Red Light Irradiation Research Articles

Red light-induced inhibition of maize (Zea mays) mesocotyl elongation: evaluation of apoplastic metabolites.

Light is a crucial factor affecting plant growth and development. Besides providing the energy for photosynthesis, light serves as a sensory cue to control the adaptation of plants to environmental changes. We used the etiolated maize (Zea mays ) seedlings as a model system to study the red light-regulated growth. Exposure of the maize seedlings to red light resulted in growth inhibition of mesocotyls. We demonstrate for the first time (to the best our knowledge) that red light affected the patterns of apoplastic fluid (AF) metabolites extracted from the mesocotyl segments. By means of the untargeted gas chromatography-mass spectrometry (GC-MS)-based metabolomics approach, we identified 44 metabolites in the AF of maize mesocotyls and characterised the dynamics of their relative tissue abundances. The characteristic metabolite patterns of mesocotyls dominated with mono- and disaccharides, organic acids, amino acids, and other nitrogen-containing compounds. Upon red light irradiation, the contents of β -alanine, putrescine and trans -aconitate significantly increased (P -value<0.05). In contrast, there was a significant decrease in the total ascorbate content in the AF of maize mesocotyls. The regulatory role of apoplastic metabolites in the red light-induced inhibition of maize mesocotyl elongation is discussed.

Methylene blue sensitized photo Fenton-like reaction for rapid RAFT polymerization in aqueous solution

Rapid aqueous RAFT polymerization of acrylamides (DMA, NAM) with good oxygen tolerance initiated by ˙OH generated from methylene blue (MB) activated decomposition of H2O2under red light irradiation is presented.

Molecular engineering to red-shift the absorption band of AIE photosensitizers and improve their ROS generation ability.

Photodynamic therapy (PDT) with aggregation-induced emission photosensitizers (AIE-PSs) has attracted increasing attention for their enhanced fluorescence and reactive oxygen species (ROS) generation abilities upon aggregation. However, it is difficult for AIE-PSs to simultaneously achieve long-wavelength excitation (>600 nm) and high singlet oxygen quantum yield, which restricts their application in deep-tissue PDT. In this study, four novel AIE-PSs were developed by appropriate molecular engineering, and their absorption peaks shifted from 478 to 540 nm with a tail extending to 700 nm. Meanwhile, their emission peaks were also moved from 697 nm to 779 nm with a tail extending over 950 nm. Importantly, their singlet oxygen quantum yields successfully increased from 0.61 to 0.89. Moreover, TBQ, the best photosensitizer developed by us, has been successfully applied to image-guided PDT in BALB/C mice bearing 4T1 breast cancer under red light (605 ± 5 nm) irradiation, with IC50 less than 2.5 μM at a low light dose (10.8 J cm-2). The success of this molecular engineering indicates that increasing the number of acceptors is more effective at red-shifting the absorption band of AIE-PSs than increasing the number of donors, and extending the π-conjugation of acceptors will red-shift the absorption-emission band, increase the maximum molar extinction coefficient, and improve the ROS generation ability of AIE-PSs, thus providing a new strategy for the design of advanced AIE-PSs for deep-tissue PDT.

Unlocking the reactivity of diazo compounds in red light with the use of photochemical tools.

Structurally diversified diazoalkanes can be activated under red light irradiation relying on direct photolysis, photosensitization or photoredox catalysis.

Bifunctional chimera for ligand-directed photo-degradation of oncogenic microRNA.

Targeted inhibition of oncogenic microRNAs provides a promising anti-cancer approach. Here, we report a bifunctional chimera for ligand-directed regulation of target oncogenic precursor microRNA through photo-degradation. Chimeric TGP-210-Ppa with photosensitizer pyropheophorbide a (Ppa) linked with the ligand of the oncogenic precursor miR-210 was able to bind specifically to oncogenIc pre-miRNA and produce 1O2 under red light irradiation to degrade the target pre-miRNA. This bifunctional chimera-based modification of precursor microRNA serves as a unique method for target gene regulation since photo-irradiation was able to provide temporal-spatial resolution. We demonstrated that TGP-210-Ppa prevented the generation of functional miR-210 in breast cancer cells in a photocontrollable manner. This also successfully reversed the downstream oncogenic signaling pathway mediated by miR-210 to promote cancer cell death.

9-Cyano-10-telluriumpyronin Derivatives as Red-light-activatable Raman Probes.

Photoactivatable fluorescence probes can track the dynamics of specific cells or biomolecules with high spatiotemporal resolution, but their broad absorption and emission peaks limit the number of wavelength windows that can be employed simultaneously. In contrast, the narrower peak width of Raman signals offers more scope for simultaneous discrimination of multiple targets, and therefore a palette of photoactivatable Raman probes would enable more comprehensive investigation of biological phenomena. Herein we report 9-cyano-10-telluriumpyronin (9CN-TeP) derivatives as photoactivatable Raman probes whose stimulated Raman scattering (SRS) intensity is enhanced by photooxidation of the tellurium atom. Modification to increase the stability of the oxidation product led to a julolidine-like derivative, 9CN-diMeJTeP, which is photo-oxidized at the tellurium atom by red light irradiation to afford a sufficiently stable oxidation product with strong electronic pre-resonance, resulting in a bathochromic shift of the absorption spectrum and increased SRS intensity.

Alkaline Phosphatase-Controllable and Red Light-Activated RNA Modification Approach for Precise Tumor Suppression.

RNA interference (RNAi) has proved to be a promising modality for disease treatment. However, the promise of conventional RNA therapeutics for clinical application is severely impeded by low delivery efficiency and susceptibility of RNAs to serum RNases. Therefore, developing advanced RNAi technology is an increasing demand for achieving precise medicine. Herein, for the first time, we propose an alkaline phosphatase (ALP)-controllable and red light-activated RNA modification (ALARM) approach for anti-tumor therapeutic application. An ALP-responsive NIR fluorogenic probe f-RCP consisting of a tumor-targeting cyclic RGD peptide, an ALP-activated photosensitizer CyOP, and an 1O2-susceptible furan module for RNA modification was rationally designed and synthesized. Studies have demonstrated that f-RCP can specifically target to liver carcinoma HepG2 cells and spontaneously emit activated NIR/photoacoustic signals upon cleavage by the ALP enzyme, allowing for sensitive detection of ALP-positive tumors. More notably, we surprisingly found that the capability of f-RCP producing singlet oxygen (1O2) under red light irradiation could be simultaneously unlocked, which can ignite the covalent cyclization reaction between furan and nucleobases of intracellular RNA molecules, leading to significant mitochondrial damage and severe apoptosis of tumor cells, in consequence realizing efficient tumor suppression. Most importantly, the potential therapeutic mechanism was first explored on the transcriptomic level. This delicate ALARM strategy may open up new insights into cancer gene therapy.

Red Light-Mediated Photoredox Catalysis Triggers Nitric Oxide Release for Treatment of Cutibacterium Acne Induced Intervertebral Disc Degeneration.

Intervertebral disc degeneration (IVDD) has been known as a highly prevalent and disabling disease, which is one of the main causes of low back pain and disability. Unfortunately, there is no effective cure to treat this formidable disease, and surgical interventions are typically applied. Herein, we report that the local administration of nitric oxide (NO)-releasing micellar nanoparticles can efficiently treat IVDD associated with Modic changes in a rat model established by infection with Cutibacterium acnes (C. acnes). By covalent incorporation of palladium(II) meso-tetraphenyltetrabenzoporphyrin photocatalyst and coumarin-based NO donors into the core of micellar nanoparticles, we demonstrate that the activation of the UV-absorbing coumarin-based NO donors can be achieved under red light irradiation via photoredox catalysis, although it remains a great challenge to implement photoredox catalysis reactions in biological conditions due to the complex microenvironments. Notably, the local delivery of NO can not only efficiently eradicate C. acnes pathogens but also inhibit the inflammatory response and osteoclast differentiation in the intervertebral disc tissues, exerting antibacterial, anti-inflammatory, and antiosteoclastogenesis effects. This work provides a feasible means to efficiently treat IVDD by the local administration of NO signaling molecules without resorting to a surgical approach.

Red‐Light‐Driven CO2Photoreduction into CH4and CO Enabled by Narrow‐Gap Conjugated Microporous Polymers

Herein, selective CO2photoreduction into CH4and CO with red light using conjugated microporous polymers (CMPs) at room temperature is reported. By incorporating electron‐rich pyrene and electron‐deficient fluorenone derivatives in the polymer networks to constructing intramolecular donor–acceptor system, the resulting three polymers show very broad light absorption covered from 350 to 1000 nm, with narrow gaps of 1.61–1.74 eV. In the presence of triethanolamine and 1‐benzyl‐1,4‐dihydronicotinamide as the sacrificial agents, P3 exhibits the best visible‐light reduction activity, with CH4and CO evolution rates of 932.9 and 943.4 μmol h−1 g−1, respectively. Most significantly, under the irradiation of red light (&gt;600 nm), high evolution rates of CH4and CO for P3 are achieved at 293.7 and 282.6 μmol h−1 g−1, as well as nearly 100% reaction selectivity. The better performance of P3 than P1 and P2 can be ascribed to the high absorption toward CO2and improved charge transfer under light irradiation. This work opens great opportunities for designing broadband‐responsive CMPs for solar‐driven photocatalytic conversion.

Programmable Photocatalytic Activity of Multicomponent Covalent Organic Frameworks Used as Metallaphotocatalysts.

The multicomponent approach allows to incorporate several functionalities into a single covalent organic framework (COF) and consequently allows the construction of bifunctional materials for cooperative catalysis. The well-defined structure of such multicomponent COFs is furthermore ideally suited for structure-activity relationship studies. We report a series of multicomponent COFs that contain acridine- and 2,2'-bipyridine linkers connected through 1,3,5-benzenetrialdehyde derivatives. The acridine motif is responsible for broad light absorption, while the bipyridine unit enables complexation of nickel catalysts. These features enable the usage of the framework materials as catalysts for light-mediated carbon-heteroatom cross-couplings. Variation of the node units shows that the catalytic activity correlates to the keto-enamine tautomer isomerism. This allows switching between high charge-carrier mobility and persistent, localized charge-separated species depending on the nodes, a tool to tailor the materials for specific reactions. Moreover, nickel-loaded COFs are recyclable and catalyze cross-couplings even using red light irradiation.

Green Synthesis of Antibacterial Silver Nanocolloids with Agroindustrial Waste Extracts, Assisted by LED Light

Herein, the green synthesis of silver nanoparticles (AgNPs), assisted by LED light, using the aqueous extracts of agroindustrial waste products, such as avocado seeds (ASs), cocoa pod husks (CPHs), and orange peels (OPs), is presented. Surface plasmon resonance analysis showed faster and complete NP formation when irradiated with blue LED light. Green and red light irradiation showed non- and limited nanoparticle formation. TEM analyses confirmed the semispherical morphology of the synthesized AgNPs, with the exception of OP–AgNPs, which showed agglomeration during the light irradiation. For AS–AgNPs and CPH–AgNPs, the average particle diameter was about 15 nm. Interestingly, the CPH extract demonstrated faster nanoparticle formation as compared to the AS extract (100 min vs. 250 min irradiation time, respectively). FTIR spectroscopy assessed the involvement of diverse functional groups of the bioactive phytochemicals present in the plant extracts during nanoparticle photobiosynthesis. The antioxidant activity, as determined by ferric reducing antioxidant power (FRAP) assay, varied from 1323.72 µmol TE/mL in the AS aqueous extract to 836.50 µmol TE/mL in the CPH aqueous extract. The total polyphenol content was determined according to the Folin–Ciocalteu procedure; the AS aqueous extract exhibited a higher polyphenol content (1.54 mg GAE/g) than did the CPH aqueous extract (0.948 mg GAE/g). In vitro antibacterial assays revealed that the AS–AgNPs exhibited promising antibacterial properties against pathogenic bacteria (E. Coli), whereas the CPH–AgNPs showed antibacterial activity against S. aureus and E. coli. The green synthesis of AgNPs using AS, CPH, and OP aqueous extracts reported in this work is environmentally friendly and cost-effective, and it paves the way for future studies related to agroindustrial waste valorization for the production of advanced nanomaterials, such as antibacterial AgNPs, for potential biomedical, industrial, and environmental applications.

Magnetic Systems for Regenerative Medicine

Magnetic Systems for Regenerative Medicine

Amphiphilic Metallodrug Assemblies with Red-Light-Enhanced Cellular Internalization and Tumor Penetration for Anticancer Phototherapy.

Metallodrugs are widely used in cancer treatment. The modification of metallodrugs with polyethylene glycol (PEGylation) prolongs blood circulation and improves drug accumulation in tumors; it represents a general strategy for drug delivery. However, PEGylation hinders cellular internalization and tumor penetration, which reduce therapeutic efficacy. Herein, the red-light-enhanced cellular internalization and tumor penetration of a PEGylated anticancer agent, PEGylated Ru complex (Ru-PEG), are reported upon. Ru-PEG contains a red-light-cleavable PEG ligand, anticancer Ru complex moiety, and fluorescent pyrene group for imaging and self-assembly. Ru-PEG self-assembles into vesicles that circulate in the bloodstream and accumulate in the tumors. Red-light irradiation induces dePEGylation and changes the Ru-PEG vesicles to large compound micelles with smaller diameters and higher zeta potentials, which enhance tumor penetration and cellular internalization. Red-light irradiation also generates intracellular 1 O2 , which induces the death of cancer cells. This work presents a new strategy to enhance the cellular internalization and tumor penetration of anticancer agents for efficient phototherapy.

A Tumor‐Specific Platform of Peroxynitrite Triggering Ferroptosis of Cancer Cells

AbstractPeroxynitrite (ONOO−) is a potent oxidant and nucleophile participating in a variety of pathophysiological processes as well as playing a major role in cancer therapy. However, the intracellular environment of solid tumors severely restricts the production of ONOO−, which leads to an unsatisfactory anticancer effect. Here, a tumor‐specific platform for ONOO− generation, prepared by linking a type I photosensitizer with a GSH‐responsive NO donor, is constructed to overcome the tumor hypoxic microenvironment and enhance treatment efficiency (NBS‐2S‐NO). Responding to the overexpressed glutathione (GSH) within tumors, NBS‐2S‐NO can selectively induce ONOO− generation after a cascade including red light irradiation causing superoxide radical (O2•−) production, GSH‐triggered NO release, and fast reaction between O2•− and NO. The generated ONOO− can cause oxidative damage to tumor cells, induce lipid peroxidation (LPO) during the cell death process and finally cause ferroptosis. Both in vitro and in vivo outcomes demonstrate the notable anticancer ferroptosis efficacy of this platform, suggesting not only an effective ferroptosis strategy for the design of new photosensitizers but also a worthy of reference for antioxidant regulation to enhance the oxidative damage during the tumor treatment process.

5-Aminolevulinic Acid and Red Led in Endodontics: A Narrative Review and Case Report.

The present study aims to discuss the main factors involving the use of 5-aminolevulinic acid together with red LED light and its application in endodontic treatment through a narrative review and a case report. Persistence of microorganisms remaining on chemical-mechanical preparation or intracanal dressing is reported as the leading cause of failure in endodontics. Photodynamic therapy has become a promising antimicrobial strategy as an aid to endodontic treatment. Being easy and quick to apply, it can be used both in a single session and in several sessions, as well as not allowing forms of microbial resistance. 5-aminolevulinic acid in combination with red LED light has recently been studied in many branches of medicine, with good results against numerous types of bacteria including Enterococuss faecalis. The case report showed how bacterial count of CFU decreased by half (210 CFU/mL), after 45 min of irrigation with a gel containing 5% of 5-aminolevulinic acid compared to the sample before irrigation (420 CFU/mL). The subsequent irradiation of red LED light for 7 min, the bacterial count was equal to 0. Thus, it is concluded that the use of 5-aminolevulinic acid together with red LED light is effective in endodontic treatment.

Tetrazolyl Porphyrin-Based Hydrogen-Bonded Organic Frameworks: Active Sites-Mediated Host-Guest Synergy for Advanced Antimicrobial Applications.

Hydrogen-bonded organic frameworks (HOFs) with multiple functions and permanent pores have received widespread attention due to their potential applications in gas adsorption/separation, drug delivery, photocatalysis, proton conduction, and other fields. Herein, we constructed a three-dimensional (3D) HOF with 1D square channels by utilizing a dual-functional tetrazolyl porphyrin ligand bearing an active center of the porphyrin core and open sites of nitrogen atoms through π-π stacking and hydrogen-bonding interaction self-assembly. The structure exhibits both solvent resistance and thermal stability, and especially, maintains these after being transformed into nanoparticles. Meanwhile, the active sites exposed on the inner wall of the pores can interact well with the photoactive cationic dye molecules to form an effective host-guest (H-G) system, which can realize boosted photosensitized singlet oxygen (1O2) production under red light irradiation and synergistic sterilization toward Staphylococcus aureus (S. aureus) with an inhibition ratio as high as 99.9%. This work provides a valuable design concept for HOF-related systems in pursuit of promoted photoactivity.

Effect of Amino Acids on Folates Accumulation in Wheat Seedlings during Germination under Red Light Radiation.

Deficiency of folates can cause various health problems, and germination is a potential way to enrich folates in grain-based food materials. In the present study, the effects of six amino acids (phenylalanine, tyrosine, tryptophan, glutamate, γ-aminobutyric acid, and p-aminobenzoic acid) on folate accumulation during wheat germination under red light radiation were investigated, and an optimized combination of amino acids for promoting folate enrichment was established. The results showed that applying phenylalanine, tyrosine, tryptophan, glutamate, or p-aminobenzoic acid to wheat seedlings during germination can significantly increase the content of total folates through activating the synthesis of the precursors for folate synthesis (pterin and p-aminobenzoic acid) or condensation of these two moieties. Meanwhile, up-regulation of corresponding genes was observed by measuring their expressions to investigate the mechanism for promoting the accumulation of folates. The highest content of folates (ca. 417 µg/100 g DW) was observed when the germinated wheat was cultured with a mixture of 1.5 mM phenylalanine, 0.5 mM tyrosine, 0.5 mM tryptophan, 0.75 mM p-aminobenzoic acid, and 0.5 mM glutamic acid, which was 50% higher than the control seedlings. This study established a promising and practical approach to enhance the accumulation of folates in wheat seedlings.

Effect of Light Irradiation on Sugar, Phenolics, and GABA Metabolism on Postharvest Grape (Vitis vinifera L.) During Storage

The impact of red and blue light-emitting diodes (LEDs) irradiation on the sugar metabolism and γ-aminobutyric acid in postharvest table grapes stored at 4 °C for 21 days after harvest were explored. Grape clusters were exposed to red and blue light irradiation at the same intensity (500 lx). The findings revealed that red and blue light treatments enhanced total soluble solids (TSS) and total acidity (TA) content. Furthermore, red-light irradiation retained higher phenolic compound during storage than blue light and control. Red-light radiation sustained higher levels of phenolic biosynthesis-related enzymes, including phenylalanine ammonia-lyase (PAL), tyrosine ammonia-lyase (TAL), cinnamate 4-hydroxylase (C4H), and p-coumarate ligase (4CL), than blue light irradiation and control. The results showed that red light increased glucose, fructose, and sucrose levels, which were 32.19, 33.18, and 2.95 mg g−1, compared with those in blue light and control at the end of storage and enhancing the sucrose synthase synthesis (SS-synthesis) and acid invertase (AI), while blue light enhanced sucrose synthase cleavage (SS-cleavage). In addition, red light irradiation increased glutamic acid decarboxylase (GAD) activity while red and blue light irradiation inhibited γ-aminobutyric acid transaminase (GABA-T) activity by 22.14 and 20.71 U g−1 at 21 days of storage, compared to control, leading to γ-aminobutyric acid (GABA) accumulation. These findings suggest that red and blue light will help in maintaining the quality of grape during postharvest storage.

Organogold(III) Complexes Display Conditional Photoactivities: Evolving From Photodynamic into Photoactivated Chemotherapy in Response to O2 Consumption for Robust Cancer Therapy.

Photodynamic therapy (PDT) is a spatiotemporally controllable, powerful approach in combating cancers but suffers from low activity under hypoxia, whereas photoactivated chemotherapy (PACT) operates in an O2 -independent manner but compromises the ability to harness O2 for potent photosensitization. Herein we report that cyclometalated gold(III)-alkyne complexes display a PDT-to-PACT evolving photoactivity for efficient cancer treatment. On the one hand, the gold(III) complexes can act as dual photosensitizers and substrates, leading to conditional PDT activity in oxygenated condition that progresses to highly efficient PACT (ϕ up to 0.63) when O2 is depleted in solution and under cellular environment. On the other hand, the conditional PDT-to-PACT reactivity can be triggered by external photosensitizers in a similar manner in vitro and in vivo, giving additional tumor-selectivity and/or deep tissue penetration by red-light irradiation that leads to robust anticancer efficacy.

Red-light controlled supramolecular co-assembly transformations of stiff stilbene and donor acceptor stenhouse adduct amphiphiles

Amphiphiles are of great interest in the search of biomimicking supramolecular assembly for their assembling into complex and hierarchical structures in aqueous media across multiple length-scale. Incorporations of photoswitching units into amphiphiles provide a means to control the morphology of the resultant assembled structures by light irradiation, which is non-invasive and generally biocompatible. The use of light to induce morphological changes offers several extra merits, including selective excitation of photoswitches by different wavelengths, high temporal- and spatial-resolution. Macroscopic soft materials assembled from donor-acceptor Stenhouse adducts (DASA) amphiphiles (DA) in aqueous media are generally suffered from absorption peak broadening due to aggregation and requires strong white-light irradiation to induce a morphological change. Herein, we provide a new strategy for the restoration of red-light sensitivity of DA in aqueous medium, which requires a co-assembly system of DA with a six-membered fused ring stiff stilbene amphiphile (6SA). This 6SA:DA co-assembly forms supramolecular structures in both microscopic and macroscopic length-scale. Morphological changes of these supramolecular structures can be fine adjusted with red-light irradiation. The structural design, supramolecular assemblies and co-assemblies, and macroscopic scaffolds of photoresponsive SA and DA could enable potential visible-light controlled soft functional materials with improved biocompatibility and photosensitivity.