ ndụ fọdụrụnụ nwere ruthenium fọdụrụnụ: 31.7% (30.6 ± 3.4 ng / mg protein) maka RuDA na 42.9% (47.2 ± 4.5 ng / mg protein) maka RuDA-NPs.N'ozuzu, Ore na NP Ore na-akwakọba na mitochondria.Iji nyochaa dysfunction mitochondrial, anyị jiri JC-1 na MitoSOX Red staining iji chọpụta ike mitochondrial membrane na ikike mmepụta superoxide, n'otu n'otu.Dị ka egosiri na Fig.27 nke mgbakwunye, a na-ahụ ọkụ na-acha akwụkwọ ndụ akwụkwọ ndụ siri ike (JC-1) na uhie (MitoSOX Red) na sel ndị a na-emeso ma RuDA na RuDA-NP n'okpuru 808 nm laser irradiation, na-egosi na ma RuDA na RuDA-NP na-egbuke egbuke. Ọ nwere ike ime ka mitochondrial membrane depolarization na mmepụta superoxide nke ọma.Tụkwasị na nke ahụ, a na-ekpebi usoro nke ọnwụ cell site na iji nyocha cytometry na-asọpụta nke annexin V-FITC/propidium iodide (PI).Dị ka egosiri na foto 6E, mgbe ejiri 808 nm laser mee ihe, RuDA na RuDA-NP mere ka ọnụ ọgụgụ apoptosis n'oge dị elu dị elu (quadrant nke ala aka nri) na mkpụrụ ndụ MDA-MB-231 ma e jiri ya tụnyere PBS ma ọ bụ PBS gbakwunyere laser.mkpụrụ ndụ edozi.Agbanyeghị, mgbe etinyere Vc, ọnụego apoptosis nke RuDA na RuDA-NP belatara nke ukwuu site na 50.9% na 52.0% ruo 15.8% na 17.8%, n'otu n'otu, nke na-akwado ọrụ dị mkpa nke ROS na fotocytotoxicity nke RuDA na RuDA-NP..Na mgbakwunye, a hụrụ ntakịrị mkpụrụ ndụ necrotic n'òtù niile a nwalere (quadrant n'elu aka ekpe), na-atụ aro na apoptosis nwere ike ịbụ ụdị ọnwụ sel kachasị nke RuDA na RuDA-NP kpatara.
Ebe ọ bụ na mmebi nrụgide oxidative bụ isi ihe na-achọpụta apoptosis, ihe nuklia metụtara erythroid 2, ihe 2 (Nrf2) 62, bụ isi nchịkwa nke usoro antioxidant, nyochara na RuDA-NPs-emeso MDA-MB-231.Usoro omume nke RuDA NP na-ebute site na irradiation.N'otu oge ahụ, a chọpụtakwara okwu nke protein heme oxygenase 1 (HO-1).Dị ka e gosiri na foto 6F na ihe mgbakwunye 29, RuDA-NP-mediated phototherapy mụbara ọkwa Nrf2 na HO-1 ma e jiri ya tụnyere ìgwè PBS, na-egosi na RuDA-NP nwere ike ịkpali ụzọ mgbaàmà nrụgide oxidative.Na mgbakwunye, iji mụọ mmetụta photothermal nke RuDA-NPs63, a tụlekwara ngosipụta nke protein ujo okpomọkụ Hsp70.O doro anya na mkpụrụ ndụ ejiri RuDA-NPs + 808 nm laser irradiation gosipụtara mmụba nke Hsp70 ma e jiri ya tụnyere ìgwè abụọ ndị ọzọ, na-egosipụta nzaghachi cellular na hyperthermia.
Nsonaazụ dị ịrịba ama na vitro kpaliri anyị inyocha arụmọrụ in vivo nke RuDA-NP na ụmụ oke gba ọtọ nwere etuto MDA-MB-231.A mụrụ nkesa anụ ahụ nke RuDA NP site n'ịchọpụta ọdịnaya nke ruthenium na imeju, obi, splin, akụrụ, ngụgụ, na etuto ahụ.Dị ka e gosiri na fig.7A, ọdịnaya kachasị nke Ore NP na akụkụ ahụ nkịtị pụtara na oge nlele mbụ (4 h), ebe a na-ekpebi ọdịnaya kachasị na anụ ahụ tumo 8 awa mgbe ịgba ọgwụ mgbochi, ikekwe n'ihi Ore NP.Mmetụta EPR nke LF.Dị ka nsonaazụ nkesa si kwuo, a na-ewere oge kachasị mma nke ọgwụgwọ na NP ore 8 awa mgbe nchịkwa gasịrị.Iji gosi usoro nchịkọta nke RuDA-NP na saịtị tumor, a na-enyocha ihe onwunwe fotoacoustic (PA) nke RuDA-NP site na ịdekọ akara PA nke RuDA-NP n'oge dị iche iche mgbe ịgbanyechara ya.Nke mbụ, a na-enyocha akara ngosi PA nke RuDA-NP na vivo site na ịdekọ ihe oyiyi PA nke saịtị tumo mgbe ịgbanye intratumoral nke RuDA-NP.Dị ka e gosiri na Mgbakwunye 30, RuDA-NP gosipụtara akara ngosi PA siri ike, na enwere mmekọrịta dị mma n'etiti ntinye uche RuDA-NP na ike mgbaàmà PA (Nkọwa 30A).Mgbe ahụ, na vivo PA ihe oyiyi nke saịtị tumo ka edekọtara mgbe ịgba ọgwụ mgbochi nke RuDA na RuDA-NP n'oge dị iche iche mgbe ịgba ọgwụ gasịrị.Dị ka e gosiri na Figure 7B, mgbaàmà PA nke RuDA-NP si na saịtị tumor ji nwayọọ nwayọọ na-abawanye na oge wee rute n'elu ala dị larịị na 8 awa mgbe ịgba ọgwụ mgbochi, na-adabere na nsonaazụ nkesa anụ ahụ kpebisiri ike site na nyocha ICP-MS.N'ihe gbasara RuDA (Mgbakwunye 30B), akara mgbaàmà PA kachasị elu pụtara 4 awa mgbe ịgba ọgwụ mgbochi, na-egosi ngwa ngwa nke ntinye nke RuDA n'ime ụbụrụ.Na mgbakwunye, a nyochara omume excretory nke RuDA na RuDA-NP site n'ịchọpụta ọnụọgụ ruthenium na mmamịrị na nsị site na iji ICP-MS.Ụzọ bụ isi nke mkpochapụ maka RuDA (Mgbakwunye 31) na RuDA-NPs (Fig 7C) bụ site na nsị, a na-ahụkwa nkwụsị nke ọma nke RuDA na RuDA-NP n'oge ọmụmụ ụbọchị 8, nke pụtara na RuDA. na RuDA-NP nwere ike ikpochapụ nke ọma n'anụ ahụ na-enweghị nsi ogologo oge.
A. Ex vivo nkesa RuDA-NP na anụ ahụ òké kpebisiri ike site na ọdịnaya Ru (pasent nke a na-achịkwa dose nke Ru (ID) kwa gram nke anụ ahụ) n'oge dị iche iche mgbe a gbasịrị ya.Data bụ pụtara ± ọkọlọtọ ndiiche (n = 3). Nnwale t na-ejikọtaghị ọnụ, akụkụ abụọ * p <0.05, **p <0.01, na ***p <0.001. Nnwale t na-ejikọtaghị ọnụ, akụkụ abụọ * p <0.05, **p <0.01, na ***p <0.001. Ụdị ihe eji eme ihe t-критерии * p <0,05, **p <0,01 na *** p <0,001. T-ule ọdụdụ abụọ anaghị ejikọ * p<0.05, **p<0.01, na ***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 na *** p <0,001. T-ule ọdụdụ abụọ anaghị ejikọ * p<0.05, **p<0.01, na ***p<0.001.Ihe onyonyo B PA nke saịtị vivo tumor na 808 nm mkpali mgbe nchịkwa intravenous nke RuDA-NPs (10 µmol kg-1) n'oge dị iche iche.Mgbe nchịkwa intravenous nke RuDA NPs (10 μmol kg-1), a na-ewepụ C Ru na ụmụ oke nwere mmamịrị na nsị n'oge dị iche iche.Data bụ pụtara ± ọkọlọtọ ndiiche (n = 3).
A mụrụ ikike ikpo ọkụ nke RuDA-NP na vivo na ụmụ oke gba ọtọ nwere etuto MDA-MB-231 na RuDA maka ntụnyere.Dị ka e gosiri na fig.8A na ihe mgbakwunye 32, otu njikwa (saline) gosipụtara obere mgbanwe okpomọkụ (ΔT ≈ 3 Celsius C) mgbe 10 nkeji na-aga n'ihu.Agbanyeghị, okpomọkụ nke RuDA-NPs na RuDA mụbara ngwa ngwa na oke okpomọkụ nke 55.2 na 49.9 Celsius C, n'otu n'otu, na-enye hyperthermia zuru oke maka ọgwụgwọ ọrịa kansa vivo.Mmụba a na-ahụ anya na okpomọkụ dị elu maka RuDA NPs (ΔT ≈ 24 ° C) ma e jiri ya tụnyere RuDA (ΔT ≈ 19 ° C) nwere ike ịbụ n'ihi na ọ na-eme ka ọ dịkwuo mma na nchịkọta na anụ ahụ tumor n'ihi mmetụta EPR.
Onyonyo ọkụ infrared nke ụmụ oke nwere etuto MDA-MB-231 ejiri laser 808 nm gbasa n'oge dị iche iche awa 8 ka ịgbabachara.E gosiputara onyonyo nnochite anya nke nkwugharị ndu anọ sitere na otu ọ bụla.B ọnụ ọgụgụ tumor na C Nkezi etuto dị iche iche nke oke oke n'oge ọgwụgwọ.D Akpụkpọ anụ dị iche iche nke oke oke.Irradiate na a laser na a wavelength nke 808 nm na ike nke 0.5 W / cm2 maka 10 nkeji (300 J / cm2).Mpempe mpe mpe mpe mpe mpe mpe mpe akwa, pụtara ± ọkọlọtọ ọkọlọtọ (n = 3). Nnwale t na-ejikọtaghị ọnụ, akụkụ abụọ * p <0.05, **p <0.01, na ***p <0.001. Nnwale t na-ejikọtaghị ọnụ, akụkụ abụọ * p <0.05, **p <0.01, na ***p <0.001. Ụdị ihe eji eme ihe t-критерии * p <0,05, **p <0,01 na *** p <0,001. T-ule ọdụdụ abụọ anaghị ejikọ * p<0.05, **p<0.01, na ***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 na *** p <0,001. T-ule ọdụdụ abụọ anaghị ejikọ * p<0.05, **p<0.01, na ***p<0.001. E H&E na-agbapụta onyonyo nke akụkụ ahụ na etuto ahụ sitere na otu ọgwụgwọ dị iche iche, gụnyere Saline, Saline + Laser, RuDA, RuDA + Laser, RuDA-NPs, na RuDA-NPs + Laser otu. E H&E na-agbapụta onyonyo nke akụkụ ahụ na etuto ahụ sitere na otu ọgwụgwọ dị iche iche, gụnyere Saline, Saline + Laser, RuDA, RuDA + Laser, RuDA-NPs, na RuDA-NPs + Laser otu. 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. Ihe onyonyo E H&E nke akụkụ ahụ dị ukwuu na etuto ahụ sitere na otu ọgwụgwọ dị iche iche, gụnyere saline, saline + laser, RuDA, RuDA + Laser, RuDA-NPs, na RuDA-NPs + Laser otu.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+ 激兀、RuDA、RuDA、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, физиологический раствор + лазер, RuDA, RuDA + лазер, RuDA-NPs и RuDA-NPs + лазер. E H & E ntụpọ nke isi akụkụ na etuto si dị iche iche ọgwụgwọ dị iche iche gụnyere saline, saline + laser, RuDA, RuDA + laser, RuDA-NPs, na RuDA-NPs + laser.Ogwe ọnụ ọgụgụ: 60µm.
A tụlere mmetụta nke phototherapy na vivo na RuDA na RuDA NP nke ụmụ oke gba ọtọ nwere etuto MDA-MB-231 na-agbanye RuDA ma ọ bụ RuDA NP n'otu dose nke 10.0 µmol kg-1 site na akwara ọdụ, wee 8. awa mgbe injection.irradiation laser nwere ogologo ogologo nke 808 nm.Dị ka e gosiri na foto 8B, a na-abawanye ụba nke tumor na saline na laser dị iche iche, na-egosi na saline ma ọ bụ laser 808 irradiation nwere mmetụta dị nta na uto tumor.Dị ka ọ dị n'ime otu saline, a na-ahụkwa uto tumor ngwa ngwa na ụmụ oke na-emeso ya na RuDA-NPs ma ọ bụ RuDA na enweghị irradiation laser, na-egosipụta obere nsi ojii ha.N'ụzọ dị iche, mgbe irradiation laser gasịrị, ma ọgwụgwọ RuDA-NP na RuDA kpalitere nkwụghachi azụ tumor dị ịrịba ama na mbelata olu tumor nke 95.2% na 84.3%, n'otu n'otu, ma e jiri ya tụnyere otu saline na-emeso ya, na-egosi ezigbo synergistic PDT., nke mmetụta RuDA/CHTV kwadoro.- NP ma ọ bụ Ore. E jiri ya tụnyere RuDA, RuDA NP gosipụtara mmetụta phototherapeutic ka mma, nke bụ isi n'ihi mmetụta EPR nke RuDA NP.A na-enyochakwa nsonaazụ mgbochi tumor site na ibu arọ nke a na-ewepụ n'ụbọchị 15 ọgwụgwọ (Fig 8C na Fig. 33).Ọnụ ọgụgụ tumor nke dị na RuDA-NP na-agwọ ụmụ oke na RuDA na-emeso ụmụ oke bụ 0.08 na 0.27 g, n'otu n'otu, nke dị ọkụ karịa na otu njikwa (1.43 g).
Na mgbakwunye, a na-edekọ oke ahụ nke ụmụ oke kwa ụbọchị atọ iji mụọ nsi ọchịchịrị nke RuDA-NPs ma ọ bụ RuDA na vivo.Dị ka egosiri na eserese 8D, ọ nweghị nnukwu ọdịiche dị na ịdị arọ ahụ ka a hụrụ maka otu ọgwụgwọ niile. Ọzọkwa, a na-eme hematoxylin na eosin (H&E) nke akụkụ ahụ ndị bụ isi (obi, imeju, splin, ngụgụ na akụrụ) sitere na otu ọgwụgwọ dị iche iche. Ọzọkwa, a na-eme hematoxylin na eosin (H&E) nke akụkụ ahụ ndị bụ isi (obi, imeju, splin, ngụgụ, na akụrụ) sitere na otu ọgwụgwọ dị iche iche. Кроме того, было проведено окрашивание гематоксилином и эозином (H&E) основных органов (сердца, печени, селезенки, легких и почек) из разных групп лечения. Na mgbakwunye, a na-eme hematoxylin na eosin (H&E) nke akụkụ ahụ ndị bụ isi (obi, imeju, splin, ngụgụ, na akụrụ) sitere na otu ọgwụgwọ dị iche iche.此外，对不同治疗组的主要器官（心脏、肝脏、脾脏、肺和肾脏）要器官（心脏、肝脏、脾脏、肺和肾脏）进器官（心脏, (H&E) Кроме того, проводили окрашивание гематоксилином и эозином (H&E) основных органов (сердца, печени, селезенки, легких и почек) в различных группах лечения. Tụkwasị na nke ahụ, a na-eme hematoxylin na eosin (H&E) nke akụkụ ndị bụ isi (obi, imeju, splin, ngụgụ, na akụrụ) n'ime otu ọgwụgwọ dị iche iche.Dị ka e gosiri na fig.8E, ihe onyonyo H&E na-agbapụta nke akụkụ ise bụ isi sitere na RuDA-NPs na ndị otu RuDA egosighi ihe ọ bụla pụtara ìhè ma ọ bụ mmebi akụkụ ahụ. 8E, ihe onyonyo H&E na-agbapụta nke akụkụ ise bụ isi sitere na RuDA-NPs na ndị otu RuDA egosighi ihe ọ bụla pụtara ìhè ma ọ bụ mmebi akụkụ ahụ.Dị ka e gosiri na fig.8E, изображения nke H&E пяти 8E, H&E ihe onyonyo nke akụkụ ise dị mkpa sitere na RuDA-NPs na ndị otu RuDA na-egosi enweghị mmerụ ahụ ma ọ bụ ọnya akụkụ ahụ doro anya.如图8E 所示，来自RuDA-NPs 和RuDA 组的五个主要器官的H&E如图8E 所示，来自RuDA-NPs 和RuDA 组的五个主要器官的H&E Как показано на рисунке 8E, изображения окрашивания H&E пяти : RuDA-NPs na RuDA Dị ka egosiri na foto 8E, H & E na-eme ka ihe oyiyi nke akụkụ ise dị mkpa sitere na RuDA-NPs na RuDA egosighi ihe ọ bụla doro anya ma ọ bụ mmebi akụkụ ahụ.Nsonaazụ ndị a gosiri na ọ nweghị RuDA-NP ma ọ bụ RuDA gosipụtara akara nsi na vivo. Ọzọkwa, H&E ntụpọ onyogho nke etuto ahụ gosiri na ma RuDA + Laser na RuDA-NPs + Laser otu nwere ike ịkpata oké ọrịa cancer cell mbibi, na-egosipụta ndị kasị mma na vivo phototherapeutic irè nke RuDA na RuDA-NPs. Ọzọkwa, H&E ntụpọ onyogho nke etuto ahụ gosiri na ma RuDA + Laser na RuDA-NPs + Laser otu nwere ike ịkpata oké ọrịa cancer cell mbibi, na-egosipụta ndị kasị mma na vivo phototherapeutic irè nke RuDA na RuDA-NPs.Na mgbakwunye, ihe onyonyo nwere ntụpọ hematoxylin-eosin gosipụtara na ma ndị RuDA + Laser na RuDA-NPs + Laser dị iche iche nwere ike ibute mbibi mkpụrụ ndụ kansa nke ukwuu, na-egosipụta nrụpụta fototherapeutic dị elu nke RuDA na RuDA-NP na vivo.此外，肿瘤的H&E 染色图像显示，RuDA + Laser 和RuDA-NPs + LaserRuda + Laser 和 ruda-nps + laser 和 ruda-nps + laser 和. . .Na mgbakwunye, hematoxylin na eosin nwere ntụpọ tumor gosiri na ma RuDA + Laser na RuDA-NPs + Laser otu butere mbibi siri ike nke mkpụrụ ndụ kansa, na-egosipụta nrụpụta fototherapeutic dị elu nke RuDA na RuDA-NP na vivo.
N'ikpeazụ, Ru (II) -arene (RuDA) organometallic complex nke nwere ụdị ligands DA-dị ka e mere iji kwado usoro ISC site na iji usoro nchịkọta.RuDA synthesized nwere ike ịgbakọta onwe ya site na mmekọrịta ndị na-abụghị covalent iji mepụta sistemu supramolecular sitere na RuDA, si otú a na-eme ka nhazi 1O2 na ngbanwe nke ọma nke photothermal maka ọgwụgwọ ọrịa cancer na-ebute ọkụ.Ọ bụ ihe kwesịrị ịrịba ama na monomeric RuDA emepụtaghị 1O2 n'okpuru laser irradiation na 808 nm, ma ọ nwere ike ịmepụta nnukwu ego nke 1O2 na steeti a chịkọtara, na-egosipụta ezi uche na arụmọrụ nke nhazi anyị.Ọmụmụ ihe ndị sochirinụ egosila na mgbakọ supramolecular na-enye RuDA na-emeziwanye fotophysical na fotochemical, dị ka absorption redshift na photobleaching resistance, nke na-achọsi ike maka nhazi PDT na PTT.Ma nnwale in vitro na in vivo egosila na ndị RuDA NP nwere ezigbo biocompatibility na ezigbo mkpokọta na etuto ahụ na-egosipụta ọmarịcha ọrụ mgbochi ọrịa kansa na-ebute ọkụ n'elu irradiation laser na ogologo nke 808 nm.Ya mere, RuDA NP dị ka bimodal supramolecular PDT/PTW reagents ga-eme ka setịpụ fotosentizer na-arụ ọrụ n'ogologo nm karịa 800 nm.Nhazi echiche nke sistemu supramolecular na-enye ụzọ dị mma maka fotosensitizer na-arụ ọrụ NIR nwere mmetụta fotosensitizing mara mma.
E nwetara kemịkalụ niile na ihe mgbaze sitere n'aka ndị na-ebubata ahịa ma jiri ya mee ihe n'emeghị ka ọ dị ọcha ọzọ.A zụtara RuCl3 n'aka Boren Precious Metals Co., Ltd. (Kunming, China).[(η6-p-cym) Ru (fendio) Cl] Cl (fendio = 1,10-phenanthroline-5,6-dione) na 4,7-bis [4- (N, N-diphenylamino) phenyl] -5 ,6-Diamino-2,1,3-benzothiadiazole bụ synthesized dị ka ọmụmụ gara aga64,65.Edekọrọ ihe nkiri NMR na Bruker Avance III-HD 600 MHz spectrometer na Southeast University Analytical Test Center iji d6-DMSO ma ọ bụ CDCl3 dị ka ihe mgbaze.A na-enye mgbanwe kemịkalụ na ppm.N'ihe gbasara tetramethylsilane, a na-enye ndị na-emekọrịta ihe na J na ụkpụrụ zuru oke na hertz.Emere mkpebi dị elu mass spectrometry (HRMS) na ngwa Agilent 6224 ESI/TOF MS.Emere ihe nyocha nke C, H, na N na Vario MICROCHNOS elemental analyzer (Elementar).A tụrụ ihe nkiri UV na-ahụ anya na Shimadzu UV3600 spectrophotometer.Edekọkwara ụdị ọkụ ọkụ na Shimadzu RF-6000 spectrofluorimeter.Edekọrọ ihe nkiri EPR na ngwa Bruker EMXmicro-6/1.A mụrụ morphology na nhazi nke ihe atụ ndị a kwadebere na FEI Tecnai G20 (TEM) na Bruker Icon (AFM) ngwá ọrụ na-arụ ọrụ na voltaji nke 200 kV.Emere mgbasa ọkụ dị ike (DLS) na nyocha Nanobrook Omni (Brookhaven).A tụrụ ihe onwunwe fotoelectrochemical na nhazi nke electrochemical (CHI-660, China).E nwetara onyonyo fotoacoustic site na iji usoro FUJIFILM VisualSonics Vevo® LAZR.Enwetara ihe oyiyi confocal site na iji microscope confocal Olympus FV3000.Emere nyocha FACS na cytometer eruba BD Calibur.Emere nnwale chromatography mmiri dị elu (HPLC) na sistemụ Waters Alliance e2695 site na iji ihe nchọpụta 2489 UV/Vis.Edere ule chromatography Gel Permeation (GPC) na ngwa Thermo ULTIMATE 3000 site na iji 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) na glacial acetic acid (30 ml) ka kpaliri na reflux reflux maka awa 12.A na-ewepụ ihe mgbaze na vacuo site na iji ihe mgbapụta rotary.A na-eme ka ihe fọdụrụnụ dị ọcha site na chromatography kọlụm flash (silica gel, CH2Cl2: MeOH = 20: 1) iji nweta RuDA dị ka ntụ ntụ ndụ ndụ (mkpụrụ: 877.5 mg, 80%).ike.A gbakọrọ maka C64H48Cl2N8RuS: C 67.84, H 4.27, N 9.89.Achọpụtara: 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).13C nmr (150 MHZ, D6-DMSO), PPM) 158.03, 138.51, 130.5.5.6.81, 103.49, 103.49, 103.49, 103.49) , 103. , 86.52, 84.75, 63.29, 30.90, 22.29, 18.83.ESI-MS: m/z [M-Cl]+ = 1097.25.
Njikọ nke 4,7-bis [4- (N, N-diethylamino) phenyl-5,6-diamino-2,1,3-benzothiadiazole (L2): L2 na-arụ ọrụ na nzọụkwụ abụọ.Pd (PPh3) 4 (46 mg, 0.040 mmol) agbakwunyere na N, N-diethyl-4- (tributylstannyl) aniline (1.05 g, 2.4 mmol) na 4,7-dibromo-5,6-dinitro ngwọta - 2, 1,3-benzothiadiazole (0.38 g, 1.0 mmol) na toluene akọrọ (100 ml).A na-emegharị ngwakọta ahụ na 100 ° C maka awa 24.Mgbe ewepụchara toluene na vacuo, a na-eji mmanụ mmanụ ether sachaa ihe siri ike nke rụpụtara.Mgbe ahụ, ngwakọta nke ngwakọta a (234.0 mg, 0.45 mmol) na ntụ ntụ (0.30 g, 5.4 mmol) na acetic acid (20 ml) na-akpali na 80 ° C. maka awa 4.A na-agbanye ngwakọta mmeghachi omume n'ime mmiri ma na-anakọta ihe siri ike na-acha aja aja site na nzacha.A sachara ngwaahịa a ugboro abụọ site na oghere sublimation iji nye akwụkwọ ndụ akwụkwọ ndụ siri ike (126.2 mg, 57% mkpụrụ).ike.A gbakọrọ maka C26H32N6S: C 67.79, H 7.00, N 18.24.Achọpụtara: 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).13C 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.
A kwadebere ma sachaa ngwakọta ndị ahụ na-eso usoro yiri RuDA.ike.A gbakọrọ maka C48H48Cl2N8RuS: C 61.27, H 5.14, N 11.91.Chọtara: 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).13C nmr (151 MHZ, CDCL3) 158.20, 158.74, 138.76, 118.76, 105.76, 84.2.0, 87.0, 87.0, 87.75, 87.7.7, 87.75, 87.75, 87.75, 84.7.75, 87.7.75, 87.75, 87.7.7., 38.06, 31.22, 29.69, 22.29, 19.19, 14.98, 12.93.ESI-MS: m/z [M-Cl]+ = 905.24.
A gbazere RuDA na MeOH/H2O (5/95, v / v) na ntinye nke 10 μM.A tụrụ ụdịdị dị iche iche nke RuDA na nkeji ise ọ bụla na Shimadzu UV-3600 spectrophotometer n'okpuru irradiation nwere ọkụ laser nwere ogologo ogologo nke 808 nm (0.5 W/cm2).Edere ụdịdị ICG n'okpuru otu ọnọdụ dị ka ọkọlọtọ.
Edere ihe ngosi EPR na spectrometer Bruker EMXmicro-6/1 nwere ike microwave nke 20 mW, nyocha nyocha nke 100 G, yana mgbanwe ubi nke 1 G. 2,2,6,6-tetramethyl-4-piperidone. (TEMP) na 5,5-dimethyl-1-pyrroline N-oxide (DMPO) ejiri mee ihe dị ka ọnyà ọkpụkpụ.Edere ụdị ihe nlegharị anya nke eletrọn maka ngwakọta agwakọta nke RuDA (50 µM) na TEMF (20 mM) ma ọ bụ DMPO (20 mM) n'okpuru ọrụ nke radieshon laser nwere ogologo ogologo nke 808 nm (0.5 W / cm2).
A na-eme atụmatụ DFT na TD-DFT maka RuDA na ọkwa PBE1PBE / 6-31 G **// LanL2DZ na ngwọta mmiri na-eji usoro Gaussian 1666,67,68.Ihe nkesa HOMO-LUMO, oghere na eletrọn nke obere ume singlet nwere obi ụtọ steeti RuDA ka e ji atụmatụ GaussView (ụdị 5.0).
Anyị buru ụzọ nwaa iji tụọ arụmọrụ ọgbọ nke 1O2 RuDA site na iji ihe ngosi UV-visible spectroscopy na ICG (ΦΔ = 0.002) dị ka ọkọlọtọ, mana fotodegradation nke ICG na-emetụta nsonaazụ ya.Ya mere, a tụrụ mkpụrụ nke quantum nke 1O2 RuDA site n'ịchọpụta mgbanwe na ike nke ABDA fluorescence na ihe dịka 428 nm mgbe ejiri laser na-agba ọsọ nke 808 nm (0.5 W / cm2).Emere nnwale na RuDA na RuDA NPs (20 μM) na mmiri / DMF (98/2, v / v) nwere ABDA (50 μM).A na-agbakọ mkpụrụ nke 1O2 site na iji usoro a: ΦΔ (PS) = ΦΔ (ICG) × (rFS/APS)/(rICG/AICG).rPS na rICG bụ ọnụego mmeghachi omume nke ABDA nwere 1O2 enwetara site na fotosensitizer na ICG, n'otu n'otu.APS na AICG bụ nnabata nke photosensitizer na ICG na 808 nm, n'otu n'otu.
A na-eme nha AFM n'ọnọdụ mmiri mmiri site na iji ọnọdụ nyocha na sistemụ Bruker Dimension Icon AFM.N'iji usoro mepere emepe nke nwere mkpụrụ ndụ mmiri mmiri, a na-eji ethanol sachaa mkpụrụ ndụ ahụ ugboro abụọ ma jiri mmiri nke nitrogen kpoo ya.Fanye mkpụrụ ndụ akpọnwụwo n'ime isi anya nke microscope.Ngwa ngwa tinye dobe nke sample n'ime ọdọ mmiri nke mmiri mmiri na-etinye ya na cantilever na-eji sterile plastic sirinji na a agịga na-adịghị ọcha.A na-etinye dobe ọzọ ozugbo na ihe nlele ahụ, ma mgbe isi ihe anya na-agbada, mmiri abụọ ahụ na-ejikọta, na-eme meniscus n'etiti ihe nlele na mmiri mmiri mmiri.A na-eme nha AFM site na iji SCANASYST-FLUID V nke nitride cantilever (Bruker, hardness k = 0.7 N m-1, f0 = 120-180 kHz).
Enwetara chromatogram HPLC na sistemu Waters e2695 nke nwere kọlụm Phoenix C18 (250 × 4.6 mm, 5 µm) na-eji ihe nchọpụta 2489 UV/Vis.Ogologo ogologo nke ihe nchọpụta bụ 650 nm.Usoro mkpanaaka A na B bụ mmiri na methanol, n'otu n'otu, na usoro mgbaba mkpanaka bụ 1.0 ml·min-1.gradient (ihe mgbaze B) bụ nke a: 100% site na nkeji 0 ruo 4, 100% ruo 50% site na nkeji 5 ruo 30, wee tọgharịa na 100% site na nkeji 31 ruo 40.A na-agbaze ore na ngwakọta ngwakọta nke methanol na mmiri (50/50, site na olu) na ntinye nke 50 μM.Olu injection bụ 20 μl.
Edere nyocha GPC na ngwa Thermo ULTIMATE 3000 nke nwere kọlụm PL aquagel-OH MIXED-H abụọ (2 × 300 × 7.5 mm, 8 µm) yana ihe nchọta ihe nleba anya ERC RefratoMax520.E ji mmiri kpochie kọlụm GPC n'ọsọ ọsọ nke 1 ml/min na 30 Celsius.A gbazere NP nke ore na ngwọta PBS (pH = 7.4, 50 μM), olu injection bụ 20 μL.
A tụrụ fotocurrents na nhazi nke electrochemical (CHI-660B, China).Nzaghachi optoelectronic mgbe agbanyere na gbanyụọ laser (808 nm, 0.5 W/cm2) tụrụ na voltaji nke 0.5 V n'ime igbe ojii, n'otu n'otu.A na-eji cell electrode atọ ọkọlọtọ mee ihe na L-shaped glassy carbon electrode (GCE) dị ka electrode na-arụ ọrụ, ọkọlọtọ calomel electrode (SCE) dị ka electrode ntụaka, na diski platinum dị ka electrode counter.A na-eji ngwọta 0.1 M Na2SO4 mee ihe dị ka electrolyte.
A zụrụ ahịrị mkpụrụ ndụ kansa ara mmadụ MDA-MB-231 n'aka KeyGEN Biotec Co., LTD (Nanjing, China, nọmba katalọgụ: KG033).A na-akụ mkpụrụ ndụ n'ime monolayer na Dulbecco's Modified Eagle's Medium (DMEM, nnukwu glucose) agbakwunyere ihe ngwọta nke 10% fetal bovine serum (FBS), penicillin (100 μg/ml) na streptomycin (100 μg/ml).Azụlitere mkpụrụ ndụ niile na 37ºC n'ime ikuku iru mmiri nwere 5% CO2.
Ejiri nyocha MTT iji chọpụta cytotoxicity nke RuDA na RuDA-NP na ọnụnọ na enweghị irradiation ọkụ, na ma ọ bụ na-enweghị Vc (0.5 mM).A na-etolite mkpụrụ ndụ cancer MDA-MB-231 na efere 96-well na njupụta cell nke ihe dịka 1 x 105 sel / ml / ọma ma tinye ya maka awa 12 na 37.0 ° C na ikuku nke 5% CO2 na 95% ikuku.RuDA na RuDA NP gbazere na mmiri ka agbakwunyere na sel.Mgbe awa iri na abụọ nke incubation gasịrị, a na-ekpughere mkpụrụ ndụ ahụ na 0.5 W cm -2 laser radieshon n'ogologo nke 808 nm maka nkeji 10 (300 J cm -2) wee tinye ya n'ọchịchịrị maka awa 24.A na-etinyezi mkpụrụ ndụ ahụ na MTT (5 mg / ml) maka awa 5 ọzọ.N'ikpeazụ, gbanwee ọkara ka ọ bụrụ DMSO (200 µl) iji gbazee kristal formazan na-acha odo odo na-esi na ya pụta.A tụrụ ụkpụrụ OD site na iji onye na-agụ microplate nwere ogologo ogologo nke 570/630 nm.A gbakọrọ uru IC50 maka nlele ọ bụla site na iji sọftụwia SPSS sitere na usoro nzaghachi dose enwetara na opekata mpe nnwale atọ nọọrọ onwe ha.
A na-agwọ mkpụrụ ndụ MDA-MB-231 na RuDA na RuDA-NP na ntinye nke 50 μM.Mgbe awa 12 gasịrị, a na-eji laser mee ka sel ndị ahụ nwee ike nke 808 nm na ike nke 0.5 W / cm2 maka 10 min (300 J / cm2).N'ime otu vitamin C (Vc), a na-eji 0.5 mM Vc gwọọ mkpụrụ ndụ tupu ọkụ ọkụ laser.A na-etinye mkpụrụ ndụ n'ime ọchịchịrị maka awa 24 ọzọ, wee jiri calcein AM na propidium iodide (20 μg/ml, 5 μl) mee ihe maka nkeji 30, wee saa ya na PBS (10 μl, pH 7.4).oyiyi nke mkpụrụ ndụ ntụpọ.
Oge nzipu: Sep-23-2022
