Potential of using medicinal plant extracts as photosensitizers for antimicrobial photodynamic therapy.

Antimicrobial photodynamic therapy (APDT) is a promising approach to overcome antimicrobial resistance. However, for widespread implementation of this approach, approved photosensitizers are needed. In this study, we used commercially available preparations (Calendulae officinalis floridis extract, Chamomillae recutitae floridis extract, Achillea millefolii herbae extract; Hypericum perforatum extract; Eucalyptus viminalis folia extract) as photosensitizers for inactivation of gram-negative (Pseudomonas aeruginosa) and gram-positive (Staphylococcus aureus) bacteria. Spectral-luminescent analysis has shown that the major chromophores are of chlorophyll (mainly chlorophyll a and b) and hypericin nature. The extracts are efficient generators of singlet oxygen with quantum yield (Î³Δ ) from 0.40 to 0.64 (reference compound, methylene blue with Î³Δ = 0.52). In APDT assays, bacteria before irradiation were incubated with extracts for 30 min. After irradiation and 24 h of incubation, colony-forming units (CFU) were counted. Upon exposure of P. aeruginosa to radiation of 405 nm, 590 nm, and 660 nm at equal energy dose of 30 J/cm2 (irradiance - 100 mW/cm2 , exposure time - 5 min), the most pronounced effect is observed with blue light (>3 log10 reduction); in case of S. aureus, the effect is approximately equivalent for light of indicated wavelengths and dose (>4 log10 reduction).

Development of natural attapulgite derived ferromanganese spinel oxides as heterogeneous catalysts for persulfate activation of tetracycline degradation.

Ferromanganese spinel oxides (MnFe2O4, MFO) have been proven effective in activating persulfate for pollutants removal. However, their inherent high surface energy often leads to agglomeration, diminishing active sites and consequently restricting catalytic performance. In this study, using Al-MCM-41 (MCM) mesoporous molecular sieves derived from natural attapulgite as a support, the MFO/MCM composite was synthesized through dispersing MnFe2O4 nanoparticles on MCM carrier by a simple hydrothermal method, which can effectively activate persulfate (PS) to degrade Tetracycline (TC). The addition of Al-MCM-41 can effectively improve the specific surface area and adsorption performance of MnFe2O4, but also reduce the leaching amount of metal ions. The MFO/MCM composite exhibited superior catalytic reactivity towards PS and 84.3% removal efficiency and 64.7% mineralization efficiency of TC (20 mg/L) was achieved in 90 min under optimized conditions of 0.05 mg/L catalyst dosage, 5 mM PS concentration, room temperature and no adjustment of initial pH. The effects of various stoichiometric MFO/MCM ratio, catalyst dosage, PS concentration, initial pH value and co-existing ions on the catalytic performance were investigated in detail. Moreover, the possible reaction mechanism in MFO-MCM/PS system was proposed based on the results of quenching tests, electron paramagnetic resonance (EPR) and XPS analyses. Finally, major degradation intermediates of TC were detected by liquid chromatography mass spectrometry technologies (LC-MS) and four possible degradation pathways were proposed. This study enhances the design approach for developing highly efficient, environmentally friendly and low-cost catalysts for the advanced treatment process of antibiotic wastewater.

Near infra-red absorbing Quinolizidine fused curcuminoid-BF2 chelate and its applications in photodynamic therapy using MCF-7 and A549 cells.

Metal-free near-infrared absorbing photosensitizers (PS) have been considered promising candidates for photodynamic therapy. Curcumin, curcuminoid, and its derivatives have therapeutic values due to their anti-inflammatory, antifungal, and antiproliferative properties. Curcuminoid-BF2 chelates have also been studied as cell imaging probes, however, their applications in photodynamic therapy are rare. In this article, we describe the synthesis and therapeutic evaluation of quinolizidine fused curcuminoid-BF2 chelate (Quinolizidine CUR-BF2) containing an acid-sensitive group. This donor-acceptor-donor curcuminoid-BF2 derivative exhibits absorption and emission in the deep red region with an absorption band maximum of ∼647 nm and a weak emission band at approximately 713 nm. It is interesting to note that this derivative has a high molar extinction coefficient (164,655 M-1cm-1). Quinolizidine CUR-BF2 possesses intramolecular charge transfer properties, facilitating the production of singlet oxygen (1O2), which plays a crucial role in cell death. Additionally, Quinolizidine CUR-BF2 can enable the selective release of active ingredients in an acidic medium (pH 5). Furthermore, the nanoaggregates of PS were prepared by encapsulating Quinolizidine CUR-BF2 within Pluronic F127 block co-polymer for better water-dispersibility and enhanced cellular uptake. Dark cytotoxicity of nanoaggregates was found to be negligible, whereas they exhibited significant photoinduced cytotoxicity towards cancer cells (MCF-7 and A549) under irradiation of 635 nm light. Further, the cell death pathway using Quinolizidine CUR-BF2 nanoaggregates as PS is found to occur through apoptosis. Specifically, the present study deals with the successful preparation of Quinolizidine CUR-BF2 nanoaggregates for enhanced water-dispersibility and cellular uptake as well as the efficacy evaluation of developed nanoaggregates for photodynamic therapy.

BP@Au undergoes rapid degradation and releases singlet oxygen under dark conditions: Doping effect and detrimental effects on superoxide-producing marine algae.

Black phosphorus (BP) shows encouraging utility in many fields, and metal doping has been suggested as an efficient way to improve stability. However, controversial results and inconsistent mechanisms have been reported for doping modulation and stability change. We observed the unforeseen evolution of singlet oxygen (1O2) from BP integrated with gold nanoparticles (BP@Au) under dark conditions, and this led to rapid BP deterioration, even though enhanced stability is commonly thought via surface doping. Briefly, the BP reacted with oxygen and water to yield superoxide (O2•-) and hydrogen peroxide. Au0 acted as an enzyme mimic and catalyzed the conversion of these derivatives, and Au0 was converted to a mixture of Au3+ and Au+. The O2•- was converted to 1O2 via direct donation of electrons to the Au3+/+. The Au-catalyzed redox reactions accelerated the degradation of the BP nanosheets. BP@Au showed significant toxicity toward marine alga that produce O2•- in the dark, as indicated by a more than 30% reduction in cell viability after 12 h of incubation with 7.56 mg/L BP@Au. The novelty of this work lies in the demonstration of a dopant-related degradation pathway of BP that shows unrevealed toxicity toward O2•--producing marine algae.

Ratiometric singlet oxygen self-detecting and oxygen self-supplying nanosensor for real-time photodynamic therapy feedback and therapeutic effect enhancement.

Integration of singlet oxygen (1O2) detection that provides necessary therapeutic feedback into nanotheranostics for hypoxic tumor photodynamic therapy (PDT) is desirable but still challenging. Herein, we report a nanosensor (denominated PAPD) by combining dual-channel ratiometric sensing and oxygen-augmenting strategies, which synergistically realizes real-time 1O2 self-detection, O2 self-supply and enhanced phototherapy. PAPD nanosensor is constructed by encapsulating anthracene-based 1O2 sensitive fluorophore (DPA) into porphyrin metal-organic frameworks (PCN-224), decorating gold nanoparticles (AuNPs) as nanoenzymes, and coating polyethylene glycol thiol (PEG-SH) by the Au-S bond. PCN-224 serves as 1O2 reference fluorescence (FL) agent and photosensitizer. Once PCN-224-induced 1O2 is synthesized, the dual-channel ratiometric FL signal of PAPD actualizes sensitive, accurate and dynamic 1O2 visualization and gives real-time therapeutic information correlated with the therapeutic progression. Additionally, the catalase-like activity of PAPD possesses in situ O2 production via intracellular H2O2 decomposition and accelerates 1O2 yields for amplifying the tumor cell killing efficiency. Moreover, the ratiometric 1O2 self-detection affords the capacity to evaluate the O2 self-supplying effect in tumor 4T1 cells. Consequently, the rational-designed nanosensor PAPD provides a paradigm for real-time therapeutic evaluation and precise hypoxic tumor treatment clinically.

Exploring Low-Power Single-Pulsed Laser-Triggered Two-Photon Photodynamic/Photothermal Combination Therapy Using a Gold Nanostar/Graphene Quantum Dot Nanohybrid.

Combined photodynamic/photothermal therapy (PDT/PTT) has emerged as a promising cancer treatment modality due to its potential synergistic effects and identical treatment procedures. However, its clinical application is hindered by long treatment times and complicated treatment operations when separate illumination sources are required. Here, we present the development of a new nanohybrid comprising thiolated chitosan-coated gold nanostars (AuNS-TCS) as the photothermal agent and riboflavin-conjugated N,S-doped graphene quantum dot (Rf-N,S-GQD) as the two-photon photosensitizer (TP-PS). The nanohybrid demonstrated combined TP-PDT/PTT when a low-power, single-pulsed laser irradiation was applied, and the localized surface plasmon resonance of AuNS was in resonance with the TP-absorption wavelength of Rf-N,S-GQD. The TCS coating significantly enhanced the colloidal stability of AuNSs while providing a suitable substrate to electrostatically anchor negatively charged Rf-N,S-GQDs. The plasmon-enhanced singlet oxygen (1O2) generation effect led to boosted 1O2 production both extracellularly and intracellularly. Notably, the combined TP-PDT/PTT exhibited significantly improved phototherapeutic outcomes compared to individual strategies against 2D monolayer cells and 3D multicellular tumor spheroids. Overall, this study reveals a successful single-laser-triggered, synergistic combined TP-PDT/PTT based on a plasmonic metal/QD hybrid, with potential for future investigation in clinical settings.

Sulfonamide Porphyrins as Potent Photosensitizers against Multidrug-Resistant Staphylococcus aureus (MRSA): The Role of Co-Adjuvants.

Sulfonamides are a conventional class of antibiotics that are well-suited to combat infections. However, their overuse leads to antimicrobial resistance. Porphyrins and analogs have demonstrated excellent photosensitizing properties and have been used as antimicrobial agents to photoinactivate microorganisms, including multiresistant Staphylococcus aureus (MRSA) strains. It is well recognized that the combination of different therapeutic agents might improve the biological outcome. In this present work, a novel meso-arylporphyrin and its Zn(II) complex functionalized with sulfonamide groups were synthesized and characterized and the antibacterial activity towards MRSA with and without the presence of the adjuvant KI was evaluated. For comparison, the studies were also extended to the corresponding sulfonated porphyrin TPP(SO3H)4. Photodynamic studies revealed that all porphyrin derivatives were effective in photoinactivating MRSA (>99.9% of reduction) at a concentration of 5.0 µM upon white light radiation with an irradiance of 25 mW cm-2 and a total light dose of 15 J cm-2. The combination of the porphyrin photosensitizers with the co-adjuvant KI during the photodynamic treatment proved to be very promising allowing a significant reduction in the treatment time and photosensitizer concentration by six times and at least five times, respectively. The combined effect observed for TPP(SO2NHEt)4 and ZnTPP(SO2NHEt)4 with KI seems to be due to the formation of reactive iodine radicals. In the photodynamic studies with TPP(SO3H)4 plus KI, the cooperative action was mainly due to the formation of free iodine (I2).

Screening of antioxidant capacity of Nepali medicinal plants with a novel singlet oxygen scavenging assay.

Pollutant exposure due to industrial development increases oxidative stress in human bodies. Dietary intake of antioxidant shows a protective effect against oxidative damage induced by oxidative stress. Therefore, the development of natural antioxidants is needed. In this study, the antioxidant activities of some Nepali medicinal plant extracts were measured. Using Rose bengal and 3,3',5,5'-tetramethylbenzidine, a novel assay was utilized to evaluate the singlet oxygen scavenging capacity, and showed a strong correlation with other antioxidant assays. Also, antioxidant capacities based on four assays including the singlet oxygen scavenging assay were highly correlated (≥ 0.858) with the total phenolic contents in the medicinal plant extracts. Among the selected extracts, Persicaria capitata, Elaphoglossum marginatum and Eurya acuminata showed the highest antioxidant capacities. Overall, this study presents a novel approach for evaluating singlet oxygen scavenging capacity, and performed a screening of antioxidant capacities of 54 Nepali herbal medicines. Supplementary Information: The online version contains supplementary material available at 10.1007/s10068-022-01175-z.

Excitation-Wavelength-Dependent Functionalities of Temporally Controlled Sensing and Generation of Singlet Oxygen by a Photoexcited State Engineered Rhodamine 6G-Anthracene Conjugate.

The present study provides design guidance for unique multipotent molecules that sense and generate singlet oxygen (1 O2 ). A rhodamine 6G-aminomethylanthracene-linked donor-acceptor molecule (RA) is designed and synthesized for demonstrating wavelength-dependent functionalities as follows; (i) RA acts as a conventional fluorogenic 1 O2 sensor molecule like the commercially available reagent, singlet oxygen sensor green (SOSG), when it absorbs ultraviolet (UV)-visible light and reacts with 1 O2 . (ii) RA acts as a temporally controlled 1 O2 sensing reagent under the longer wavelength (∼700 nm) photosensitization. RA enters an intermediate state after capturing 1 O2 and does not become strongly fluorescent until it is exposed to UV, blue, or green light. (iii) RA acts as an efficient photosensitizer to generate 1 O2 under green light illumination. The spin-orbit charge transfer mediated intersystem crossing (SOCT-ISC) process achieves this function, and RA shows a potential cancer-killing effect on pancreatic cancer cells. The wavelength-switchable functionalities in RA offer to promise molecular tools to apply 1 O2 in a spatiotemporal manner.

Assessment of the antioxidant activities of representative optical and geometric isomers of astaxanthin against singlet oxygen in solution by a spectroscopic approach.

Astaxanthin (AST) is a natural antioxidant and has been widely applied as a food supplement. While astaxanthin has many isomers, there are few studies comparing its physicochemical properties. In this work, we were concerned about their antioxidant activities against external oxidative stresses, and specifically, the singlet oxygen (1O2) quenching capacities of the representative optical and geometric isomers of astaxanthin were examined. Methylene blue (MB) was used as the photosensitizer to produce 1O2, and 1,3-diphenylisobenzofuran (DPBF) was used to probe 1O2. Our results showed that the 1O2 quenching capacities of the optical isomers, including 3S,3'S, 3R,3'S, and 3R,3'R all-trans-astaxanthin, are identical. In contrast, the 1O2 quenching capacity of cis-astaxanthin is higher than that of all-trans-astaxanthin. As such, this work provides an effective spectroscopic approach to assessing the antioxidant activities of various forms of astaxanthin against singlet oxygen, and demonstrates the remarkable difference among the geometric isomers.

Synthesis of a versatile mitochondria-targeting small molecule for cancer near-infrared fluorescent imaging and radio/photodynamic/photothermal synergistic therapies.

Although as a mainstay modal for cancer treatment, the clinical effect of radiotherapy (RT) does not yet meet the need of cancer patients. Developing tumour-preferential radiosensitizers or combining RT with other treatments has been acknowledged highly necessary to enhance the efficacy of RT. The present study reported a multifunctional bioactive small-molecule (designated as IR-83) simultaneously exhibiting tumour-preferential accumulation, near-infrared imaging and radio/photodynamic/photothermal therapeutic effects. IR-83 was designed and synthesized by introducing 2-nitroimidazole as a radiosensitizer into the framework of heptamethine cyanine dyes inherently with tumour-targeting and photosensitizing effects. As results, IR-83 preferentially accumulated in tumours, suppressed tumour growth and metastasis by integrating radio/photodynamic/photothermal multimodal therapies. Mechanism studies showed that IR-83 accumulated in cancer cell mitochondria, induced excessive reactive oxygen species (ROS), and generated high heat after laser irradiation. On one hand, these phenomena led to mitochondrial dysfunction and a sharp decline in oxidative phosphorylation to lessen tissue oxygen consumption. On the other hand, excessive ROS in mitochondria destroyed the balance of antioxidants and oxidative stress balance by down-regulating the intracellular antioxidant system, and subsequently sensitized ionizing radiation-generated irreversible DNA double-strand breaks. Therefore, this study presented a promising radiosensitizer and a new alternative strategy to enhance RT efficacy via mitochondria-targeting multimodal synergistic treatment.

Emerging Strategies in Enhancing Singlet Oxygen Generation of Nano-Photosensitizers Toward Advanced Phototherapy.

The great promise of photodynamic therapy (PDT) has thrusted the rapid progress of developing highly effective photosensitizers (PS) in killing cancerous cells and bacteria. To mitigate the intrinsic limitations of the classical molecular photosensitizers, researchers have been looking into designing new generation of nanomaterial-based photosensitizers (nano-photosensitizers) with better photostability and higher singlet oxygen generation (SOG) efficiency, and ways of enhancing the performance of existing photosensitizers. In this paper, we review the recent development of nano-photosensitizers and nanoplasmonic strategies to enhance the SOG efficiency for better PDT performance. Firstly, we explain the mechanism of reactive oxygen species generation by classical photosensitizers, followed by a brief discussion on the commercially available photosensitizers and their limitations in PDT. We then introduce three types of new generation nano-photosensitizers that can effectively produce singlet oxygen molecules under visible light illumination, i.e., aggregation-induced emission nanodots, metal nanoclusters (< 2 nm), and carbon dots. Different design approaches to synthesize these nano-photosensitizers were also discussed. To further enhance the SOG rate of nano-photosensitizers, plasmonic strategies on using different types of metal nanoparticles in both colloidal and planar metal-PS systems are reviewed. The key parameters that determine the metal-enhanced SOG (ME-SOG) efficiency and their underlined enhancement mechanism are discussed. Lastly, we highlight the future prospects of these nanoengineering strategies, and discuss how the future development in nanobiotechnology and theoretical simulation could accelerate the design of new photosensitizers and ME-SOG systems for highly effective image-guided photodynamic therapy.

Graphene Oxide-Gold Nanorods Nanocomposite-Porphyrin Conjugate as Promising Tool for Cancer Phototherapy Performance.

The cancer mortality rate has increased, and conventional cancer treatments are known for having many side effects. Therefore, it is imperative to find a new therapeutic agent or modify the existing therapeutic agents for better performance and efficiency. Herein, a synergetic phototherapeutic agent based on a combination of photothermal and photodynamic therapy is proposed. The phototherapeutic agent consists of water-soluble cationic porphyrin (5,10,15,20-tetrakis(N-methylpyridinium-3-yl)porphyrin, TMePyP), and gold nanorods (AuNRs) anchored on graphene-oxide (GO) sheet. The TMePyP was initially synthesized by Adler method, followed by methylation, while GO and AuNRs were synthesized using Hummer's and seed-mediated methods, respectively. The structural and optical properties of TMePyP were confirmed using UV-Vis, zeta analyzer, PL, FTIR and NMR. The formation of both GO and AuNRs was confirmed by UV-Vis-NIR, FTIR, TEM and zeta analyzer. TMePyP and AuNRs were anchored on GO to form GO@AuNRs-TMePyP nanocomposite. The as-synthesized nanocomposite was stable in RPMI and PBS medium, and, on irradiation, produced high heat than the bare AuNRs, with high photothermal efficiency. In addition, the nanocomposite produced higher singlet oxygen than TMePyP with high biocompatibility in the absence of light. These results indicated that the as-synthesized nanocomposite is a promising dual photodynamic and photothermal agent for cancer therapy.

Singlet Oxygen "Afterglow" Therapy with NIR-II Fluorescent Molecules.

Improving singlet oxygen (1 O2 ) lifespan by fractionated delivery in dark and hypoxic conditions is a better way to achieve enhanced phototherapeutic efficacy. Herein, three boron dipyrromethene (BODIPY) dyes are synthesized to demonstrate that anthracence-functionalized BODIPY, namely ABDPTPA is an efficient heavy-atom-free photosensitizer for the reversible capture and release of 1 O2 . The spin-orbit charge-transfer intersystem crossing of ABDPTPA promises a high 1 O2 quantum yield of 60% in dichloromethane. Under light irradiation, the anthracene group reacts with 1 O2 to produce endoperoxide. Interestingly, after termination of irradiation, the endoperoxide undergoes thermal cycloreversion to produce 1 O2 , and regenerates the anthracene module to achieve 1 O2 "afterglow," which results in a prolonged half lifetime of 1 O2 for 9.2 min. In vitro cytotoxicity assays indicate that ABDPTPA nanoparticles have a low half-maximal inhibitory concentration (IC50 ) of 3.6 µg mL-1 on U87MG cells. Further, the results of near-infrared-II fluorescence-imaging-guided phototherapy indicate that ABDPTPA nanoparticles can inhibit tumor proliferation even at a low dose (200 µg mL-1 , 100 µL) without any side effects. Therefore, the study provides a generalized 1 O2 "afterglow" strategy to enhance phototheranostics for complete tumor regression.

A Photosensitive Polymeric Carrier with a Renewable Singlet Oxygen Reservoir Regulated by Two NIR Beams for Enhanced Antitumor Phototherapy.

Photodynamic therapy (PDT), which utilizes photosensitizer to convert molecular oxygen into singlet oxygen (1 O2 ) upon laser irradiation to ablate tumors, will exacerbate the already oxygen shortage of most solid tumors and is thus self-limiting. Herein, a sophisticated photosensitive polymeric material (An-NP) that allows sustained 1 O2 generation and sufficient oxygen supply during the entire phototherapy is engineered by alternatively applying PDT and photothermal therapy (PTT) controlled by two NIR laser beams. In addition to a photosensitizer that generates 1 O2 , An-NP consists of two other key components: a molecularly designed anthracene derivative capable of trapping/releasing 1 O2 with superior reversibility and a dye J-aggregate with superb photothermal performance. Thus, in 655 nm laser-triggered PDT process, An-NP generates abundant 1 O2 with extra 1 O2 being trapped via the conversion into EPO-NP; while in the subsequent 785 nm laser-driven PTT process, the converted EPO-NP undergoes thermolysis to liberate the captured 1 O2 and regenerates An-NP. The intratumoral oxygen level can be replenished during the PTT cycle for the next round of PDT to generate 1 O2 . The working principle and phototherapy efficacy are preliminarily demonstrated in living cells and tumor-bearing mice, respectively.

N-doped biochar from sewage sludge for catalytic peroxydisulfate activation toward sulfadiazine: Efficiency, mechanism, and stability.

Sewage sludge-derived biochar (SBC) could remove organic contaminants in environment and reuse the sludge effectively. In this study, urea-doped SBC (NSBC) was prepared, characterized, and applied as heterogeneous catalytics to peroxydisulfate (PDS) activation. Sulfadiazine (SD), a widely used antibiotic, was used as a model pollutant to evaluate the efficiency and mechanism of this system. The degradation rate of SD increased to 100% after 4 h when 1 g/L of NSBC was added to the system with a SD concentration of 20 mg/L. In this study, it was confirmed that there were two important pathways in the degradation of SD by NSBC/PDS system: the free radical on the surface of NSBC and the nonradical (1O2) in the solution. The doping of N atoms makes neighboring C atoms positively charged, thereby making the direct transfer of electrons with S2O82- and the generation of 1O2 via nonradical pathway easy. In addition, the CO functional group formed during the pyrolysis of NSBC can produce 1O2 in a similar way. A total of 22 SD degradation products were identified, and 4 possible pathways were proposed. This study provide supplement for the degradation mechanism of organic compounds by carbon-based materials.

Photothermal Responsive Singlet Oxygen Nanocarriers for Hypoxic Cancer Cell Ablation.

Hypoxia in aggressively proliferating tumor cells has been demonstrated to restrict the efficiency of photodynamic therapy owing to its oxygen (O2 )-dependent generation of singlet oxygen (1 O2 ) from photosensitizers under light irradiation. To address this problem, we propose a small-molecule dye-based 1 O2 capturing agent, B1. B1 not only bears a near-infrared absorbing azo-boron dipyrromethene backbone, but also has 1,4-dimethylnaphthalene, which facilitates the capture of 1 O2 to form endoperoxide (B1-SO). B1-SO undergoes a reversible reaction via near-infrared photothermal stimulation, thus allowing 1 O2 release. Based on this mechanism, stable B1-SO containing micelles (B1-SO NPs) were prepared and employed as 1 O2 nanocarriers to ablate cancer cells in vitro. Taking advantage of this O2 -independent 1 O2 releasing ability, B1-SO NPs were demonstrated to have efficient cytotoxicity under near-infrared irradiation, especially in a hypoxic environment. The unique O2 -independent 1 O2 generation process of B1-SO NPs suggests they can be used as novel cancer phototherapy agents.

Changes in Light Energy Utilization in Photosystem II and Reactive Oxygen Species Generation in Potato Leaves by the Pinworm Tuta absoluta.

We evaluated photosystem II (PSII) functionality in potato plants (Solanum tuberosum L.) before and after a 15 min feeding by the leaf miner Tuta absoluta using chlorophyll a fluorescence imaging analysis combined with reactive oxygen species (ROS) detection. Fifteen minutes after feeding, we observed at the feeding zone and at the whole leaf a decrease in the effective quantum yield of photosystem II (PSII) photochemistry (ΦPSII). While at the feeding zone the quantum yield of regulated non-photochemical energy loss in PSII (ΦNPQ) did not change, at the whole leaf level there was a significant increase. As a result, at the feeding zone a significant increase in the quantum yield of non-regulated energy loss in PSII (ΦNO) occurred, but there was no change at the whole leaf level compared to that before feeding, indicating no change in singlet oxygen (1O2) formation. The decreased ΦPSII after feeding was due to a decreased fraction of open reaction centers (qp), since the efficiency of open PSII reaction centers to utilize the light energy (Fv'/Fm') did not differ before and after feeding. The decreased fraction of open reaction centers resulted in increased excess excitation energy (EXC) at the feeding zone and at the whole leaf level, while hydrogen peroxide (H2O2) production was detected only at the feeding zone. Although the whole leaf PSII efficiency decreased compared to that before feeding, the maximum efficiency of PSII photochemistry (Fv/Fm), and the efficiency of the water-splitting complex on the donor side of PSII (Fv/Fo), did not differ to that before feeding, thus they cannot be considered as sensitive parameters to monitor biotic stress effects. Chlorophyll fluorescence imaging analysis proved to be a good indicator to monitor even short-term impacts of insect herbivory on photosynthetic function, and among the studied parameters, the reduction status of the plastoquinone pool (qp) was the most sensitive and suitable indicator to probe photosynthetic function under biotic stress.

A review of advanced nanoformulations in phototherapy for cancer therapeutics.

Phototherapy has the potential to play a greater role in oncology. Phototherapy converts light energy into either chemical energy or thermal energy, which eventually destroys cancer cells after a series of biological reactions. With nanotechnology applications in cancer therapeutics, it has become possible to prepare smart drug carriers with multifunctional properties at the nanoscale level. These nanocarriers may be able to deliver the drug molecules to the target site more efficiently in the form of nanoparticles. Several intrinsic and extrinsic properties of these nanocarriers help target the tumor cells exclusively, and by utilizing these features, drug molecules can be delivered to the tumor cells specifically, which results in high tumor uptake and better therapeutic effects ultimately. Nanocarriers can also be designed to carry different drugs together to provide a platform for combination therapy like chemo-photodynamic therapy and chemo-photodynamic-photothermal therapy. In combination therapy, co-delivery of all different drugs is crucial to obtain their synergistic effects, and with the help of nanocarriers, it is possible to co-deliver these drugs by loading them together onto the nanocarriers.

Peroxidase-mimicking evodiamine/indocyanine green nanoliposomes for multimodal imaging-guided theranostics for oral squamous cell carcinoma.

Here, evodiamine (EVO) and the photosensitizer indocyanine green (ICG) were integrated into a liposomal nanoplatform for noninvasive diagnostic imaging and combinatorial therapy against oral squamous cell carcinoma (OSCC). EVO, as an active component extracted from traditional Chinese medicine, not only functioned as an antitumor chemotherapeutic agent but was also capable of 68Ga-chelation, thus working as a contrast agent for positron emission tomography/computed tomography (PET/CT) imaging. Moreover, EVO could exhibit peroxidase-like catalytic activity, converting endogenous tumor H2O2 into cytotoxic reactive oxygen species (ROS), enabling Chemo catalytic therapy beyond the well-known chemotherapy effect of EVO. As proven by in vitro and in vivo experiments, guided by optical imaging and PET/CT imaging, we show that the theragnostic liposomes have a significant inhibiting effect on in situ tongue tumor through photodynamic therapy combined with chemodynamic chemotherapy.