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1.
J Mater Chem B ; 9(4): 1131-1137, 2021 01 28.
Artigo em Inglês | MEDLINE | ID: mdl-33432961

RESUMO

Persistent luminescence nanoparticles (PLNPs) emitting in the NIR window (700-1700 nm) have shown great promise in the field of fluorescence imaging due to their unique properties, including the absence of in situ excitation and low optical scattering in tissues. However, they are still facing some challenges, such as irregular shape, wide size distribution and poor persistent luminescence performance. Here, we report a facile mesoporous template method for synthesizing mSiO2@Zn0.6Ca0.4Ga2O4:Cr3+,Yb3+ (mSiO2@ZCGO) persistent luminescent nanoparticles, which show a regular morphology and a size of about 69 nm. In addition, these nanocrystals exhibit persistent luminescence in multi-NIR windows, the first infrared window (∼696 nm of Cr3+ emission) and second infrared window (∼1000 nm of Yb3+ emission). Under illumination of a 254 nm UV lamp for 10 min, the persistent time of Cr3+ ions and Yb3+ ions lasted more than 120 min and 10 min, respectively. In particular, the NIR persistent emission of mSiO2@ZCGO could be stimulated by soft X-ray, which is beneficial to long-term imaging in deep tissues. The optical penetration length of Yb3+ ions persistent luminescence was evaluated to be 2.8 mm. These results demonstrate the great promise of mSiO2@ZCGO for deep-tissue bio-imaging.


Assuntos
Luminescência , Nanopartículas/química , Imagem Óptica , Compostos de Cálcio/química , Cromo/química , Germânio/química , Raios Infravermelhos , Óxidos/química , Tamanho da Partícula , Dióxido de Silício/química , Propriedades de Superfície , Itérbio/química , Óxido de Zinco/química
2.
Nanoscale ; 12(26): 14180-14187, 2020 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-32602515

RESUMO

Persistent luminescence nanophosphors (PLNPs) emitting in the second near-infrared window (1000-1700 nm, NIR-II) are emerging as one promising class of in vivo bio-imaging agents due to their unique advantages including non-autofluorescence and low optical scattering in tissues. Currently, it remains a great challenge to synthesize nanosized lanthanide-doped inorganic NIR-II phosphors with a good persistent luminescence performance. Herein, we present a salt microemulsion method for synthesizing Ce3+, Cr3+, Nd3+ codoped Y3(Al/Ga)5O12 nanocrystals, which generate multi-wavelength persistent luminescence in the visible (∼508 nm, 5d1→ 4f of Ce3+), the first near-infrared window (∼890 nm, 4F3/2→4I9/2 of Nd3+) and NIR-II (∼1063 nm, 4F3/2→4I11/2 of Nd3+) regions. Under illumination of a 410 nm diode (3 W) for 10 min, the observed duration time of NIR-II persistent luminescence is as long as 60 min at room temperature. Moreover, the persistent luminescence can be excited efficiently by multiple excitation sources including a blue diode, white LEDs and an X-ray generator, which is crucial for deep tissue imaging applications. By comparing the penetration depth between NIR-I and NIR-II persistent luminescence through chicken breast, we prove that NIR-II photons exhibit a deeper optical penetration length (3.9 mm) than that of the NIR-I ones (2.5 mm). In addition, the NIR signals can still be detected 3 min after ceasing the excitation source by a small animal imaging system (InGaAs detector) when the thickness of the covering chicken breast is 20 mm. These results show great promise for Y3(Al/Ga)5O12:Ce3+,Cr3+,Nd3+ nanocrystals as a PLNP for bio-imaging applications with deep penetration depth and a high signal-to-noise ratio.

3.
Chem Asian J ; 15(7): 1147-1155, 2020 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-32030909

RESUMO

When the 1,1,4,4-tetraanilinobutadiene skeleton is attached with two halogenated aryl units at the 2,3-positions, they undergo facile two-electron oxidation to give stable dicationic dyes which exhibit a near-infrared (NIR) absorption whereas the neutral dienes show only pale color. Therefore, a distinct electrochromic response with an absorption change in the NIR region is achieved, which is attracting considerable recent attention from the viewpoint of bioimaging. Herein, we demonstrate that the redox potentials of the 1,1,4,4-tetraanilinobutadiene can be precisely controlled by the donating properties of the amino group on the aniline unit as well as the number of halogen atoms on the aryl units at 2,3-positions on the butadiene. In contrast, the NIR absorption bands mainly depend on the number of halogen atoms irrespective to the donating properties of aniline unit. Thus, the hexaarylbutadiene skeleton is proven to be a versatile scaffold to develop less-explored organic NIR electrochromic materials, whose redox and spectroscopic properties can be finely tuned by modifying/attaching the proper substituents.

4.
Nat Commun ; 11(1): 446, 2020 01 23.
Artigo em Inglês | MEDLINE | ID: mdl-31974383

RESUMO

Afterglow luminescent probes with high signal-to-background ratio show promise for in vivo imaging; however, such probes that can be selectively delivered into target sites and switch on afterglow luminescence remain limited. We optimize an organic electrochromic material and integrate it into near-infrared (NIR) photosensitizer (silicon 2,3-naphthalocyanine bis(trihexylsilyloxide) and (poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]) containing nanoparticles, developing an H2S-activatable NIR afterglow probe (F12+-ANP). F12+-ANP displays a fast reaction rate (1563 ± 141 M-1 s-1) and large afterglow turn-on ratio (~122-fold) toward H2S, enabling high-sensitivity and -specificity measurement of H2S concentration in bloods from healthy persons, hepatic or colorectal cancer patients. We further construct a hepatic-tumor-targeting and H2S-activatable afterglow probe (F12+-ANP-Gal) for noninvasive, real-time imaging of tiny subcutaneous HepG2 tumors (<3 mm in diameter) and orthotopic liver tumors in mice. Strikingly, F12+-ANP-Gal accurately delineates tumor margins in excised hepatic cancer specimens, which may facilitate intraoperative guidance of hepatic cancer surgery.


Assuntos
Carcinoma Hepatocelular/diagnóstico por imagem , Sulfeto de Hidrogênio/análise , Neoplasias Hepáticas/diagnóstico por imagem , Substâncias Luminescentes/química , Imagem Molecular/métodos , Animais , Neoplasias Colorretais/sangue , Cistationina beta-Sintase/análise , Cistationina beta-Sintase/metabolismo , Cistationina gama-Liase/análise , Cistationina gama-Liase/metabolismo , Células Hep G2 , Humanos , Sulfeto de Hidrogênio/sangue , Sulfeto de Hidrogênio/química , Neoplasias Hepáticas/sangue , Neoplasias Hepáticas Experimentais/diagnóstico por imagem , Substâncias Luminescentes/síntese química , Camundongos Endogâmicos BALB C , Nanopartículas/química , Fármacos Fotossensibilizantes/química , Polímeros/química , Compostos de Vinila/química , Ensaios Antitumorais Modelo de Xenoenxerto
5.
J Am Chem Soc ; 140(47): 16340-16352, 2018 11 28.
Artigo em Inglês | MEDLINE | ID: mdl-30384600

RESUMO

Electrochromic materials (EMs) are widely used color-switchable materials, but their applications as stimuli-responsive biomaterials to monitor and control biological processes remain unexplored. This study reports the engineering of an organic π-electron structure-based EM (dicationic 1,1,4,4-tetraarylbutadiene, 12+) as a unique hydrogen sulfide (H2S)-responsive chromophore amenable to build H2S-activatable fluorescent probes (12+-semiconducting polymer nanoparticles, 12+-SNPs) for in vivo H2S detection. We demonstrate that EM 12+, with a strong absorption (500-850 nm), efficiently quenches the fluorescence (580, 700, or 830 nm) of different fluorophores within 12+-SNPs, while the selective conversion into colorless diene 2 via H2S-mediated two-electron reduction significantly recovers fluorescence, allowing for non-invasive imaging of hepatic and tumor H2S in mice in real time. Strikingly, EM 12+ is further applied to design a near-infrared photosensitizer with tumor-targeting and H2S-activatable ability for effective photodynamic therapy (PDT) of H2S-related tumors in mice. This study demonstrates promise for applying EMs to build activatable probes for molecular imaging of H2S and selective PDT of tumors, which may lead to the development of new EMs capable of detecting and regulating essential biological processes in vivo.


Assuntos
Compostos de Anilina/uso terapêutico , Corantes Fluorescentes/uso terapêutico , Sulfeto de Hidrogênio/análise , Fármacos Fotossensibilizantes/uso terapêutico , Estilbenos/uso terapêutico , Compostos de Anilina/síntese química , Compostos de Anilina/farmacologia , Compostos de Anilina/toxicidade , Animais , Linhagem Celular Tumoral , Desenho de Fármacos , Feminino , Corantes Fluorescentes/síntese química , Corantes Fluorescentes/farmacologia , Corantes Fluorescentes/toxicidade , Células HEK293 , Humanos , Sulfeto de Hidrogênio/química , Sulfeto de Hidrogênio/metabolismo , Raios Infravermelhos , Fígado/metabolismo , Camundongos , Camundongos Endogâmicos BALB C , Imagem Molecular/métodos , Nanopartículas/química , Neoplasias/diagnóstico , Neoplasias/tratamento farmacológico , Neoplasias/metabolismo , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/efeitos da radiação , Fármacos Fotossensibilizantes/toxicidade , Polímeros/química , Células RAW 264.7 , Oxigênio Singlete/metabolismo , Estilbenos/síntese química , Estilbenos/farmacologia , Estilbenos/toxicidade , Tiadiazóis/química , Compostos de Vinila/química , Ensaios Antitumorais Modelo de Xenoenxerto
6.
Acta Biomater ; 72: 256-265, 2018 05.
Artigo em Inglês | MEDLINE | ID: mdl-29588255

RESUMO

Precise diagnosis of lymph node metastasis to guide lymphadenectomy is highly important for gastric cancer therapy in clinics. Though surgical dissection of regional metastatic lymph nodes remains the only way for gastric cancer therapy, the extended dissection may cause unavoidable postoperative risk of complications. It is still lack of effective method enabling the accurate removal of metastatic gastric cancer cells in lymph nodes with minimum injuries to normal tissue. Herein, we report a new fluorescent copper sulfide (CuS) nanoparticle (RGD-CuS-Cy5.5) enabling both non-invasive multimodality imaging and targeting photothermal therapy (PTT) of metastatic gastric cancer cells in lymph nodes. We demonstrate that RGD-CuS-Cy5.5 can easily drain into sentinel lymph nodes (SLN) after injection into primary tumors, and selectively enter into metastatic gastric MNK45 tumor cells via αvß3 integrin-mediated endocytosis. The resulting strong near-infrared (NIR) fluorescence and computed tomography (CT) contrast in metastatic SLN compared to normal SLN can precisely differentiate SLN metastasis of gastric cancers. Guided by the imaging, localized PTT with RGD-CuS-Cy5.5 is conducted upon irradiation with an 808 nm laser, resulting in complete removal of metastatic gastric tumor cells in SLN without obvious toxicity. Moreover, RGD-CuS-Cy5.5 can also allow for the rapid and non-invasive self-monitoring of PTT efficacy against metastatic SLNs in living mice. This study highlights the potential of using RGD-CuS-Cy5.5 for imaging-guided and targeting PTT of SLN metastasis in vivo, which may be applicable for the metastatic gastric cancer therapy in clinics. STATEMENT OF SIGNIFICANCE: RGD-CuS-Cy5.5 nanoparticles possess NIR fluorescence and CT signals for in vivo bimodality imaging of lymph node metastasis. Strong photothermal property under irradiation at 808 nm for efficient PTT. Easy drain into sentinel lymph nodes and selective enter metastatic gastric cancer cells via αvß3 integrin-mediated endocytosis. Rapid and non-invasive monitoring of therapeutic efficacy against lymph node metastasis.


Assuntos
Meios de Contraste , Cobre , Sistemas de Liberação de Medicamentos/métodos , Hipertermia Induzida , Nanopartículas , Imagem Óptica , Fototerapia , Neoplasias Gástricas , Sulfetos , Tomografia Computadorizada por Raios X , Animais , Linhagem Celular Tumoral , Meios de Contraste/química , Meios de Contraste/farmacocinética , Meios de Contraste/farmacologia , Cobre/química , Cobre/farmacocinética , Cobre/farmacologia , Feminino , Humanos , Metástase Linfática/diagnóstico por imagem , Metástase Linfática/prevenção & controle , Camundongos , Camundongos Nus , Nanopartículas/química , Nanopartículas/uso terapêutico , Neoplasias Gástricas/diagnóstico por imagem , Neoplasias Gástricas/tratamento farmacológico , Neoplasias Gástricas/metabolismo , Sulfetos/química , Sulfetos/farmacocinética , Sulfetos/farmacologia
7.
J Biomater Sci Polym Ed ; 29(6): 646-662, 2018 04.
Artigo em Inglês | MEDLINE | ID: mdl-29376484

RESUMO

The enhancement of tumor intracellular drug uptake and resistance against nonspecific protein adsorption are essential for an injectable anticancer drug carrier. In the present study, a new type of redox/pH-responsive zwitterionic nanoparticles (NPs) was prepared using poly-L-glutamic acid and cystamine in aqueous solutions under mild conditions. The NPs showed surface charge convertible feature in response to pH change of the solutions. The NPs demonstrated excellent anti nonspecific protein adsorption. In vitro release profiles of the NPs, they showed redox/pH dual sensitivities in vitro release. The effective intracellular delivery behaviors were verified through investigation of cell viability, and confocal laser scanning microscopy observation of HeLa cells after incubation with the DOX-loaded NPs. The NPs were non-cytotoxic and would have potential applications as a drug delivery vehicle for enhancing intracellular uptake of anticancer drugs.


Assuntos
Cistamina/química , Portadores de Fármacos/química , Nanopartículas/química , Ácido Poliglutâmico/química , Transporte Biológico , Preparações de Ação Retardada , Doxorrubicina/química , Portadores de Fármacos/metabolismo , Portadores de Fármacos/toxicidade , Estabilidade de Medicamentos , Células HeLa , Humanos , Concentração de Íons de Hidrogênio , Espaço Intracelular/metabolismo , Teste de Materiais , Nanopartículas/toxicidade , Oxirredução , Propriedades de Superfície
8.
Mater Sci Eng C Mater Biol Appl ; 61: 278-85, 2016 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-26838851

RESUMO

Zwitterionic nanoparticles have excellent serum stability. In this study, pH/redox responsive polymer was synthesized through a modification of dextran using succinic acid, followed by crosslinking with cystamine. The polymer could self-assemble into stable nanoparticles (NPs) in aqueous solution. The NPs carried certain amount of free carboxyl and amino groups on the surface, which endowed the NPs excellent anti-protein adsorption ability. The surface charge was negative at pH7.4 and was converted to positive at pH5.0. It was revealed that the NPs showed little non-specific protein adsorption and had excellent serum stability, and the NPs could be internalized in Hela cells rapidly. This result was ascribed to the charge reversible feature of the NPs. Doxorubicin (DOX) was loaded in the NPs for release studies in vitro. The DOX-loaded NPs exhibited obvious pH and reduction sensitivities in response to the environment in tumor cells due to the introduction of carboxyl groups, amino groups and disulfide bonds in the NPs. The NPs were biocompatible, biodegradable, and could be potentially applied as anticancer drug carriers for enhancement of tumor intercellular uptake of doxorubicin.


Assuntos
Doxorrubicina , Portadores de Fármacos , Nanopartículas/química , Neoplasias/tratamento farmacológico , Doxorrubicina/química , Doxorrubicina/farmacocinética , Doxorrubicina/farmacologia , Portadores de Fármacos/química , Portadores de Fármacos/farmacocinética , Portadores de Fármacos/farmacologia , Células HeLa , Humanos , Neoplasias/metabolismo , Neoplasias/patologia
9.
J Biomater Sci Polym Ed ; 27(7): 643-56, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-26813767

RESUMO

Zwitterionic copolymers have exhibited high resistance to nonspecific protein adsorption and have wide applications in drug delivery systems. Herein, a pH-responsive poly(Lysine-alt-N,N'-bis(acryloyl) diaminohexane) was synthesized through the Michael addition polymerization between N, N'-bis(acryloyl) diaminohexane and lysine. Subsequently, nano micelles (NMs) were formed by self-assembly of the copolymer in an aqueous solution. The NMs showed a slightly negative charge in blood environment, but a positively charged surface in extracellular pH of tumor. This feature could be used to enhance permeability and retention effect, and reinforce tumor cell uptake. Vitro release studies revealed that the release of DOX from the DOX-loaded NMs was evidently faster at pH 5.0 than at pH 7.4. MTT assays revealed that NMs were nontoxic. Thus, these smart NMs were feasible candidates and could be potentially used in cancer chemotherapy.


Assuntos
Resinas Acrílicas/química , Portadores de Fármacos/química , Liberação Controlada de Fármacos , Micelas , Nanoestruturas/química , Polilisina/análogos & derivados , Polímeros/química , Células 3T3 , Resinas Acrílicas/síntese química , Animais , Antineoplásicos/química , Antineoplásicos/metabolismo , Transporte Biológico , Bovinos , Preparações de Ação Retardada , Doxorrubicina/química , Doxorrubicina/metabolismo , Portadores de Fármacos/síntese química , Células HeLa , Humanos , Concentração de Íons de Hidrogênio , Espaço Intracelular/metabolismo , Camundongos , Polilisina/síntese química , Polilisina/química , Polímeros/síntese química , Propriedades de Superfície , Água/química
10.
Macromol Biosci ; 16(3): 308-13, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-26618931

RESUMO

To enhance drug cellular uptake, a biodegradable terpolymer is synthesized using taurine, N,N-Bis (acryloyl) cystamine, and dodecylamine as raw materials by Michael addition terpolymerization. The terpolymer is transformed to zwitterionic nanoparticles (NPs) through self-assembly. The surface charge of the NPs is convertible from negative at pH 7.4 to positive at pH 6.5, which endows the NPs' excellent nonfouling feature in bloodstream and effective uptake in tumor cells. The NPs display varied morphologies from solid micelles to polymersomes and nanorods depending on molar ratios of the structural units involved. The NPs can be biodegraded in l-glutathione (GSH) solution due to the split of disulfide bonds in main chains of the terpolymers. The NPs demonstrate good pH/reducing responsiveness in drug delivery and can be potentially used as anticancer drug vehicles for enhancement of cellular uptake of anticancer drug.


Assuntos
Antineoplásicos , Plásticos Biodegradáveis , Doxorrubicina , Sistemas de Liberação de Medicamentos/métodos , Nanopartículas/química , Neoplasias/tratamento farmacológico , Células 3T3 , Animais , Antineoplásicos/química , Antineoplásicos/farmacocinética , Antineoplásicos/farmacologia , Plásticos Biodegradáveis/química , Plásticos Biodegradáveis/farmacocinética , Plásticos Biodegradáveis/farmacologia , Doxorrubicina/química , Doxorrubicina/farmacocinética , Doxorrubicina/farmacologia , Células HeLa , Humanos , Concentração de Íons de Hidrogênio , Camundongos
11.
J Biomater Sci Polym Ed ; 26(16): 1152-62, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26255582

RESUMO

Hydrophobically modified sodium alginate, poly (lactic-glycolic acid) grafting from sodium alginate (ALG-g-PLGA), was successfully synthesized through direct one-step polymerization of sodium alginate, glycolic acid, and lactic acid. ALG-g-PLGA self-assembled to colloidal nanoparticles and subsequently hydrogel microspheres were obtained by crosslinking ALG-g-PLGA nanoparticles in the solution of calcium chloride. The modified hydrogel microspheres could be used as the drug delivery vehicles for a hydrophobic ibuprofen. Compared with sodium alginate, ALG-g-PLGA demonstrated an improved drug loading rate, encapsulation efficiency, and prolonged release speed. The products, as novel and highly promising biomaterials, have potential applications.


Assuntos
Alginatos/química , Anti-Inflamatórios não Esteroides/química , Portadores de Fármacos/química , Ibuprofeno/química , Ácido Láctico/química , Nanosferas/química , Poliésteres/química , Ácido Poliglicólico/química , Alginatos/ultraestrutura , Anti-Inflamatórios não Esteroides/administração & dosagem , Anti-Inflamatórios não Esteroides/análise , Cloreto de Cálcio/química , Coloides , Preparações de Ação Retardada/administração & dosagem , Preparações de Ação Retardada/análise , Preparações de Ação Retardada/química , Portadores de Fármacos/administração & dosagem , Portadores de Fármacos/análise , Composição de Medicamentos , Liberação Controlada de Fármacos , Estabilidade de Medicamentos , Temperatura Alta/efeitos adversos , Hidrogéis , Concentração de Íons de Hidrogênio , Interações Hidrofóbicas e Hidrofílicas , Ibuprofeno/administração & dosagem , Ibuprofeno/análise , Indicadores e Reagentes , Microscopia Eletrônica de Varredura , Nanopartículas/química , Nanopartículas/ultraestrutura , Nanosferas/ultraestrutura , Copolímero de Ácido Poliláctico e Ácido Poliglicólico , Propriedades de Superfície
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