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1.
Anal Chem ; 2024 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-38327078

RESUMO

Nucleic acid is one of the most important substances in organisms, and its dynamic changes are closely related to physiological processes. Nucleic acid labeling is conducive to providing important information for the early diagnosis and treatment of pathophysiological processes. Here, we utilized the transfer mechanism between carbon sources and CDs to synthesize wavelength-adjustable N-CDs for the nucleic acid image. Along with the increased graphite nitrogen (from 10.6 to 30.1%) gradually by the precise design of the nitrogen structure in carbon sources (e.g., primary amines, secondary amines, tertiary amines, and liking graphite-nitrogen), the energy gap of CDs reduced, resulting in adjustable wavelength from visible to near-infrared range (from 461 nm/527 nm to 650 nm/676 nm). Furthermore, N-CDs exhibited a selective affinity for nucleic acids, especially RNA. Therefore, N-CDs support an efficient platform for real-time tracking of RNA dynamic changes in cells.

2.
Small ; 20(10): e2304407, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-37880907

RESUMO

Cuproptosis is a novel form of regulated cell death which guarantees to increase the efficacy of existing anticancer treatments that employ traditional apoptotic therapeutics. However, reducing the amount of undesirable Cu ions released in normal tissue and maximizing Cu-induced cuproptosis therapeutic effects at tumor sites are the major challenges. In this study, exploiting the chemical properties of copper ionophores and the tumor microenvironment, a novel method is developed for controlling the valence of copper ions that cause photoinduced cuproptosis in tumor cells. CJS-Cu nanoparticles (NPs) can selectively induce cuproptosis after cascade reactions through H2 O2 -triggered Cu2+ release, photoirradiation-induced superoxide radical (∙O2 - ) generation, and reduction of Cu2+ to Cu+ by ∙O2 - . The generated reactive oxygen species can result in glutathione depletion and iron-sulfur cluster protein damage and further augmented cuproptosis. CJS-Cu NPs effectively suppressed tumor growth and downregulated the expression of metastasis-related proteins, contributing to the complete inhibition of lung metastasis. Ultimately, this study suggests novel avenues for the manipulation of cellular cuproptosis through photochemical reactions.


Assuntos
Neoplasias Pulmonares , Nanopartículas , Humanos , Cobre , Glutationa , Superóxidos , Apoptose , Microambiente Tumoral
3.
Plant Biotechnol J ; 22(4): 802-818, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38217351

RESUMO

The microphenotype plays a key role in bridging the gap between the genotype and the complex macro phenotype. In this article, we review the advances in data acquisition and the intelligent analysis of plant microphenotyping and present applications of microphenotyping in plant science over the past two decades. We then point out several challenges in this field and suggest that cross-scale image acquisition strategies, powerful artificial intelligence algorithms, advanced genetic analysis, and computational phenotyping need to be established and performed to better understand interactions among genotype, environment, and management. Microphenotyping has entered the era of Microphenotyping 3.0 and will largely advance functional genomics and plant science.


Assuntos
Inteligência Artificial , Genômica , Fenótipo , Genômica/métodos , Genótipo , Plantas/genética
4.
Angew Chem Int Ed Engl ; : e202408769, 2024 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-38960984

RESUMO

The clinical application of photodynamic therapy (PDT) is limited by oxygen-dependence and side effects caused by photosensitizer residues. Photoinitiators based on the H-abstraction reaction can address these challenges because they can generate alkyl radical-killing cells independently of oxygen and undergo rapid bleaching following H-abstraction. Nonetheless, the development of photoinitiators for PDT has been impeded by the absence of effective design strategies. Herein, we have developed aryl-ketone substituted cyanine (ACy-R), the first red-light triggered H-abstraction photoinitiators for hypoxic cancer therapy. These ACy-R molecules inherited the near-infrared absorption of cyanine dye, and aryl-ketone modification imparted H-abstraction capability. Experimental and quantum calculations revealed that modifying the electron-withdrawing groups of the aryl (e.g., ACy-5F) improved the contribution of the O atom to the photon excitation process promoting intersystem crossing and H-abstraction ability. Particularly, ACy-5F rapidly penetrated cells and enriched in the endoplasmic reticulum. Even under severe hypoxia, ACy-5F initiated red-light induced H-abstraction with intracellular biomolecules, inducing necroptosis and ferroptosis. Moreover, ACy-5F was degraded after H-abstraction, thus avoiding the side effects of long-term phototoxicity after therapy. This study not only provides a crucial molecular tool for hypoxic tumors therapy, but also presents a promising strategy for the development of multifunctional photosensitizers and photoinitiators.

5.
Small ; 19(11): e2205825, 2023 03.
Artigo em Inglês | MEDLINE | ID: mdl-36587982

RESUMO

The combination of photodynamic therapy (PDT) and chemotherapy (chemo-photodynamic therapy) for enhancing cancer therapeutic efficiency has attracted tremendous attention in the recent years. However, limitations, such as low local concentration, non-suitable treatment light source, and uncontrollable release of therapeutic agents, result in reduced combined treatment efficacy. This study considered adenosine triphosphate (ATP), which is highly upregulated in tumor cells, as a biomarker and developed ingenious ATP-activated nanoparticles (CDNPs) that are directly self-assembled from near-infrared photosensitizer (Cy-I) and amphiphilic Cd(II) complex (DPA-Cd). After selective entry into tumor cells, the positively charged CDNPs would escape from lysosomes and be disintegrated by the high ATP concentration in the cytoplasm. The released Cy-I is capable of producing single oxygen (1 O2 ) for PDT with 808 nm irradiation and DPA-Cd can concurrently function for chemotherapy. Irradiation with 808 nm light can lead to tumor ablation in tumor-bearing mice after intravenous injection of CDNPs. This carrier-free nanoparticle offers a new platform for chemo-photodynamic therapy.


Assuntos
Nanopartículas , Neoplasias , Fotoquimioterapia , Animais , Camundongos , Cádmio , Fármacos Fotossensibilizantes/uso terapêutico , Raios Infravermelhos , Neoplasias/tratamento farmacológico
6.
J Nanobiotechnology ; 21(1): 235, 2023 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-37481565

RESUMO

Systemic administration of platinum-based drugs has obvious limitations in the treatment of advanced bladder cancer (BC) owing to lower tumor accumulation and uncontrolled release of chemotherapeutics. There is an urgent need for advanced strategies to overcome the current limitations of platinum-based chemotherapy, to achieve maximal therapeutic outcomes with reduced side effects. In this study, self-polymerized platinum (II)-polydopamine nanocomplexes (PtPDs) were tailored for efficient chemo-photoimmunotherapy of BC. PtPDs with high Pt loading content (11.3%) were degradable under the combination of a reductive tumor microenvironment and near-infrared (NIR) light irradiation, thus controlling the release of Pt ions to achieve efficient chemotherapy. In addition, polydopamine promoted stronger photothermal effects to supplement platinum-based chemotherapy. Consequently, PtPDs provided effective chemo-photothermal therapy of MB49 BC in vitro and in vivo, strengthening the immunogenic cell death (ICD) effect and robust anti-tumoral immunity response. When combined with a PD-1 checkpoint blockade, PtPD-based photochemotherapy evoked systemic immune responses that completely suppressed primary and distant tumor growth without inducing systemic toxicities. Our work provides a highly versatile approach through metal-dopamine self-polymerization for the precise delivery of metal-based chemotherapeutic drugs, and may serve as a promising nanomedicine for efficient and safe platinum-based chemotherapy for BC.


Assuntos
Nanomedicina , Neoplasias da Bexiga Urinária , Humanos , Polimerização , Indóis , Microambiente Tumoral
7.
Angew Chem Int Ed Engl ; 62(24): e202218768, 2023 06 12.
Artigo em Inglês | MEDLINE | ID: mdl-36890113

RESUMO

Conventional photocages only respond to short wavelength light, which is a significant obstacle to developing efficient phototherapy in vivo. The development of photocages activated by near-infrared (NIR) light at wavelengths from 700 to 950 nm is important for in vivo studies but remains challenging. Herein, we describe the synthesis of a photocage based on a ruthenium (Ru) complex with NIR light-triggered photocleavage reaction. The commercial anticancer drug, tetrahydrocurcumin (THC), was coordinated to the RuII center to create the Ru-based photocage that is readily responsive to NIR light at 760 nm. The photocage inherited the anticancer properties of THC. As a proof-of-concept, we further engineered a self-assembled photocage-based nanoparticle system with amphiphilic block copolymers. Upon exposure to NIR light at 760 nm, the Ru complex-based photocages were released from the polymeric nanoparticles and efficiently inhibited tumor proliferation in vivo.


Assuntos
Nanopartículas , Neoplasias , Fotoquimioterapia , Rutênio , Humanos , Fototerapia , Neoplasias/tratamento farmacológico , Polímeros/uso terapêutico , Nanopartículas/uso terapêutico
8.
J Am Chem Soc ; 144(8): 3477-3486, 2022 03 02.
Artigo em Inglês | MEDLINE | ID: mdl-35076232

RESUMO

Endoplasmic reticulum (ER) stress, caused by overproduction of reactive oxygen species (ROS), has been shown to be responsible for immunogenic cell death (ICD). Seeking ROS generator targeting ER is an optimal solution to efficiently induce ER stress. Despite clear indications of demand for ER-targeting photosensitizer, the alternative chemical tools remain limited. Herein, the first ER-localizable ICD photoinducer using thio-pentamethine cyanine dye (TCy5) to induce ER stress under mild near-infrared (NIR) irradiation has been developed. Within the ICD photoinducer design, polyfluorinated TCy5-Ph-3F possesses a selective tropism to ER accumulation and superior ROS generation capability in both normoxia and hypoxia conditions, which benefit from its low singlet-triplet gaps. Under NIR irradiation, cancer cells stained by TCy5-Ph-3F will lead to ER stress and induce massive emission of damage-associated molecular patterns, including calreticulin and heat-shock protein 70 exposure, high mobility group box 1 efflux, and adenosine triphosphate secretion. Dendritic cells maturation and CD8+ T cells activation in vivo also highlight the effectiveness. Therefore, the growth of abscopal tumors was substantially suppressed by the primary tumor treated with TCy5-Ph-3F and NIR irradiation. These results confer practical applicability that could provide a guideline for designing efficient ICD photoinducers, which will enable expanding organic molecular applications for cancer immunotherapy.


Assuntos
Linfócitos T CD8-Positivos , Neoplasias , Morte Celular , Linhagem Celular Tumoral , Corantes , Estresse do Retículo Endoplasmático , Morte Celular Imunogênica , Neoplasias/tratamento farmacológico , Espécies Reativas de Oxigênio/metabolismo
9.
J Am Chem Soc ; 144(37): 16799-16807, 2022 09 21.
Artigo em Inglês | MEDLINE | ID: mdl-36070479

RESUMO

Ultrasound-triggered remote control of biomolecular functions in cells provides unique advantages for us to interrogate nature. However, strategies to design therapeutic ultrasound-responsive functional molecules remain elusive, and rare ultrasound-cleavable chemical bonds have been developed to date. Herein, therapeutic ultrasound (1 MHz)-induced scission of urea bonds for drug release is demonstrated for the first time. Such a transformation has been verified to be initiated by hydroxyl radicals generated in the interior of cavitation bubbles, occurring specifically at the cavitation bubble-liquid interface. A series of urea-bond-containing prodrugs based on methylene blue (MB), namely MBUs, are designed. Upon sonication with low-intensity therapeutic ultrasound, the urea bonds linked with primary amines can be selectively cleaved, and free MB is released in a physiologically relevant environment, accompanied by recovered absorbance, fluorescence, and photosensitivity. Moreover, an FDA-approved alkylating agent (i.e., melphalan) bearing urea bond is also developed (MBU-Mel), successfully achieving ultrasound-triggered drug release in deep-seated cancer cells (mimic with 1 cm pigskin), showing the scalability of our ultrasound-responsive molecule platform in bioactive molecules release. This may set the starting point for therapeutic ultrasound-induced drug release, making a forward step in "sonopharmacology".


Assuntos
Pró-Fármacos , Ureia , Alquilantes , Aminas , Melfalan , Azul de Metileno/farmacologia
10.
Chemistry ; 28(2): e202103571, 2022 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-34757667

RESUMO

1,7-Di-tert-butyl-substituted aza-BODIPYs (tBu-azaBDP) were successfully obtained for the first time. The structures of tBu-azaBDP and Ph-azaBDP were confirmed by X-ray crystal analysis, and tBu-azaBDP 2 is more twisted than Ph-azaBDP 5. tBu-azaBDPs have significant photo-stability and enhanced water solubility. tBu-azaBDPs possess excellent optical properties, such as high molar extinction coefficients, broad full width half maxima, and large Stokes shifts, which is comparable to those of the parent dye Ph-azaBDP. Although the low-barrier rotation of the distal -tBu groups in tBu-azaBDPs results in low quantum yield, photothermal conversion efficiency and singlet oxygen generation ability of tBu-azaBDPs are more effective than those of Ph-azaBDP, which is highly desirable for a photothermal-photodynamic therapy agent.


Assuntos
Compostos de Boro , Fotoquimioterapia , Oxigênio Singlete
11.
Biomacromolecules ; 23(4): 1733-1744, 2022 04 11.
Artigo em Inglês | MEDLINE | ID: mdl-35107271

RESUMO

The lack of selectivity between tumor and healthy cells, along with inefficient reactive oxygen species production in solid tumors, are two major impediments to the development of anticancer Ru complexes. The development of photoinduced combination therapy based on biodegradable polymers that can be light activated in the "therapeutic window" would be beneficial for enhancing the therapeutic efficacy of Ru complexes. Herein, a biodegradable Ru-containing polymer (poly(DCARu)) is developed, in which two different therapeutics (the drug and the Ru complex) are rationally integrated and then conjugated to a diblock copolymer (MPEG-b-PMCC) containing hydrophilic poly(ethylene glycol) and cyano-functionalized polycarbonate with good degradability and biocompatibility. The polymer self-assembles into micelles with high drug loading capacity, which can be efficiently internalized into tumor cells. Red light induces the generation of singlet oxygen and the release of anticancer drug-Ru complex conjugates from poly(DCARu) micelles, hence inhibiting tumor cell growth. Furthermore, the phototherapy of polymer micelles demonstrates remarkable inhibition of tumor growth in vivo. Meanwhile, polymer micelles exhibit good biocompatibility with blood and healthy tissues, which opens up opportunities for multitherapeutic agent delivery and enhanced phototherapy.


Assuntos
Antineoplásicos , Neoplasias , Antineoplásicos/farmacologia , Antineoplásicos/uso terapêutico , Portadores de Fármacos , Humanos , Micelas , Neoplasias/tratamento farmacológico , Fototerapia , Cimento de Policarboxilato , Polietilenoglicóis/uso terapêutico , Polímeros
12.
Langenbecks Arch Surg ; 407(1): 357-364, 2022 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-34420079

RESUMO

PURPOSE: Total laparoscopic total gastrectomy (TLTG) has been limited in application because of the difficulty of intracorporeal oesophagojejunostomy. Theoretically, an intracorporeal single-stapling oesophagojejunostomy using a circular stapler could be commonly used and provide favourable outcomes for TLTG, as in open total gastrectomy(OTG), in which the use of circular staplers in oesophagojejunostomy is common and the standard procedure. This could be possible if use of a laparoscopic purse-string suture along the distal oesophagus were made easy and simple. However, the simple and optimal use of this procedure remains to be developed. METHODS: Between October 2018 and March 2020, 21 consecutive patients with gastric cancer underwent TLTG using the bracket-like suture method (BLSM) for intracorporeal circular-stapled oesophagojejunostomy in our institution. The surgical details and postoperative outcomes were analysed to evaluate this method. RESULTS: The mean operation time was 227.6 ± 13.6 min. The median time for the two-sided purse-string suture was 4 min (range, 3-5 min). It took an average of 11.5 min for the completion of purse-string suture and anvil placement. Tumour-free margins were achieved in 21 patients with a median length of 2.5 cm (range, 2-6 cm) proximal margin. Three patients developed postoperative complications. There was no mortality. During the median follow-up period of 12 months, no anastomosis-related complications were observed. CONCLUSION: The results suggest that the method cannot only facilitate safe and easy purse-string creation, using the simplest two-sided suture in a short amount of time by circular marking of the intended transection level for intracorporeal circular-stapled oesophagojejunostomy, but can also be completed by laparoscopic surgeons with basic laparoscopic suturing skills.


Assuntos
Laparoscopia , Neoplasias Gástricas , Anastomose Cirúrgica , Gastrectomia , Humanos , Neoplasias Gástricas/cirurgia , Grampeamento Cirúrgico , Técnicas de Sutura , Suturas
13.
Sensors (Basel) ; 22(7)2022 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-35408041

RESUMO

Nowadays, tool condition monitoring (TCM), which can prevent the waste of resources and improve efficiency in the process of machining parts, has developed many mature methods. However, TCM during the production of cutting tools is less studied and has different properties. The scale of the defects in the tool production process is tiny, generally between 10 µm and 100 µm for diamond tools. There are also very few samples with defects produced by the diamond tool grinding process, with only about 600 pictures. Among the many TCM methods, the direct inspection method using machine vision has the advantage of obtaining diamond tool information on-machine at a low cost and with high efficiency, and the method is accurate enough to meet the requirements of this task. Considering the specific, above problems, to analyze the images acquired by the vision system, a neural network model that is suitable for defect detection in diamond tool grinding is proposed, which is named DToolnet. DToolnet is developed by extracting and learning from the small-sample diamond tool features to intuitively and quickly detect defects in their production. The improvement of the feature extraction network, the optimization of the target recognition network, and the adjustment of the parameters during the network training process are performed in DToolnet. The imaging system and related mechanical structures for TCM are also constructed. A series of validation experiments is carried out and the experiment results show that DToolnet can achieve an 89.3 average precision (AP) for the detection of diamond tool defects, which significantly outperforms other classical network models. Lastly, the DToolnet parameters are optimized, improving the accuracy by 4.7%. This research work offers a very feasible and valuable way to achieve TCM in the manufacturing process.

14.
J Am Chem Soc ; 143(31): 12345-12354, 2021 08 11.
Artigo em Inglês | MEDLINE | ID: mdl-34323480

RESUMO

Heavy-atom-based photosensitizers usually exhibit shortened triplet-state lifetimes, which is not ideal for hypoxic tumor photodynamic therapy. Although several heavy-atom-free photosensitizers possess long triplet-state lifetimes, the clinical applicability is limited by their short excitation wavelengths, poor photon capture abilities, and intrinsically hydrophobic structures. Herein we developed a novel NIR heavy-atom-free photosensitizer design strategy by introducing sterically bulky and electron-rich moieties at the meso position of the pentamethine cyanine (Cy5) skeleton, which simultaneously enhanced intersystem crossing (ISC) and prolonged excited-state lifetime. We found that the 1O2 generation ability is directly correlated to the electron-donating ability of the meso substituent in cyanine, and the excited-state lifetime was simultaneously much elongated when the substituents were anthracene derivatives substituted at the 9-position. Our star compound, ANOMe-Cy5, exhibits intense NIR absorption, the highest 1O2 quantum yield (4.48-fold higher than Cy5), the longest triplet-state lifetime (9.80-fold longer than Cy5), and lossless emission intensity (nearly no change compared with Cy5). Such excellent photophysical properties coupled with its inherently cationic and hydrophilic nature enable the photosensitizer to realize photoablation of solid tumor and antitumor lung metastasis. This study highlights the design of a new generation of NIR photosensitizers for imaging-guided photodynamic cancer treatment.


Assuntos
Antineoplásicos/farmacologia , Carbocianinas/farmacologia , Corantes Fluorescentes/farmacologia , Fotoquimioterapia , Fármacos Fotossensibilizantes/farmacologia , Animais , Antineoplásicos/síntese química , Antineoplásicos/química , Carbocianinas/síntese química , Carbocianinas/química , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Teoria da Densidade Funcional , Ensaios de Seleção de Medicamentos Antitumorais , Corantes Fluorescentes/síntese química , Corantes Fluorescentes/química , Neoplasias Mamárias Experimentais/tratamento farmacológico , Neoplasias Mamárias Experimentais/metabolismo , Neoplasias Mamárias Experimentais/patologia , Camundongos , Camundongos Endogâmicos BALB C , Estrutura Molecular , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/química
15.
Anal Chem ; 93(40): 13539-13547, 2021 10 12.
Artigo em Inglês | MEDLINE | ID: mdl-34581571

RESUMO

Monitoring the tumor oxygen level when implementing photodynamic therapy (PDT) on malignant cancer has vital significance but remains challenging yet. Herein, by structurally manipulating a 2,4-dimethylpyrrole-engineered asymmetric BODIPY scaffold with different kinds, numbers, and positions of halogen atoms, we rationally designed several monochromophore-based bifunctional photosensitizers, named BDPs (BDP-I, BDP-II, and BDP-III), with self-sensitized photooxidation characteristics for accurate oxygen reporting and photodynamic tumor ablation. We show that different ways of halogen regulation allow available tuning of BDPs' oxygen-dependent ratiometric fluorescence turn-ons upon light irradiation as well as type-II PDT efficiencies before and after self-sensitized photooxidation. Encouragingly, measuring the specific ratiometric signals of the most promising BDP-II enabled the direct observation of initial oxygen concentration in both living 4T1 cells and a tumor-bearing mice model, affording an alternative way for evaluating oxygen supplementation strategies. Meanwhile, the "always on" PDT effect of BDP-II ensured efficient tumor ablation via apoptosis. Our research was thus believed to be of instructive significance for future application of oxygen-related auxiliary strategies and the design of unimolecular multifunctional PDT agents for cancer precision therapy.


Assuntos
Neoplasias , Fotoquimioterapia , Animais , Linhagem Celular Tumoral , Camundongos , Neoplasias/tratamento farmacológico , Oxigênio , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/uso terapêutico
16.
Plant Biotechnol J ; 19(1): 35-50, 2021 01.
Artigo em Inglês | MEDLINE | ID: mdl-32569428

RESUMO

High-throughput phenotyping is increasingly becoming an important tool for rapid advancement of genetic gain in breeding programmes. Manual phenotyping of vascular bundles is tedious and time-consuming, which lags behind the rapid development of functional genomics in maize. More robust and automated techniques of phenotyping vascular bundles traits at high-throughput are urgently needed for large crop populations. In this study, we developed a standard process for stem micro-CT data acquisition and an automatic CT image process pipeline to obtain vascular bundle traits of stems including geometry-related, morphology-related and distribution-related traits. Next, we analysed the phenotypic variation of stem vascular bundles between natural population subgroup (480 inbred lines) based on 48 comprehensively phenotypic information. Also, the first database for stem micro-phenotypes, MaizeSPD, was established, storing 554 pieces of basic information of maize inbred lines, 523 pieces of experimental information, 1008 pieces of CT scanning images and processed images, and 24 192 pieces of phenotypic data. Combined with genome-wide association studies (GWASs), a total of 1562 significant single nucleotide polymorphism (SNPs) were identified for 30 stem micro-phenotypic traits, and 84 unique genes of 20 traits such as VBNum, VBAvArea and PZVBDensity were detected. Candidate genes identified by GWAS mainly encode enzymes involved in cell wall metabolism, transcription factors, protein kinase and protein related to plant signal transduction and stress response. The results presented here will advance our knowledge about phenotypic trait components of stem vascular bundles and provide useful information for understanding the genetic controls of vascular bundle formation and development.


Assuntos
Feixe Vascular de Plantas , Zea mays , Estudos de Associação Genética , Fenótipo , Melhoramento Vegetal , Polimorfismo de Nucleotídeo Único , Zea mays/genética
17.
Chemistry ; 27(67): 16707-16715, 2021 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-34648222

RESUMO

Upconversion luminescent (UCL) triggered photodynamic therapy (PDT) affords superior outcome for cancer treatment. However, conventional UCL materials which all work by a multiphoton absorption (MPA) process inevitably need extremely high power density far over the maximum permissible exposure (MPE) to laser. Here, a one-photon absorption molecular upconversion sensitizer Cy5.5-Br based on frequency upconversion luminescent (FUCL) is designed for PDT. The unusual super heavy atom effect (SHAE) in Cy5.5-Br strongly enhances its spin-orbit coupling (0.23 cm-1 ), triplet quantum yield (11.1 %) and triplet state lifetime (18.8 µs) while the potential hot-band absorption of Cy5.5-Br is well maintained. Importantly, Cy5.5-Br can efficiently target the tumour site and kill cancer cells by destroying mitochondria under a biosafety MPE to 808 nm laser. The photostability and antitumor results are obviously superior to that of a Stokes process. This work provides a design criterion for FUCL dyes to realize effective PDT upon a biosafety optical density, possibly bringing more clinical benefits than conventional MPA materials.


Assuntos
Fotoquimioterapia , Corantes , Luminescência , Mitocôndrias , Fármacos Fotossensibilizantes/uso terapêutico
18.
Chem Soc Rev ; 49(19): 6800-6815, 2020 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-32929428

RESUMO

Chemiluminescence, the generation of light through chemiexcitation as a result of chemical reactions, has emerged as a novel tool for bioimaging and therapy in vivo. Due to the elimination of external optical excitation, it can effectively avoid background autofluorescence existing in fluorescence techniques, providing extremely high signal-to-noise ratios and sensitivity in bioimaging. Furthermore, in situ emitted photons can replace traditional excitation light to construct chemiexcited photodynamic therapy or drug release systems for the monitoring and treatment of deeply seated diseases or tumors. In this tutorial review, we will focus on the recent advancements of chemiluminescent platforms based on luminophore substrates including luminol and its derivatives, cypridina luciferin analogs, peroxyoxalates, and dioxetanes, and systematically summarize the design principles, sensing mechanisms, and bioimaging and therapeutic applications of representative chemiluminescent probes as well as theranostic agents. Finally, the potential challenges and perspectives of chemiluminescent platforms for bioimaging and therapeutics are also discussed.


Assuntos
Diagnóstico por Imagem , Luminescência , Fotoquimioterapia , Animais , Antineoplásicos/farmacologia , Fluorescência , Humanos , Peróxido de Hidrogênio/metabolismo , Limite de Detecção , Camundongos , Fármacos Fotossensibilizantes/farmacologia
19.
J Environ Manage ; 288: 112435, 2021 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-33823453

RESUMO

Sewage treatment plant (STP) is the major point source of antibiotic contamination, yet the advanced treatment of antibiotic polluted STP effluent has not been given necessary attention. This study is conducted to evaluate the removal efficiency, kinetic, and behavior of sulfonamides, quinolones, tetracyclines, and macrolides antibiotics from STP effluent in a hybrid constructed wetland (HCW) and a layered biological filter (LBF) at different hydraulic loading rates (HLRs). The results showed that the removal efficiency of antibiotics in all the HLRs was ranked as follow: quinolones of HCW (70-95%) > macrolides of HCW (58-77%) > tetracyclines of both systems (59-67%) > quinolones of LBF (28-64%) > macrolides of LBF (13-25%) > sulfonamides of both systems (<0%). The optimal HLR is 1.0 m/day for quinolones and 2.0 m/day for tetracyclines-macrolides in the HCW, and 6.4 m/day for quinolones-tetracyclines in the LBF, respectively. Although HCW performed better on the removal of most antibiotics, LBF exhibited stronger total loading toleration and higher removal loading ability to antibiotics. Among them, quinolones were markedly removed by multiple effect of substrate adsorption, microbial anaerobic degradation, and photolysis in the HCW (planted), and by filter sorption and interception in the LBF (unplanted); adsorption is the dominant elimination approach for tetracyclines in both systems; plant uptake plays a significant role on the removal of macrolides in the HCW.


Assuntos
Esgotos , Áreas Alagadas , Adsorção , Antibacterianos , Tetraciclinas , Eliminação de Resíduos Líquidos , Águas Residuárias/análise
20.
J Am Chem Soc ; 142(3): 1510-1517, 2020 01 22.
Artigo em Inglês | MEDLINE | ID: mdl-31880443

RESUMO

It remains a considerable challenge to realize complete tumor suppression and avoid tumor regrowth by rational design of photosensitizers (PSs) to improve their photon utilization. In this Article, we provide a molecular design (Icy-NBF) based on the oxygen-content-regulated deactivation process of excited states. In the presence of overexpressed nitroreductase in hypoxic cancer cells, Icy-NBF is reduced and converted into a molecule with the same skeleton (Icy-NH2), in which the deactivation of the PS under 808 nm light irradiation proceeds via a different pathway: the excited states deactivation pathway of Icy-NBF involves radiative transition and energy transfer between Icy-NBF and O2; as for Icy-NH2, the deactivation pathway is attributed to non-radiative relaxation. By varying the O2 concentration in tumor cells, the therapeutic mechanism of Icy-NBF under 808 nm light irradiation can be switched between photodynamic and photothermal therapies, which maximizes the advantages of phototherapies with no tumor regrowth. Our study provides help in designing of smart PSs with improvement of photon utilization for efficient tumor photoablation.


Assuntos
Oxigênio/química , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/química , Terapia Fototérmica/métodos , Linhagem Celular Tumoral , Humanos , Cinética
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