ABSTRACT
Photoelectrochemical (PEC) nanobiosensors integrate molecular (bio)recognition elements with semiconductor/plasmonic photoactive nanomaterials to produce measurable signals after light-induced reactions. Recent advancements in PEC nanobiosensors, using light-matter interactions, have significantly improved sensitivity, specificity, and signal-to-noise ratio in detecting (bio)analytes. Tunable nanomaterials activated by a wide spectral radiation window coupled to electrochemical transduction platforms have further improved detection by stabilizing and amplifying electrical signals. This work reviews PEC biosensors based on nanomaterials like metal oxides, carbon nitrides, quantum dots, and transition metal chalcogenides (TMCs), showing their superior optoelectronic properties and analytical performance for the detection of clinically relevant biomarkers. Furthermore, it highlights the innovative role of red light and NIR-activated PEC nanobiosensors in enhancing charge transfer processes, protecting them from biomolecule photodamage in vitro and in vivo applications. Overall, advances in PEC detection systems have the potential to revolutionize rapid and accurate measurements in clinical diagnostic applications. Their integration into miniaturized devices also supports the development of portable, easy-to-use diagnostic tools, facilitating point-of-care (POC) testing solutions and real-time monitoring.
Subject(s)
Biosensing Techniques , Electrochemical Techniques , Infrared Rays , Biosensing Techniques/methods , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Humans , Nanostructures/chemistry , Quantum Dots/chemistry , Quantum Dots/radiation effects , Animals , Photochemical Processes , Biomarkers/analysisABSTRACT
Antibacterial nanoagents have been increasingly developed due to their favorable biocompatibility, cost-effective raw materials, and alternative chemical or optical properties. Nevertheless, there is still a pressing need for antibacterial nanoagents that exhibit outstanding bacteria-binding capabilities and high antibacterial efficiency. In this study, we constructed a multifunctional cascade bioreactor (GCDCO) as a novel antibacterial agent. This involved incorporating carbon dots (CDs), cobalt sulfide quantum dots (CoSx QDs), and glucose oxidase (GOx) to enhance bacterial inhibition under sunlight irradiation. The GCDCO demonstrated highly efficient antibacterial capabilities attributed to its favorable photothermal properties, photodynamic activity, as well as the synergistic effects of hyperthermia, glucose-augmented chemodynamic action, and additional photodynamic activity. Within this cascade bioreactor, CDs played the role of a photosensitizer for photodynamic therapy (PDT), capable of generating ËO2- even under solar light irradiation. The CoSx QDs not only functioned as a catalytic component to decompose hydrogen peroxide (H2O2) and generate hydroxyl radicals (ËOH), but they also served as heat generators to enhance the Fenton-like catalysis process. Furthermore, GOx was incorporated into this cascade bioreactor to internally supply H2O2 by consuming glucose for a Fenton-like reaction. As a result, GCDCO could generate a substantial amount of reactive oxygen species (ROS), leading to a significant synergistic effect that greatly induced bacterial death. Furthermore, the in vitro antibacterial experiment revealed that GCDCO displayed notably enhanced antibacterial activity against E. coli (99+ %) when combined with glucose under simulated sunlight, surpassing the efficacy of the individual components. This underscores its remarkable efficiency in combating bacterial growth. Taken together, our GCDCO demonstrates significant potential for use in the routine treatment of skin infections among diabetic patients.
Subject(s)
Anti-Bacterial Agents , Glucose Oxidase , Photochemotherapy , Quantum Dots , Quantum Dots/chemistry , Quantum Dots/radiation effects , Glucose Oxidase/chemistry , Photochemotherapy/methods , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Escherichia coli/drug effects , Photosensitizing Agents/pharmacology , Photosensitizing Agents/chemistry , Cobalt/chemistry , Cobalt/pharmacology , Light , Carbon/chemistry , Carbon/pharmacology , Humans , Hydrogen Peroxide/pharmacology , Bioreactors , Reactive Oxygen Species/metabolismABSTRACT
Ultraviolet (UV) radiation is known to cause skin issues, such as dryness, aging, and even cancer. Among UV rays, UVB stands out for its ability to trigger problems within cells, including mitochondrial dysfunction, oxidative stress, and DNA damage. Free radicals are implicated in these cellular responses, but they are challenging to measure due to their short lifetime and limited diffusion range. In our study, we used a quantum sensing technique (T1 relaxometry) involving fluorescent nanodiamonds (FNDs) that change their optical properties in response to magnetic noise. This allowed us to monitor the free radical presence in real time. To measure radicals near mitochondria, we coated FNDs with antibodies, targeting mitochondrial protein voltage-dependent anion channel 2 (anti-VDAC2). Our findings revealed a dynamic rise in radical levels on the mitochondrial membrane as cells were exposed to UVB (3 J/cm2), with a significant increase observed after 17 min.
Subject(s)
Keratinocytes , Mitochondria , Ultraviolet Rays , Humans , Mitochondria/metabolism , Mitochondria/radiation effects , Free Radicals/chemistry , Keratinocytes/radiation effects , Keratinocytes/metabolism , Quantum Dots/chemistry , Quantum Dots/radiation effectsABSTRACT
Mitochondrial sulfur dioxide (SO2) and formaldehyde (FA) in cancer cells serve as important signal molecules in mediating multiple physiological and pathological activities. Accurate monitoring of the dynamic fluctuation of SO2 and FA in the mitochondria of cancer cells is important for insight into their relationships and functions in cancer, understanding cancer mechanism, and the role of mitochondrial homeostasis in cancer invasion and metastasis. Herein, a novel integrated two-photon semiconducting polymer dot (BF@Pdots) with dual-targeting (cancer cells and mitochondrial) and dual-emission in green and red regions, which is rationally designed through a four-step engineering strategy by using two newly synthesized functionalized polymers PFNA and FD-PSMA as precursors, has been developed for accurate tracking of the dynamic variation of SO2 and FA in the mitochondria of cancer cells. The sensing mechanism is on the basis of the fluorescence resonance energy transfer (FRET) process in BF@Pdots tuned by the reversible Michael addition reaction between the sensing-groups and SO2 (or FA). The integrated BF@Pdots nanoprobes display excellent performances in the accurate detection of the dynamic fluctuation of SO2 and FA such as precise positioning in the mitochondria of cancer cells, self-calibrating ratiometric, two-photon emission with long wavelength excitation, and fast reversible response. The BF@Pdots nanoprobes are also applied to the ratiometric detection of the dynamic fluctuation of exogenous and endogenous SO2 and FA in the mitochondria of cancer cells for the first time with satisfactory results. Taken together, this work will provide an attractive way to develop versatile integrated Pdots-based fluorescent probes through flexible molecular engineering for applications in accurate imaging of biomolecules in living systems.
Subject(s)
Fluorescent Dyes/chemistry , Formaldehyde/analysis , Mitochondria/metabolism , Polymers/chemistry , Quantum Dots/chemistry , Sulfur Dioxide/analysis , Animals , Cell Line, Tumor , Fluorenes/chemistry , Fluorenes/radiation effects , Fluorescence Resonance Energy Transfer , Fluorescent Dyes/radiation effects , Formaldehyde/metabolism , Humans , Limit of Detection , Male , Mice , Naphthalimides/chemistry , Naphthalimides/radiation effects , Neoplasms/metabolism , Photons , Polymers/radiation effects , Quantum Dots/radiation effects , RAW 264.7 Cells , Semiconductors , Sulfur Dioxide/metabolism , ZebrafishABSTRACT
The Ti3C2 MXene quantum dots (Ti3C2 MQDs) derived from Ti3C2 MXene have received much attention because of their remarkable advantages in biosensing. Nevertheless, the functionalization of Ti3C2 MQDs to improve their properties is just in its infant stage. Herein, we firstly synthesized nitrogen and boron co-doped Ti3C2 MQDs (N, B-Ti3C2 MQDs) with good water solubility, strong stability, and high optical characteristics. The N, B-Ti3C2 MQDs exhibit excitation wavelength-dependent blue photoluminescence with optimal excitation/emission peaks at 335/439 nm. Nowadays, the development of fast and real-time detection of tetracycline (TC) in animal derived food is very essential. In this work, a novel point-of-care testing (POCT) platform was established based on ratiometric fluorescence method using N, B-Ti3C2 MQDs coupled with Eu3+. Upon addition of TC in the Eu3+/N, B-MQDs system, blue fluorescence emission of N, B-Ti3C2 MQDs was quenched and red fluorescence emission of Eu3+ was enhanced gradually, which was ascribed to the synergistic inner filter effect and antenna effect. Moreover, we prepared test papers with N, B-Ti3C2 MQDs and Eu3+ for TC detection based on the change of fluorescence color, which could be recognized by color recognizer app installed in the smartphone. Therefore, great promise for POCT of TC is given with the merits of simplicity and visible detection possibility. The proposed method demonstrated a low detection limit of 20 nM. Application of the platform for TC quantification in milk samples opened a novel means for the potential use of N, B-Ti3C2 MQDs in food safety.
Subject(s)
Europium/chemistry , Fluorescent Dyes/chemistry , Point-of-Care Testing , Quantum Dots/chemistry , Tetracycline/analysis , Titanium/chemistry , Animals , Anti-Bacterial Agents/analysis , Boron/chemistry , Boron/radiation effects , Europium/radiation effects , Fluorescence , Fluorescent Dyes/radiation effects , Food Contamination/analysis , Limit of Detection , Milk/chemistry , Nitrogen/chemistry , Nitrogen/radiation effects , Paper , Quantum Dots/radiation effects , Smartphone , Spectrometry, Fluorescence/instrumentation , Spectrometry, Fluorescence/methods , Titanium/radiation effects , Ultraviolet RaysABSTRACT
Despite bismuth-based energy conversion nanomaterials having attracted extensive attention for nanomedicine, the nanomaterials suffer from major shortcomings including low tumor accumulation, long internal retention time, and undesirable photothermal conversion efficiency (PCE). To combat these challenges, bovine serum albumin and folic acid co-modified Bi2Se3 nanomedicine with rich selenium vacancies (abbreviated as VSe-BS) was fabricated for the second near-infrared (NIR-II) light-triggered photonic hyperthermia. More importantly, selenium vacancies on the crystal planes (0 1 5) and (0 1 11) of VSe-BS with similar formation energies could be distinctively observed via aberration-corrected scanning transmission electron microscopy images. The defect engineering endows VSe-BS with enhanced conductivity, making VSe-BS possess outstanding PCE (54.1%) in the NIR-II biowindow and desirable photoacoustic imaging performance. Tumor ablation studies indicate that VSe-BS possesses satisfactory therapeutic outcomes triggered by NIR-II light. These findings give rise to inspiration for further broadening the biological applications of defect engineering bismuth-based nanomaterials.
Subject(s)
Antineoplastic Agents/therapeutic use , Bismuth/therapeutic use , Contrast Media/therapeutic use , Neoplasms/drug therapy , Quantum Dots/therapeutic use , Selenium Compounds/therapeutic use , Animals , Antineoplastic Agents/chemistry , Antineoplastic Agents/radiation effects , Bismuth/chemistry , Cattle , Cell Line, Tumor , Contrast Media/chemistry , Contrast Media/radiation effects , Density Functional Theory , Female , Folic Acid/chemistry , Infrared Rays , Mice, Inbred BALB C , Models, Chemical , Neoplasms/diagnostic imaging , Photoacoustic Techniques , Photothermal Therapy , Quantum Dots/chemistry , Quantum Dots/radiation effects , Selenium Compounds/chemistry , Selenium Compounds/radiation effects , Serum Albumin, Bovine/chemistryABSTRACT
Nanotechnology has emerged as a promising solution to permanent elimination of cancer. However, nanoparticles themselves lack specificity to tumors. Due to enhanced migration to tumors, mesenchymal stem cells (MSCs) were suggested as cell-mediated delivery vehicles of nanoparticles. In this study, we have constructed a complex composed of photoluminescent quantum dots (QDs) and a photosensitizer chlorin e6 (Ce6) to obtain multifunctional nanoparticles, combining cancer diagnostic and therapeutic properties. QDs serve as energy donors-excited QDs transfer energy to the attached Ce6 via Förster resonance energy transfer, which in turn generates reactive oxygen species. Here, the physicochemical properties of the QD-Ce6 complex and singlet oxygen generation were measured, and the stability in protein-rich media was evaluated, showing that the complex remains the most stable in protein-free medium. In vitro studies on MSC and cancer cell response to the QD-Ce6 complex revealed the complex-loaded MSCs' potential to transport theranostic nanoparticles and induce cancer cell death. In vivo studies proved the therapeutic efficacy, as the survival of tumor-bearing mice was statistically significantly increased, while tumor progression and metastases were slowed down.
Subject(s)
Antineoplastic Agents/therapeutic use , Carcinoma, Lewis Lung/diagnostic imaging , Carcinoma, Lewis Lung/drug therapy , Mesenchymal Stem Cells/metabolism , Multifunctional Nanoparticles/therapeutic use , Animals , Antineoplastic Agents/chemistry , Antineoplastic Agents/metabolism , Antineoplastic Agents/radiation effects , Cadmium Compounds/chemistry , Cadmium Compounds/metabolism , Cadmium Compounds/radiation effects , Cadmium Compounds/therapeutic use , Carcinoma, Lewis Lung/metabolism , Cell Line, Tumor , Chlorophyllides/chemistry , Chlorophyllides/metabolism , Chlorophyllides/radiation effects , Chlorophyllides/therapeutic use , Female , Humans , Light , Mice, Inbred C57BL , Multifunctional Nanoparticles/chemistry , Multifunctional Nanoparticles/metabolism , Multifunctional Nanoparticles/radiation effects , Photochemotherapy/methods , Photosensitizing Agents/chemistry , Photosensitizing Agents/metabolism , Photosensitizing Agents/radiation effects , Photosensitizing Agents/therapeutic use , Precision Medicine/methods , Quantum Dots/chemistry , Quantum Dots/metabolism , Quantum Dots/radiation effects , Quantum Dots/therapeutic use , Selenium Compounds/chemistry , Selenium Compounds/metabolism , Selenium Compounds/radiation effects , Selenium Compounds/therapeutic use , Singlet Oxygen/metabolism , Sulfides/chemistry , Sulfides/metabolism , Sulfides/radiation effects , Sulfides/therapeutic use , Zinc Compounds/chemistry , Zinc Compounds/metabolism , Zinc Compounds/radiation effects , Zinc Compounds/therapeutic useABSTRACT
Herein, novel rodlike CdTe@MPA-PDA particles based on polydopamine (PDA) loaded with CdTe quantum dots (QDs) capped with mercaptopropionic acid (CdTe@MPA QDs) with atypical chemical features are evaluated as a potential actuator for photothermal therapy and oxidative stress induction. Under mild conditions established for the safe and efficient use of lasers, temperature increases of 10.2 and 7.8 °C, photothermal conversion efficiencies of 37.7 and 26.2%, and specific absorption rates of 99 and 69 W/g were obtained for CdTe@MPA-PDA and traditional PDA particles in water, respectively. The particles were set to interact with the human breast adenocarcinoma cell line MDA-MB-231. A significant cellular uptake with the majority of particles colocalized into the lysosomes was obtained at a concentration of 100 µg/mL after 24 h. Additionally, CdTe@MPA-PDA and CdTe@MPA QDs showed significantly different internalization levels and loading kinetics profiles. For the first time, the thermal lens technique was used to demonstrate the stability of particle-like CdTe@MPA-PDA after heating at pH 7 and their migration within the heating region due to the thermodiffusion effect. However, under acidic pH-type lysosomes, a performance decrease in heating was observed, and the chemical feature of the particles was damaged as well. Besides, the internalized rodlike CdTe@MPA-PDA notably enhanced the induction of oxidative stress compared with PDA alone and CdTe@MPA QDs in MDA-MB-231 cells initiating apoptosis. Combining these effects suggests that after meticulous optimizations of the conditions, the CdTe@MPA-PDA particles could be used as a photothermal agent under mild conditions and short incubation time, allowing cytoplasmatic subcellular localization. On the other hand, the same particles act as cell killers by triggering reactive oxygen species after a longer incubation time and lysosomal subcellular localization due to the pH effect on the chemical morphology features of the CdTe@MPA-PDA particles.
Subject(s)
Antineoplastic Agents/pharmacology , Oxidative Stress/drug effects , Photosensitizing Agents/pharmacology , Quantum Dots/chemistry , Reactive Oxygen Species/metabolism , Antineoplastic Agents/chemistry , Antineoplastic Agents/radiation effects , Apoptosis/drug effects , Cadmium Compounds/chemistry , Cadmium Compounds/radiation effects , Cell Line, Tumor , Cell Survival/drug effects , Humans , Indoles/chemistry , Indoles/radiation effects , Light , Photosensitizing Agents/chemistry , Photosensitizing Agents/radiation effects , Polymers/chemistry , Polymers/radiation effects , Quantum Dots/radiation effects , Tellurium/chemistry , Tellurium/radiation effectsABSTRACT
Combined therapeutic strategies for bacterial infection have attracted worldwide attention owing to their faster and more effective therapy with fewer side effects compared with monotherapy. In this work, gold-platinum nanodots (AuPtNDs) are simply and quickly synthesized by a one-step method. They not only exhibit powerful peroxidase-like activity but also confer a higher affinity for hydrogen peroxide (H2O2), which is 3.4 times that of horseradish peroxidase. Under 808 nm laser irradiation, AuPtNDs also have excellent photothermal conversion efficiency (50.53%) and strong photothermal stability. Excitingly, they can combat bacterial infection through the combination of chemodynamic and photothermal therapy. In vitro antibacterial results show that the combined antibacterial strategy has a broad-spectrum antibacterial property against both Escherichia coli (Gram negative, 97.1%) and Staphylococcus aureus (Gram positive, 99.3%). Animal experiments further show that nanodots can effectively promote the healing of bacterial infection wounds. In addition, owing to good biocompatibility and low toxicity, they are hardly traceable in the main organs of mice, which indicates that they can be well excreted through metabolism. These results reveal the application potential of AuPtNDs as a simple and magic multifunctional nanoparticle in antibacterial therapy and open up new applications for clinical anti-infective therapy in the near future.
Subject(s)
Anti-Bacterial Agents/therapeutic use , Quantum Dots/therapeutic use , Staphylococcal Skin Infections/drug therapy , Animals , Anti-Bacterial Agents/chemical synthesis , Anti-Bacterial Agents/radiation effects , Anti-Bacterial Agents/toxicity , Catalysis , Escherichia coli/drug effects , Gold/chemistry , Gold/radiation effects , Gold/therapeutic use , Gold/toxicity , HEK293 Cells , Humans , Infrared Rays , Mice, Inbred BALB C , Microbial Sensitivity Tests , Photothermal Therapy , Platinum/chemistry , Platinum/radiation effects , Platinum/therapeutic use , Platinum/toxicity , Quantum Dots/chemistry , Quantum Dots/radiation effects , Quantum Dots/toxicity , Staphylococcus aureus/drug effects , Wound Healing/drug effectsABSTRACT
In the present study, the novel Ag/cellulose nanocrystal (CNC)-doped CeO2 quantum dots (QDs) with highly efficient catalytic performance were synthesized using one pot co-precipitation technique, which were then applied in the degradation of methylene blue and ciprofloxacin (MBCF) in wastewater. Catalytic activity against MBCF dye was significantly reduced (99.3%) for (4%) Ag dopant concentration in acidic medium. For Ag/CNC-doped CeO2 vast inhibition domain of G-ve was significantly confirmed as (5.25-11.70 mm) and (7.15-13.60 mm), while medium- to high-concentration of CNC levels were calculated for G + ve (0.95 nm, 1.65 mm), respectively. Overall, (4%) Ag/CNC-doped CeO2 revealed significant antimicrobial activity against G-ve relative to G + ve at both concentrations, respectively. Furthermore, in silico molecular docking studies were performed against selected enzyme targets dihydrofolate reductase (DHFR), dihydropteroate synthase (DHPS), and DNA gyrase belonging to folate and nucleic acid biosynthetic pathway, respectively to rationalize possible mechanism behind bactericidal potential of CNC-CeO2 and Ag/CNC-CeO2.
Subject(s)
Anti-Bacterial Agents/pharmacology , Cellulose/chemistry , Cerium/chemistry , Coloring Agents/chemistry , Quantum Dots/chemistry , Silver/pharmacology , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/metabolism , Anti-Bacterial Agents/radiation effects , Bacterial Proteins/chemistry , Bacterial Proteins/metabolism , Catalysis/radiation effects , Cellulose/chemical synthesis , Cellulose/metabolism , Cellulose/radiation effects , Cerium/metabolism , Cerium/radiation effects , Ciprofloxacin/chemistry , DNA Gyrase/chemistry , DNA Gyrase/metabolism , Dihydropteroate Synthase/chemistry , Dihydropteroate Synthase/metabolism , Escherichia coli/drug effects , Escherichia coli/enzymology , Light , Methylene Blue/chemistry , Microbial Sensitivity Tests , Molecular Docking Simulation , Protein Binding , Quantum Dots/metabolism , Quantum Dots/radiation effects , Silver/chemistry , Silver/metabolism , Silver/radiation effects , Staphylococcus aureus/drug effects , Tetrahydrofolate Dehydrogenase/chemistry , Tetrahydrofolate Dehydrogenase/metabolism , Water Pollutants, Chemical/chemistry , Water Purification/methodsABSTRACT
Phototherapy exhibits significant potential as a novel tumor treatment method, and the development of highly active photosensitizers and photothermal agents has drawn considerable attention. In this work, S and N atom co-doped carbon dots (S,N-CDs) with an absorption redshift effect were prepared by hydrothermal synthesis with lysine, o-phenylenediamine, and sulfuric acid as raw materials. The near-infrared (NIR) absorption features of the S,N-CDs resulted in two-photon (TP) emission, which has been used in TP fluorescence imaging of lysosomes and tumor tissue pH and real-time monitoring of apoptosis during tumor phototherapy, respectively. The obtained heteroatom co-doped CDs can be used not only as an NIR imaging probe but also as an effective photodynamic therapy/photothermal therapy (PDT/PTT) therapeutic agent. The efficiencies of different heteroatom-doped CDs in tumor treatment were compared. It was found that the S,N-CDs showed higher therapeutic efficiency than N-doped CDs, the efficiency of producing 1O2 was 27%, and the photothermal conversion efficiency reached 34.4%. The study provides new insight into the synthesis of carbon-based nanodrugs for synergistic phototherapy and accurate diagnosis of tumors.
Subject(s)
Antineoplastic Agents/therapeutic use , Fluorescent Dyes/therapeutic use , Neoplasms/diagnostic imaging , Neoplasms/drug therapy , Photosensitizing Agents/therapeutic use , Quantum Dots/therapeutic use , Animals , Antineoplastic Agents/chemistry , Antineoplastic Agents/radiation effects , Apoptosis/drug effects , Carbon/chemistry , Carbon/radiation effects , Fluorescent Dyes/chemistry , Fluorescent Dyes/radiation effects , Fluorometry , HeLa Cells , Humans , Hydrogen-Ion Concentration , Lysosomes/metabolism , Mice, Nude , Neoplasms/metabolism , Nitrogen/chemistry , Nitrogen/radiation effects , Photons , Photosensitizing Agents/chemistry , Photosensitizing Agents/radiation effects , Phototherapy , Quantum Dots/chemistry , Quantum Dots/radiation effects , Singlet Oxygen/metabolism , Sulfur/chemistry , Sulfur/radiation effectsABSTRACT
Carbon dots (CDs) are photoluminescent nanomaterials with wide-ranging applications. Despite their photoactivity, it remains unknown whether CDs degrade under illumination and whether such photodegradation poses any cytotoxic effects. Here, we show laboratory-synthesized CDs irradiated with light degrade into molecules that are toxic to both normal (HEK-293) and cancerous (HeLa and HepG2) human cells. Eight days of irradiation photolyzes 28.6-59.8% of the CDs to <3 kilo Dalton molecules, 1431 of which are detected by high-throughput, non-target high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry. Molecular network and community analysis further reveal 499 cytotoxicity-related molecules, 212 of which contain polyethylene glycol, glucose, or benzene-related structures. Photo-induced production of hydroxyl and alkyl radicals play important roles in CD degradation as affected by temperature, pH, light intensity and wavelength. Commercial CDs show similar photodegraded products and cytotoxicity profiles, demonstrating that photodegradation-induced cytotoxicity is likely common to CDs regardless of their chemical composition. Our results highlight the importance of light in cytocompatibility studies of CDs.
Subject(s)
Carbon/toxicity , Cytotoxins/toxicity , Quantum Dots/toxicity , Benzene Derivatives/chemistry , Benzene Derivatives/toxicity , Carbon/chemistry , Carbon/radiation effects , Cell Survival/drug effects , Cytotoxins/chemistry , Glucose/chemistry , Glucose/toxicity , HEK293 Cells , HeLa Cells , Humans , Hydrogen-Ion Concentration , Hydroxyl Radical/chemistry , Hydroxyl Radical/toxicity , Kinetics , Light , Photolysis , Polyethylene Glycols/chemistry , Polyethylene Glycols/toxicity , Quantum Dots/chemistry , Quantum Dots/radiation effects , TemperatureABSTRACT
Intratumoral hypoxia significantly constrains the susceptibility of solid tumors to oxygen-dependent photodynamic therapy (PDT), and effort to reverse such hypoxia has achieved limited success to date. Herein, we developed a novel engineered bacterial system capable of targeting hypoxic tumor tissues and efficiently mediating the photodynamic treatment of these tumors. For this system, we genetically engineered Escherichia coli to express catalase, after which we explored an electrostatic adsorption approach to link black phosphorus quantum dots (BPQDs) to the surface of these bacteria, thereby generating an engineered E. coli/BPQDs (EB) system. Following intravenous injection, EB was able to target hypoxic tumor tissues. Subsequent 660 nm laser irradiation drove EB to generate reactive oxygen species (ROS) and destroy the membranes of these bacteria, leading to the release of catalase that subsequently degrades hydrogen peroxide to yield oxygen. Increased oxygen levels alleviate intratumoral hypoxia, thereby enhancing BPQD-mediated photodynamic therapy. This system was able to efficiently kill tumor cells in vivo, exhibiting good therapeutic efficacy. In summary, this study is the first to report the utilization of engineered bacteria to facilitate PDT, and our results highlight new avenues for BPQD-mediated cancer treatment.
Subject(s)
Antineoplastic Agents/therapeutic use , Hypoxia/drug therapy , Neoplasms/drug therapy , Phosphorus/therapeutic use , Photosensitizing Agents/therapeutic use , Quantum Dots/therapeutic use , Animals , Antineoplastic Agents/chemistry , Antineoplastic Agents/radiation effects , Catalase/genetics , Catalase/metabolism , Cell Engineering , Cell Line, Tumor , Cell Membrane/drug effects , Escherichia coli/drug effects , Escherichia coli/enzymology , Escherichia coli/genetics , Hypoxia/etiology , Mice, Inbred BALB C , Neoplasms/complications , Oxygen/metabolism , Phosphorus/chemistry , Phosphorus/radiation effects , Photochemotherapy , Photosensitizing Agents/chemistry , Photosensitizing Agents/radiation effects , Quantum Dots/chemistry , Quantum Dots/radiation effects , Reactive Oxygen Species/metabolismABSTRACT
The immunosuppressive tumor microenvironment has caused great obstacles to tumor immunotherapy, especially where less tumor-associated antigens are released from tumor sites. Herein, a Ag2S QD/DOX/Bestatin@PC10ARGD genetically engineered polypeptide hydrogel PC10ARGD as a sustained-release material was developed for mammary carcinoma treatment. A near-infrared silver sulfide (Ag2S) QD as a photosensitizer was encapsulated into the hydrophobic cavity formed by the self-assembly of the polypeptide nanogel (PC10ARGD) for photothermal therapy. The water-soluble drug DOX and Bestatin were integrated into the PC10ARGD hydrogel. The photothermal effect could trigger the sustained release of the DOX, which could be applied to initiate in situ vaccination. Bestatin as an immune-adjuvant drug could amplify the body's immune function. The results of in vivo therapy tests exhibited that the Ag2S QD/DOX/Bestatin@PC10ARGD hydrogel with laser irradiation could activate anti-tumor immune effects that inhibit the growth of primary tumors and distal lung metastatic nodules. Meanwhile, a safer lower-temperature with multiple laser irradiation treatment strategy exhibited more effective tumor-killing performance (84.4% tumor inhibition rate) and promoted the penetration of immune cells into the tumor tissue. The CD8+ and CD4+ cytotoxic T cells ratio was increased by 5.3 and 10 times, respectively, thus exhibiting a good prognostic signal. The multifunctional polypeptide hydrogel as a green manufacturing and engineering material is promising to serve as a cancer vaccine for anticancer applications.
Subject(s)
Adjuvants, Immunologic/therapeutic use , Antineoplastic Agents/therapeutic use , Breast Neoplasms/drug therapy , Drug Carriers/chemistry , Hydrogels/chemistry , Peptides/chemistry , Adjuvants, Immunologic/administration & dosage , Adjuvants, Immunologic/chemistry , Animals , Antineoplastic Agents/administration & dosage , Antineoplastic Agents/chemistry , CD4-Positive T-Lymphocytes/metabolism , CD8-Positive T-Lymphocytes/metabolism , Cell Line, Tumor , Doxorubicin/administration & dosage , Doxorubicin/chemistry , Doxorubicin/therapeutic use , Drug Carriers/administration & dosage , Drug Carriers/toxicity , Drug Liberation , Drug Therapy , Female , Hydrogels/administration & dosage , Hydrogels/toxicity , Infrared Rays , Injections, Subcutaneous , Leucine/administration & dosage , Leucine/analogs & derivatives , Leucine/chemistry , Leucine/therapeutic use , Mice, Inbred BALB C , Peptides/administration & dosage , Peptides/toxicity , Photosensitizing Agents/administration & dosage , Photosensitizing Agents/radiation effects , Photosensitizing Agents/therapeutic use , Photothermal Therapy , Quantum Dots/administration & dosage , Quantum Dots/radiation effects , Quantum Dots/therapeutic use , Silver Compounds/administration & dosage , Silver Compounds/radiation effects , Silver Compounds/therapeutic useABSTRACT
An intramolecular photoelectrochemical (PEC) system is designed from the novel electron donor YYYHWRGWV (Y3-H) peptide ligand for the first time. The bifunctional nonapeptide cannot only rely on the HWRGWV sequence as a site-oriented immobilizer to recognize the crystallizable fragment (Fc) domains of the antibody but also acts as electron donors for PEC generation via three tyrosine (Y) of the N-terminal. The Bi2WO6/AgInS2 heterojunction with a significant visible-light absorption is utilized as a photoelectric generator, and the motivation is ascribed to a proven proposition, namely, that short-wavelength illuminant radiates proteins, causing a decline in bioactivity of immune protein. An innovative biosensor is fabricated using the above strategies for the detection of CYFRA21-1, a biomarker of squamous cell lung carcinoma. This sort of PEC-based sensing platform shows convincing experimental data and could be an effective candidate for clinical application in the future due to their extremely skillful conception.
Subject(s)
Antigens, Neoplasm/blood , Biomarkers, Tumor/blood , Biosensing Techniques/methods , Electrochemical Techniques/methods , Keratin-19/blood , Peptides/chemistry , Tyrosine/chemistry , Antibodies, Immobilized/chemistry , Antibodies, Immobilized/immunology , Antigens, Neoplasm/immunology , Biomarkers, Tumor/immunology , Bismuth/chemistry , Electrons , Humans , Indium/chemistry , Indium/radiation effects , Keratin-19/immunology , Light , Limit of Detection , Photochemistry/methods , Quantum Dots/chemistry , Quantum Dots/radiation effects , Silver Compounds/chemistry , Silver Compounds/radiation effects , Tungsten Compounds/chemistry , Tungsten Compounds/radiation effectsABSTRACT
A new fluorescence turn-on sensing platform has been developed applicable for sensitive profiling of multiple chemical and biological analytes, using azobenzene-quantum dot as a new stimuli-responsive optical nanoprobe. An azobenzene-carrying compound bis [4, 4'-(dithiophenyl azo)-1, 3-benzenediamine] (DTPABDA) is for the first time reported to be used for conjugation with CdSe/ZnS core/shell quantum dots (QDs) via the ligand exchange reaction. Due to the photo-induced electron-transfer (PET) effect, the electron-withdrawing azobenzene groups of DTPABDA can significantly cause the photoluminescence (PL) of QDs quenched. The QDs' PL can be subsequently reignited by the removal of azo moiety cleavable through three types of specific reactions: the dithionite reduction, hypochlorite oxidation, and azoreductase enzymatic catalysis, respectively. By monitoring of reaction-induced recovery of FL signals at 560 nm with an excitation of 450 nm, such azobenzene-QDs conjugates served as a new nanoprobe enabling the fluorescence turn-on sensing of dithionite, hypochlorite, and azoreductase with high sensitivity, broad linear range, and good selectivity. The successful detection of target analytes in real samples reveals the potential of our method in practical applications, such as biosensing, environmental and industrial monitoring. Graphical abstract A new stimuli-responsive fluorescence probe is reported for the sensitive detection of sodium dithionite, hypochlorite, and azoreductase. The probe consists of QDs with an azobenzene-carrying compound as a ligand. The fluorescence of QDs could be quenched by the azo group and subsequently recovered via the removal of azo group by these three compounds, resulting in the "turn-on" sensing of these compounds with high sensitivity, broad linear range, and good selectivity. The successful detection of azoreductase in serum samples reveals the practical use of this method.
Subject(s)
Dithionite/analysis , Fluorescent Dyes/chemistry , Hypochlorous Acid/analysis , Nitroreductases/blood , Quantum Dots/chemistry , Azo Compounds/chemical synthesis , Azo Compounds/chemistry , Cadmium Compounds/chemistry , Cadmium Compounds/radiation effects , Fluorescent Dyes/chemical synthesis , Humans , Light , Limit of Detection , Proof of Concept Study , Quantum Dots/radiation effects , Selenium Compounds/chemistry , Selenium Compounds/radiation effects , Spectrometry, Fluorescence/methods , Sulfides/chemistry , Sulfides/radiation effects , Zinc Compounds/chemistry , Zinc Compounds/radiation effectsABSTRACT
Silver nanoparticle (Ag NP)-coated carbon quantum dot (CQD) core-shell-structured nanocomposites (CQD@Ag NCs) were developed for fluorescent imaging of intracellular superoxide anion (O2â¢-). The morphology of CQD@Ag NCs was investigated by transmission electron microscopy, and the composition was characterized by X-ray diffraction and X-ray photoelectron spectroscopy. CQDs display blue fluorescence with excitation/emission maxima at 360/440 nm, and the fluorescence was quenched by Ag NPs in CQD@Ag NCs. In the presence of O2â¢-, Ag NPs were oxide-etched and the fluorescence of CQDs was recovered. A linearity between the relative fluorescence intensity and O2â¢- solution concentration within the range 0.6 to 1.6 µM was found, with a detection limit of 0.3 µM. Due to their high sensitivity, selectivity, and low cytotoxicity, the as-synthesized CQD@Ag NCs have been successfully applied for imaging of O2â¢- in MCF-7 cells during the whole process of autophagy induced by serum starvation. In our perception, the developed method provides a cost-effective, sensitive, and selective tool in bioimaging and monitoring of intracellular O2â¢- changes, and is promising for potential biological applications. Graphical abstract Illustration of the synthesis of carbon quantum Dot@Silver nanocomposites (CQD@Ag NCs), and CQD@Ag NCs as a "turn-on" nanoprobe for fluorescent imaging of intracellular superoxide anion.
Subject(s)
Fluorescent Dyes/chemistry , Nanocomposites/chemistry , Quantum Dots/chemistry , Superoxides/analysis , Carbon/chemistry , Carbon/radiation effects , Carbon/toxicity , Fluorescent Dyes/radiation effects , Fluorescent Dyes/toxicity , Humans , Limit of Detection , MCF-7 Cells , Metal Nanoparticles/chemistry , Metal Nanoparticles/radiation effects , Metal Nanoparticles/toxicity , Microscopy, Fluorescence , Nanocomposites/radiation effects , Nanocomposites/toxicity , Quantum Dots/radiation effects , Quantum Dots/toxicity , Silver/chemistry , Silver/radiation effects , Silver/toxicity , Ultraviolet RaysABSTRACT
A photoelectrochemical platform for thrombin determination was developed based on Au-rGO-CuS as multiple signal amplification elements. CuInS2 QDs was used to sensitize burr-shape TiO2 (b-TiO2) to obtain a strong photocurrent. Under the specific recognition between aptamer and thrombin, a sandwichlike structure was formed and the Au-rGO-CuS-labeled aptamer (S2@Au-rGO-CuS) was immobilized on the electrode surface. This induced a sharp decrease in photocurrent. The phenomenon is mainly due to the fact that CuS NPs can competitively consume the light energy and electron donor with CuInS2/b-TiO2. The rGO can increase the amount of CuS NPs and the Au NPs can accelerate charge transferring which depress the recombination of photogenerated electrons and holes in CuS to further enhance the competitive capacity of CuS. The sandwichlike structure has a steric hindrance effect. Therefore, the S2@Au-rGO-CuS has a multiple signal amplification function for thrombin determination. Under optimal conditions, the PEC aptasensor exhibited a wide linear concentration range from 0.1 pM to 10 nM with a low detection limit of 30 fM (S/N = 3) for thrombin. Besides, the designed aptasensor performed well in the assay of human serum sample, indicating good potential for the determination of thrombin in real samples. Graphical abstract.
Subject(s)
Aptamers, Nucleotide/chemistry , Biosensing Techniques/methods , Electrochemical Techniques/methods , Quantum Dots/chemistry , Thrombin/analysis , Copper/chemistry , Copper/radiation effects , DNA/chemistry , Gold/chemistry , Graphite/chemistry , Humans , Immobilized Nucleic Acids/chemistry , Indium/chemistry , Indium/radiation effects , Light , Limit of Detection , Photochemical Processes , Quantum Dots/radiation effects , Thrombin/chemistry , Titanium/chemistryABSTRACT
Ferroptosis is an iron-dependent form of regulated cell death. In this study, a ratiometric fluorescent probe, gold carbon dots (GCDs) consisting of carbon skeleton and gold nanoclusters, was used for in situ imaging to monitor redox status in biothiols (glutathione and cysteine) and ferric metabolism of cancer cells in ferroptosis. The as-prepared GCDs can selectively respond to biothiols, interestingly, the fluorescence may be switched to sense ferric ions without interference by biothiols under proper conditions. The robust GCDs-probe exhibits excellent photobleaching resistance and can reversibly respond to intracellular biothiols/ferric ion with high temporal resolution. The 8 h real-time imaging of living cells was employed to track the fluctuation of biothiols, showing the change of redox status in ferroptosis. In addition, release of ferric ions in cells was monitored. The real-time imaging of depletion of biothiols and release of ferric ion in cells indicates the GCDs-probe can monitor how the ferroptosis regulates redox status in biothiols and ferric metabolism.
Subject(s)
Cysteine/analysis , Ferroptosis/physiology , Fluorescent Dyes/chemistry , Glutathione/analysis , Iron/analysis , Quantum Dots/chemistry , Carbon/chemistry , Carbon/radiation effects , Cell Line, Tumor , Cysteine/chemistry , Cysteine/metabolism , Ferroptosis/drug effects , Fluorescent Dyes/radiation effects , Glutathione/chemistry , Glutathione/metabolism , Gold/chemistry , Gold/radiation effects , Humans , Iron/metabolism , Light , Metal Nanoparticles/chemistry , Metal Nanoparticles/radiation effects , Microscopy, Confocal , Microscopy, Fluorescence , Neoplasms/metabolism , Oxidation-Reduction , Piperazines/pharmacology , Quantum Dots/radiation effectsABSTRACT
BACKGROUND: Stimulus-responsive degradable mesoporous organosilica nanoparticles (MONs) have shown great promise as drug carriers via enhancing the efficiency of drug delivery and accelerating the degradation of nanocarriers. However, it remains a great challenge to develop novel light-enabled spatial and temporal degradable MONs with both superior responsiveness for efficient anti-cancer drug delivery and safe exocytosis. RESULTS: We report a novel photo-responsive degradable hollow mesoporous organosilica nanoplatform (HMONs@GOQD). The platform is based on organosilica nanoparticles (HMONs) containing singlet oxygen (1O2)-responsive bridged organoalkoxysilanes and wrapped graphene oxide quantum dots (GOQDs). The unique hollow mesoporous structure of the HMONs guarantees an excellent drug loading and release profile. During light irradiation, 1O2 produced by the GOQDs leads to the degradation of the organosilica nanoparticles, resulting in enhanced local drug release. CONCLUSIONS: We carried out in vitro and in vivo experiments using DOX as a model drug; DOX-HMONs@GOQDs exhibited high biocompatibility, accelerated degradation, and superior therapeutic efficacy during light irradiation, indicating a promising platform for clinical cancer therapy.