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1.
Borate glasses doped with trivalent europium were prepared by the conventional melt quenching technique, in the chemical composition of (49.99-x)B2O3 + 25Li2O + 25LiF+xEu2O3 by varying the concentration of the rare earth ion in the order 0.01, 0.1, 1, 2 and 3 wt% and their structural, luminescence and thermal behavior have been reported. The XRD and FTIR spectra reveal the glass structure and the functional groups. The UV–VIS, luminescence spectra and lifetime of the Eu3+ ions were measured. The local site symmetry around the Eu3+ ions were evaluated through the luminescence intensity ratio (R) of the 5D0 → 7F2 to 5D0 → 7F1 transitions. Optical measurements have been carried out to explore the optical properties such as bonding parameters, Judd–Ofelt parameters, stimulated emission cross-section, transition probability, branching ratio, radiative lifetime, etc. The lifetime measurements of the 5D0 level as a function of the concentration of Eu3+ ion have been found and is comparable to other reported for Eu3+ doped borate, phosphate glasses and higher than that for the tellurite glasses. The thermal properties such as glass transition, crystallization and melting temperatures of the Eu3+ glasses were studied through the DSC traces in the temperature range of 30−1200 °C at a heating rate of 10 °C per minute. The change in optical properties with the variation of Eu3+ ion concentration have been discussed and compared with similar results.  相似文献   

2.
This work reports a newly designed pH-activatable and aniline-substituted aza-boron-dipyrromethene as a trifunctional photosensitizer to achieve highly selective tumor imaging, efficient photodynamic therapy (PDT) and therapeutic self-monitoring through encapsulation in a cRGD-functionalized nanomicelle. The diethylaminophenyl is introduced in to the structure for pH-activatable near-infrared fluorescence and singlet oxygen (1O2) generation, and bromophenyl is imported to increase the 1O2 generation efficiency upon pH activation by virtue of its heavy atom effect. After encapsulation, the nanoprobe can target αvβ3 integrin-rich tumor cells via cRGD and is activated by physiologically acidic pH for cancer discrimination and PDT. The fascinating advantage of the nanoprobe is near-infrared implementation beyond 800 nm, which significantly improves the imaging sensitivity and increases the penetration depth of the PDT. By monitoring the fluorescence decrease in the tumor region after PDT, the therapeutic efficacy is demonstrated in situ and in real time, which provides a valuable and convenient self-feedback function for PDT efficacy tracking. Therefore, this rationally designed and carefully engineered nanoprobe offers a new paradigm for precise tumor theranostics and may provide novel opportunities for future clinical cancer treatment.  相似文献   

3.
Lumazine (pteridine-2,4(1H,3H)-dione, LU) was investigated for its efficiency of singlet oxygen (1O2) production and quenching in aqueous solution. The quantum yield of 1O2 production (ΦΔ) was determined by measurements of the 1O2 luminescence in the near-infrared upon continuous excitation of the sensitizer. Values of ΦΔ are sensitive to the pH and were found to be 0.44 ± 0.01 and 0.080 ± 0.004 in acidic and alkaline media, respectively. The photochemical stability of LU was investigated under different pH conditions, in the presence and in the absence of O2. The photochemical consumption of LU in aqueous solution at room temperature under irradiation at 350 nm was followed by UV–vis spectrophotometry and HPLC. Values of the quantum yields of LU disappearance are low, indicating that LU is rather photostable under physiological conditions.  相似文献   

4.
Herein we describe a photosensitizer (PS) with the capacity to perform multiple logic operations based on a pyrene‐containing phthalocyanine (Pc) derivative. The system presents three output signals (fluorescence at 377 and 683 nm, and singlet oxygen (1O2) production), which are dependent on three inputs: two chemical (concentration of dithiothreitol (DTT) and acidic pH) and one physical (visible light above 530 nm for 1O2 sensitization). The multi‐input/multioutput nature of this PS leads to single‐, double‐, and triple‐mode activation pathways of its fluorescent and photodynamic functions, through the interplay of various interrelated AND, ID, and INHIBIT gates. Dual fluorescence emissions are potentially useful for orthogonal optical imaging protocols while 1O2 is the main reactive species in photodynamic therapy (PDT). We thus expect that this kind of PS logic system will be of great interest for multimodal cellular imaging and therapeutic applications.  相似文献   

5.
To develop new fluorescent and afterglow materials, Mn2+ and Eu3+ co-doped ZnO–GeO2 glasses and glass ceramics were prepared by a sol–gel method and their optical properties were investigated by measuring luminescence, excitation and afterglow spectra, and luminescence quantum yield (QY). Under UV irradiation at 254 nm, some glasses and all of the glass ceramics showed green luminescence peaking at 534 nm due to the 4T1 → 6A1 transition of tetrahedrally coordinated Mn2+ ions. The strongest luminescence was observed in a glass ceramic of 0.1MnO–0.3Eu2O3–25ZnO–75GeO2 heat treated at 900 °C, with QY of 49.8%. All of the green-luminescent glasses and glass ceramics showed green afterglow, and the afterglow lasting for more than 60 min was obtained in a glass ceramic heat treated at 900 °C. It is considered that the Eu3+ ions may behave as electron trapping centers to be associated with the occurrence of the green afterglow due to the Mn2+ ions in the co-doped system.  相似文献   

6.
This preclinical study examines light fluence, photodynamic therapy (PDT) dose and “apparent reacted singlet oxygen,” [1O2]rx, to predict local control rate (LCR) for Photofrin‐mediated PDT of radiation‐induced fibrosarcoma (RIF) tumors. Mice bearing RIF tumors were treated with in‐air fluences (50–250 J cm?2) and in‐air fluence rates (50–150 mW cm?2) at Photofrin dosages of 5 and 15 mg kg?1 and a drug‐light interval of 24 h using a 630‐nm, 1‐cm‐diameter collimated laser. A macroscopic model was used to calculate [1O2]rx and PDT dose based on in vivo explicit dosimetry of the drug concentration, light fluence and tissue optical properties. PDT dose and [1O2]rx were defined as a temporal integral of drug concentration and fluence rate, and singlet oxygen concentration consumed divided by the singlet oxygen lifetime, respectively. LCR was stratified for different dose metrics for 74 mice (66 + 8 control). Complete tumor control at 14 days was observed for [1O2]rx ≥ 1.1 mm or PDT dose ≥1200 μm J cm?2 but cannot be predicted with fluence alone. LCR increases with increasing [1O2]rx and PDT dose but is not well correlated with fluence. Comparing dosimetric quantities, [1O2]rx outperformed both PDT dose and fluence in predicting tumor response and correlating with LCR.  相似文献   

7.
Aurivillius phases have been routinely known as excellent ferroelectrics and have rarely been deemed as materials that luminesce in the near-infrared (NIR) region. Herein, it is shown that the Aurivillius phases can demonstrate broadband NIR luminescence that covers telecommunication and biological optical windows. Experimental characterization of the model system Bi2.14Sr0.75Ta2O9−x, combined with theoretical calculations, help to establish that the NIR luminescence originates from defective [Bi2O2]2+ layers. Importantly, the generality of this finding is validated based on observations of a rich bank of NIR luminescence characteristics in other Aurivillius phases. This work highlights that incorporating defects into infinitely repeating [Bi2O2]2+ layers can be used as a powerful tool to space-selectively impart unusual luminescence emitters to Aurivillius-phase ferroelectrics, which not only offers an optical probe for the examination of defect states in ferroelectrics, but also provides possibilities for coupling of the ferroelectric property with NIR luminescence.  相似文献   

8.
Nanocarriers are employed to deliver photosensitizers for photodynamic therapy (PDT) through the enhanced penetration and retention effect, but disadvantages including the premature leakage and non-selective release of photosensitizers still exist. Herein, we report a 1O2-responsive block copolymer (POEGMA-b-P(MAA-co-VSPpaMA) to enhance PDT via the controllable release of photosensitizers. Once nanoparticles formed by the block copolymer have accumulated in a tumor and have been taken up by cancer cells, pyropheophorbide a (Ppa) could be controllably released by singlet oxygen (1O2) generated by light irradiation, enhancing the photosensitization. This was demonstrated by confocal laser scanning microscopy and in vivo fluorescence imaging. The 1O2-responsiveness of POEGMA-b-P(MAA-co-VSPpaMA) block copolymer enabled the realization of self-amplified photodynamic therapy by the regulation of Ppa release using NIR illumination. This may provide a new insight into the design of precise PDT.  相似文献   

9.
Traditional photodynamic therapy (PDT) is dependent on externally applied light and oxygen, and the depth of penetration of these factors can be insufficient for the treatment of deep infections. The short half-life and short diffusion distance of reactive oxygen species (ROS) also limit the antibacterial efficiency of PDT. Herein, we designed a targeting singlet oxygen delivery system, CARG-Py, for irradiation-free and oxygen-free PDT. This system was converted to the “singlet oxygen battery” CARG-1O2 and released singlet oxygen without external irradiation or oxygen. CARG-1O2 is composed of pyridones coupled to a targeting peptide that improves the utilization of singlet oxygen in deep multidrug-resistant bacterial infections. CARG-1O2 was shown to damage DNA, protein, and membranes by increasing the level of reactive oxygen inside bacteria; the attacking of multiple biomolecular sites caused the death of methicillin-resistant Staphylococcus aureus (MRSA). An in vivo study in a MRSA-infected mouse model of pneumonia demonstrated the potential of CARG-1O2 for the efficient treatment of deep infections. This work provides a new strategy to improve traditional PDT for irradiation- and oxygen-free treatment of deep infections while improving convenience of PDT.  相似文献   

10.
Image-guided photodynamic therapy (PDT) has received growing attention due to its non-invasiveness and precise controllability. However, the PDT efficiency of most photosensitizers are decreased in living system due to the aggregation-caused singlet oxygen (1O2) generation decreasing. Herein, we present an Iridium (III) pyridylpyrrole complex (Ir-1) featuring of aggregation-induced emission (AIE) and 1O2 generation characteristics for image-guided PDT of cancer. Ir-1 aqueous solution exhibits bright red phosphorescence peaked at 630 nm, large Stokes shift of 227 nm, and good 1O2 generation ability. The 1O2 generating rate of Ir-1 in EtOH/water mixture solution is 2.3 times higher than that of Rose Bengal. In vitro experimental results revealed that Ir-1 has better biocompatibility and higher phototoxicity compared with clinically used photosensitizers (Rose Bengal and Ce6), suggesting that Ir-1 can serve as a photosensitizer for image-guided PDT of cancer.  相似文献   

11.
We report the synthesis and photophysical characterization of novel halogenated dipyrrolonaphthyridine-diones (X2–DPNDs, X = Cl, Br, and I), as candidates for photodynamic therapy (PDT) application. Apart from the heavy atom-induced spin-orbit coupling (SOC) dynamics in the investigated X2–DPNDs, it was found that the position of the halogen atom (relative to the nitrogen of the pyrrole ring) also influenced the triplet excited state behavior. Interestingly, the faster/efficiency sensitization of 3O2 to 1O2 using X2–DPND correlates with the rate of triplet population, kISC >1.6 × 108 s−1 for I2–DPND vs kISC >2.9 × 109 s−1 for Cl2–DPND and Br2–DPND (where τISC = 343 ± 3 ps for I2–DPND and τISC = 5–6 ns for Cl2–DPND and Br2–DPND are the lowest time constants/values for ISC). Furthermore, the heavy atom-induced SOC in Cl2–DPND and Br2–DPND did not lead to a reduction of the corresponding fluorescence (ca 75% vs 67% for the parent DPND). The attractive photophysical characteristics of Cl2/Br2–DPND put them on the landscape as not only promising PDT agents but also as fluorescence probes. The present study is a stepping stone in the development of novel organic photosystems for synergistic photomedicinal applications.  相似文献   

12.
Nanocarriers are employed to deliver photosensitizers for photodynamic therapy (PDT) through the enhanced penetration and retention effect, but disadvantages including the premature leakage and non‐selective release of photosensitizers still exist. Herein, we report a 1O2‐responsive block copolymer (POEGMA‐b‐P(MAA‐co‐VSPpaMA) to enhance PDT via the controllable release of photosensitizers. Once nanoparticles formed by the block copolymer have accumulated in a tumor and have been taken up by cancer cells, pyropheophorbide a (Ppa) could be controllably released by singlet oxygen (1O2) generated by light irradiation, enhancing the photosensitization. This was demonstrated by confocal laser scanning microscopy and in vivo fluorescence imaging. The 1O2‐responsiveness of POEGMA‐b‐P(MAA‐co‐VSPpaMA) block copolymer enabled the realization of self‐amplified photodynamic therapy by the regulation of Ppa release using NIR illumination. This may provide a new insight into the design of precise PDT.  相似文献   

13.
A technique is introduced that monitors the depletion of intracellular ground state oxygen concentration ([3O2]) during photodynamic therapy of Mat‐LyLu cell monolayers and cell suspensions. The photosensitizer Pd(II) meso‐tetra(4‐carboxyphenyl)porphine (PdT790) is used to manipulate and indicate intracellular [3O2] in both of the in vitro models. The Stern–Volmer relationship for PdT790 phosphorescence was characterized in suspensions by flowing nitrogen over the suspension while short pulses of 405 nm light were used to excite the sensitizer. The bleaching of sensitizer and the oxygen consumption rate were also measured during continuous exposure of the cell suspension to the 405 nm laser. Photodynamic therapy (PDT) was conducted in both cell suspensions and in cell monolayers under different treatment conditions while the phosphorescence signal was acquired. The intracellular [3O2] during PDT was calculated by using the measured Stern–Volmer relationship and correcting for sensitizer photobleaching. In addition, the amount of oxygen that was consumed during the treatments was calculated. It was found that even at large oxygen consumption rates, cells remain well oxygenated during PDT of cell suspensions. For monolayer treatments, it was found that intracellular [3O2] is rapidly depleted over the course of PDT.  相似文献   

14.
The distributions of light and tissue oxygenation (StO2) within the chest cavity were determined for 15 subjects undergoing macroscopic complete resection followed by intraoperative photodynamic therapy (PDT) as part of a clinical trial for the treatment of malignant pleural mesothelioma (MPM). Over the course of light delivery, detectors at each of eight different sites recorded exposure to variable fluence rate. Nevertheless, the treatment-averaged fluence rate was similar among sites, ranging from a median of 40–61 mW cm−2 during periods of light exposure to a detector. StO2 at each tissue site varied by subject, but posterior mediastinum and posterior sulcus were the most consistently well oxygenated (median StO2 >90%; interquartile ranges ~85–95%). PDT effect on StO2 was characterized as the StO2 ratio (post-PDT StO2/pre-PDT StO2). High StO2 pre-PDT was significantly associated with oxygen depletion (StO2 ratio < 1), although the extent of oxygen depletion was mild (median StO2 ratio of 0.8). Overall, PDT of the thoracic cavity resulted in moderate treatment-averaged fluence rate that was consistent among treated tissue sites, despite instantaneous exposure to high fluence rate. Mild oxygen depletion after PDT was experienced at tissue sites with high pre-PDT StO2, which may suggest the presence of a treatment effect.  相似文献   

15.
Photodynamic therapy (PDT) is a way of treating malignant tumors and hyperproliferative diseases. It is based on the use of photosensitizer, herein the chlorophyll a (chl a), and a light of an appropriate wavelength. The interaction of the photosensitizer (PS) with the light produces reactive oxygen species (ROS), powerful oxidizing agents, which cause critical damage to the tissue. To solubilize chl a in aqueous solution and to obtain it as monomer, we have used cyclodextrins, carriers which are able to interact with the pigment and form the inclusion complex. The aim of this study is to examine which types of ROS are formed by Chl a/cyclodextrin complexes in phosphate buffered solution and cell culture medium, using specific molecules, called primary acceptors, which react selectively with the reactive species. In fact the changes of the absorption and the emission spectra of these molecules after the illumination of the PS provide information on the specific ROS formation. The 1O2 formation has been tested using chemical methods based on the use of Uric Acid (UA), 9,10‐diphenilanthracene (DPA) and Singlet oxygen sensor green (SOSG) and by direct detection of Singlet Oxygen (1O2) luminescence decay at 1270 nm. Moreover, 2,7‐dichlorofluorescin and ferricytochrome c (Cyt Fe3+) have been used to detect the formation of hydrogen peroxide and superoxide radical anion, which reduces Fe3+ of the ferricytochrome to Fe2+, respectively.  相似文献   

16.
The photochemical, photophysical and photobiological studies of a mixture containing cis-[Ru(H-dcbpy)2(Cl)(NO)] (H2-dcbpy = 4,4′-dicarboxy-2,2′-bipyridine) and Na4[Tb(TsPc)(acac)] (TsPc = tetrasulfonated phthalocyanines; acac = acetylacetone), a system capable of improving photodynamic therapy (PDT), were accomplished. cis-[Ru(H-dcbpy)2(Cl)(NO)] was obtained from cis-[Ru(H2-dcbpy)2Cl2]·2H2O, whereas Na4[Tb(TsPc)(acac)] was obtained by reacting phthalocyanine with terbium acetylacetonate. The UV–Vis spectrum of cis-[Ru(H-dcbpy)2(Cl)(NO)] displays a band in the region of 305 nm (λmax in 0.1 mol L−1 HCl)(π–π*) and a shoulder at 323 nm (MLCT), while the UV–Vis spectrum of Na4[Tb(TsPc)(acac)] presents the typical phthalocyanine bands at 342 nm (Soret λmax in H2O) and 642, 682 (Q bands). The cis-[Ru(H-dcbpy)2(Cl)(NO)] FTIR spectrum displays a band at 1932 cm−1 (Ru–NO+). The cyclic voltammogram of the cis-[Ru(H-dcbpy)2(Cl)(NO)] complex in aqueous solution presented peaks at E = 0.10 V (NO+/0) and E = −0.50 V (NO0/−) versus Ag/AgCl. The NO concentration and 1O2 quantum yield for light irradiation in the λ > 550 nm region were measured as [NO] = 1.21 ± 0.14 μmol L−1 and øOS = 0.41, respectively. The amount of released NO seems to be dependent on oxygen concentration, once the NO concentration measured in aerated condition was 1.51 ± 0.11 μmol L−1 The photochemical pathway of the cis-[Ru(H-dcbpy)2(Cl)(NO)]/Na4[Tb(TsPc)(acac)] mixture could be attributed to a photoinduced electron transfer process. The cytotoxic assays of cis-[Ru(H-dcbpy-)2(Cl)(NO)] and of the mixture carried out with B16F10 cells show a decrease in cell viability to 80% in the dark and to 20% under light irradiation. Our results document that the simultaneous production of NO and 1O2 could improve PDT and be useful in cancer treatment.  相似文献   

17.
When irradiated, fullerene efficiently generates reactive oxygen species (ROS) and is an attractive photosensitizer for photodynamic therapy (PDT). Ideally, photosensitizers for PDT should be water-soluble and tumor-specific. Because cancer cells endocytose glucose more effectively than normal cells, the characteristics of fullerene as a photosensitizer were improved by combining it with glucose. The cytotoxicity of PDT was studied in several cancer cell lines cultured with C60-(Glc)1 (d -glucose residue pendant fullerene) and C60-(6Glc)1 (a maltohexaose residue pendant fullerene) subsequently irradiated with UVA1. PDT alone induced significant cytotoxicity. In contrast, PDT with the glycoconjugated fullerene exhibited no significant cytotoxicity against normal fibroblasts, indicating that PDT with these compounds targeted cancer cells. To investigate whether the effects of PDT with glycoconjugated fullerene were because of the generation of singlet oxygen (1O2), NaN3 was added to cancer cells during irradiation. NaN3 extensively blocked PDT-induced apoptosis, suggesting that PDT-induced cell death was a result of the generation of 1O2. Finally, to investigate the effect of PDT in vivo, melanoma-bearing mice were injected intratumorally with C60-(Glc)1 and irradiated with UVA1. PDT with C60-(Glc)1 suppressed tumor growth. These findings indicate that PDT with glycoconjugated fullerene exhibits tumor-specific cytotoxicity both in vivo and in vitro via the induction of 1O2.  相似文献   

18.
Recently, photodynamic therapy (PDT) has been extensively applied in clinical and coadjuvant treatment of various kinds of tumors. However, the photosensitizer (PS) of PDT still lack of high production of singlet oxygen (1O2), low cytotoxicity and high biocompatibility. Herein, we propose a facile method for establishing a new core-shell structured Sn nanocluster@carbon dots (CDs) PS. Firstly, Sn4+@S-CDs complex is synthesized using the sulfur-doped CDs (S-CDs) and SnCl4 as raw materials, and subsequently the new PS (Sn nanocluster@CDs) is obtained after vaporization of Sn4+@S-CDs solution. Remarkably, the obtained Sn nanocluster@CDs show an enhanced fluorescence as well as a higher 1O2 quantum yield (QY) than S-CDs. The high 1O2 QY (58.3%) irradiated by the LED light (400–700 nm, 40 mW/cm2), induce the reduction of 4T1 cancer cells viability by 25%. More intriguingly, no visible damage happens to healthy cells, with little impact on liver tissue due to renal excretion, both in vitro and in vivo experiments demonstrate that Sn nanocluster@CDs may become a promising PS, owning a high potential for application in PDT.  相似文献   

19.
Li  ZhaoBo  Wang  JianGuang  Chen  JingRong  Lei  WanHua  Wang  XueSong  Zhang  BaoWen 《中国科学:化学(英文版)》2010,53(9):1994-1999

pH-responsive 1O2 photosensitizing systems may serve as selective photodynamic therapy (PDT) agents by targeting the acidic interstitial fluid of many kinds of tumors. In this work, a natural and clinically used photosensitizer (Hypocrellin B, HB) and a pH indicator (Bromocresol Purple, BCP) were co-encapsulated in organically modified silica nanoparticles. BCP successfully regulated the 1O2 generation efficiency of HB through the “inner filter” effect, which shows much stronger 1O2 generation ability in an acidic than in a basic environment. In vitro experiments also demonstrated that HB-doped nanoparticles are effective in killing tumor cells by PDT.

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20.
The phase relations in the Fe-rich part of the pseudo-binary system SrO–Fe2O3 (>33 mol% Fe2O3) were reinvestigated between 800 and 1500 °C in air. A combination of microscopy, electron probe micro-analysis, powder X-ray diffraction and thermal analysis was used to determine phase relations, crystal structure parameters and phase transition temperatures. M-type hexagonal ferrite SrFe12O19 (85.71 mol% Fe2O3) is stable up to 1410 °C. No indication of a significant phase width was found; Sr4Fe6O13±δ appears as a second phase in compositions with <85.71±0.2 mol% Fe2O3. Sr4Fe6O13±δ itself is stable between 800 and 1250 °C. Two other hexagonal ferrites were found to exist at high temperatures only: W-type SrFe2+2Fe3+16O27 is stable between 1350 and 1440 °C and X-type ferrite Sr2Fe2+2Fe3+28O46 between 1350 and 1420 °C, respectively, which is shown here for the first time. These findings in combination with previously published data were used to derive a corrected phase diagram of the Fe-rich part of the pseudo-binary system SrO–Fe2O3.  相似文献   

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