Blue LED Irradiation Research Articles

Photochemically Driven Palladium- Phosphinoacridine Catalysis: A Carboxylative Approach for Arylcarbamate Synthesis.

In this study, we demonstrate that phosphinoacridines are efficient bidentate ligands for palladium-catalyzed carboxylative C-N coupling reactions under blue LED irradiation. This method facilitates the direct synthesis of arylcarbamates using a range of non-activated aryl halides, such as iodides and bromides, with various amines under atmospheric pressure of CO2. The optimized conditions exhibit high tolerance to sensitive functional groups, resulting in very good to excellent yields of the desired products. This approach expands the scope of palladium-catalyzed carboxylation reactions and offers an environmentally friendly route to arylcarbamates.

Synthesis of 2‐Aryl‐2H‐1,2,3‐triazoles via P(OMe)3‐Promoted Intramolecular Transannulation of 4‐Diazenylisoxazol‐5(4H)‐ones

AbstractTrimethyl phosphite promotes the synthesis of 2,4,5‐trisubstituted 2H‐1,2,3‐triazoles. The protocol developed affords a two‐step method towards triazoles from available reagents. 3,4‐Disubstituted isoxazolones are initially coupled with diazonium tetrafluoroborates. The subsequent reaction is triggered by a single electron transfer from the phosphite to the diazenylisoxazolone under heating or blue LED irradiation at room temperature. The radical anion cascade proceeds via a ring opening/decarboxylation/cyclization sequence. The synthesized triazoles show promising fluorescence in the region from 340 nm to 450 nm with a quantum yield up to 81.6%. The emission energy depends slightly on the substituent nature at the triazole carbon atoms. If an electron‐donor group is introduced into the N2 substituent of the triazole ring, it results in a bathochromic shift of the luminescence energy.

Photolytic ortho-Selective Amino Pyridylation of Aryl Isocyanates with N-Amino Pyridinium Ylides for the Synthesis of N-Arylsulfonyl Ureas.

Herein, we report an expedient synthesis of aryl sulfonyl ureas 4 and 5 from N-amino pyridinium ylides and aryl isocyanates. N-Aminopyridinium ylides 3 are synthesized via blue light-emitting diode irradiation of pyridine/isoquinoline and appropriate iminoiodinanes. The strategy involved a hitherto unknown carboamination of imine moieties (of aryl isocyanates) via a three-component reaction of pyridine derivatives/isoquinoline 1, N-aryl sulfonyl iminoiodinanes 2, and numerous aryl isocyanates at room temperature in 2-methyl tetrahydrofuran to afford the target compounds in moderate to excellent yields. N-Arylpyridinium ylides 3 (as intermediates) undergo a [3+2] cycloaddition with the aryl isocyanates followed by the aromatization of the pyridine/isoquinoline moiety to afford compounds 4. On the basis of the substitution pattern among the reactants, in some cases pyridine extrusion occurs during the reaction to afford depyridinylated aryl sulfonyl ureas 5. In general, isocyanates are used as dipolarophiles in [3+2] cycloaddition reactions. However, regioselective amino pyridylation of these species is a first. Control experiments and density functional theory calculations elucidate the reaction mechanism. The batch process of the protocol could be seamlessly transferred to the photoflow synthesis.

Benzodiazole-Based Covalent Organic Frameworks for Enhanced Photocatalytic Dehalogenation of Phenacyl Bromide Derivatives.

Covalent organic frameworks (COFs) have garnered significant interest within the scientific community due to their distinctive ability to act as organic semiconductors responsive to visible light. This unique attribute makes them up-and-coming candidates for facilitating photocatalytic organic reactions. Herein, two donor-acceptor COFs, TPE-BSD-COF and TPE-BD-COF, have been designed and synthesized by incorporating electron-rich tetraphenylethylene and electron-deficient benzoselenadiazole and benzothiadiazole units into the framework through a Schiff-base polycondensation reaction. Both COFs exhibit exceptional crystallinity and enduring porosity. TPE-BSD-COF and TPE-BD-COF exhibit broad light absorption capabilities, a narrow optical band gap, and low electrochemical impedance spectrum (EIS) levels, indicating that the two COFs are effective heterogeneous photocatalysts for the reductive dehalogenation of phenacyl bromide derivatives under blue LED irradiation. A high photocatalytic yield of 98% and 95% was achieved by TPE-BSD-COF and TPE-BD-COF catalysts, respectively, within only one hour.

Formate Salt as a Bifunctional Reagent for Hydroxylation and Carbonylation Reactions Under Photochemically Driven Nickel Catalysis.

In this study, we disclose for the first time that formate salt can be used as a bifunctional reagent for the synthesis of phenol derivatives and as a CO source for carbonylative cross-coupling processes using the COware gas reactor under activation free conditions. Key to this success is the in-situ synthesis of aryl formate via an unprecedented nickel/organophotocatalyst system under blue LED irradiation. This developed system demonstrated high applicability to various aryl iodide substrates for synthesizing phenol derivatives. Moreover, the generated CO could be utilized in a range of carbonylative C-heteroatom and C-C processes. Notably, commercially available H13COONa salt can serve as a bifunctional reagent for both synthesizing phenols and generating 13CO.

Induction of Endoplasmic Reticulum Stress and Aryl Hydrocarbon Receptor Pathway Expression by Blue LED Irradiation in Oral Squamous Cell Carcinoma.

Photobiomodulation therapy, as an emerging treatment modality, has been widely used in dentistry. However, reports on blue light therapy for oral cancer are scarce. This study investigated the effects of 457 and 475 nm LED irradiation on SCC-25 cells and explored the potential mechanisms underlying the impact of blue light. Both wavelengths were found to inhibit cell viability, induce oxidative stress, and cause cell cycle arrest without leading to cell death. Notably, the inhibitory effect of 457 nm blue light on cell proliferation was more sustained. Transcriptome sequencing was performed to explore the underlying mechanisms, revealing that blue light induced endoplasmic reticulum stress in SCC-25 cells, with 457 nm light showing a more pronounced effect. Moreover, 457 nm blue light upregulated the expression of the aryl hydrocarbon receptor pathway, indicating potential therapeutic prospects for the combined use of blue light and pharmacological agents.

Photosensitized Reductive Elimination of Gold(III) to Enable Esterification of Aryl Iodides with Carboxylic Acids.

Compared to the well-established transition metal-catalyzed cross-coupling reactions, Au(I)/Au(III)-catalyzed cross-coupling reactions have lagged behind. Despite some advancements, achieving gold-catalyzed C-O coupling with carboxylic acids via an Au(III) carboxylate intermediate remains challenging due to the thermal unfavorability of the critical reductive elimination step. Here, we present the first photosensitized reductive elimination of gold(III) to enable esterification of aryl iodides with carboxylic acids. In the presence of a (P, N)-gold(I) catalyst and a photosensitizer benzophenone under blue LED irradiation, esterification derivatives were obtained from aryl iodides with both aryl and alkyl (1°, 2°, 3°) carboxylic acids. Mechanistic and modeling studies support that energy transfer (EnT) from a photosensitizer produces an excited-state gold(III) complex that couples aryl iodides with carboxylic acids. This photoinduced energy-transfer strategy has been applied in several other photosensitized gold catalysis reactions, indicating its potential for further applications.

Oxidative Substitution of Organocopper(II) by a Carbon-Centered Radical.

Copper-catalyzed coupling reactions of alkyl halides are believed to prominently involve copper(II) species and alkyl radicals as pivotal intermediates, with their exact interaction mechanism being the subject of considerable debate. In this study, a visible light-responsive fluoroalkylcopper(III) complex, [(terpy)Cu(CF3)2(CH2CO2tBu)] Trans-1, was designed to explore the mechanism. Upon exposure to blue LED irradiation, Trans-1 undergoes copper-carbon bond homolysis, generating Cu(II) species and carbon-centered radicals, where the carbon-centered radical then recombines with the Cu(II) intermediate, resulting in the formation of Cis-1, the Cis isomer of Trans-1. Beyond this, a well-defined fluoroalkylcopper(II) intermediate ligated with a sterically hindered ligand was isolated and underwent full characterization and electronic structure studies. The collective experimental, computational, and spectroscopic findings in this work strongly suggest that organocopper(II) engages with carbon-centered radicals via an "oxidative substitution" mechanism, which is likely the operational pathway for copper-catalyzed C-H bond trifluoromethylation reactions.

Nickel-Catalyzed C(sp2)–S Cross-Coupling with mpg-CN under Blue LED Irradiation

Nickel-Catalyzed C(sp2)–S Cross-Coupling with mpg-CN under Blue LED Irradiation

Reductive Cyclopropanation through Bismuth Photocatalysis.

We present here a catalytic method based on a low-valent Bi complex capable of cyclopropanation of double bonds under blue LED irradiation. The catalysis features various unusual Bi-based organometallic steps, namely, (1) two-electron inner sphere oxidative addition of Bi(I) complex to CH2I2, (2) light-induced homolysis of the Bi(III)-CH2I bond, (3) subsequent iodine abstraction-ring-closing, and (4) reduction of Bi(III) to Bi(I) with an external reducing agent to close the cycle. Stoichiometric organometallic experiments support the proposed mechanism. This protocol represents a unique example of a reductive photocatalytic process based on low-valent bismuth radical catalysis.

Novel Halogenated Curcumin-Mediated Photodynamic Inactivation for the Preservation of Small Yellow Croaker (Larimichthys polyactis).

A novel class of halogenated curcumin, X-Cur (X = F, Cl, or Br), was synthesized, and its photosensitivity was evaluated. The results showed that Br-Cur with the highest singlet oxygen (1O2) generation capacity exhibited a better photodynamic inactivation (PDI) effect on the small yellow croaker (Larimichthys polyactis) than curcumin. This was attributed to the heavy atom effect of Br, which resulted in Br-Cur having the smallest singlet-triplet energy difference ΔEst(S1-T3) (0.140 eV) and the largest spin-orbit coupling value (0.642262 cm-1). When L. polyactis was treated with 0.025 wt % Br-Cur and exposed to blue LED irradiation (450 nm, 20 mW/cm2) for 20 min, the increase in the total volatile basic nitrogen content (28.23 ± 2.38 mg/100 g on day 6), pH, and total viable count (6.13 ± 0.06 log CFU/g on day 6) could be effectively controlled. Accordingly, Br-Cur is a promising photosensitizer for PDI preservation.

Efficient Oxidation with Singlet Oxygen from 5,10,15,20-Tetraphenylporphyrin under Blue LED Irradiation and Air Atmosphere: Simplified Preparation of Key Building Blocks for Natural Product Synthesis

AbstractA method for preparing important building blocks for natural product synthesis has been developed using singlet oxygen generated from 5,10,15,20-tetraphenylporphyrin under blue LED irradiation. Using this method, the allylic oxidation of dicyclopentadiene proceeded smoothly in air atmosphere with an 87% yield. The conditions, using TPP under blue LED irradiation, were expanded to include the oxidation of cyclopentadiene. The approach offers a simple and cost-effective method of synthesizing important building blocks for natural product synthesis.

Photoinduced Asymmetric Formal Siloxycarbene Insertion into sp3 C-H Bonds Enabled by Chiral Phosphoric Acid.

We disclosed herein an enantioselective formal siloxycarbene insertion reaction enabled by chiral phosphoric acid and blue LED irradiation. This is the first time the asymmetric siloxycarbene insertion into an sp3 C-H bond under transition-metal free conditions has been realized. The reaction features good isolated yields (up to 92%), high enantioselectivity (up to 99:1 er), mild reaction conditions, and good compatibility. Moreover, this method also provides a green and efficient method to construct a chiral quaternary carbon center.

Development of an Easy-To-Handle Redox Active Group for Alcohols: Catalytic Transformation of Tertiary Alcohols to Nitriles.

The generation of radical intermediates via SET-mediated deoxygenation of activated alcohol derivatives is desirable, as alcohols can be utilized in various radical-mediated reactions. Herein, we introduce α-N-phthalimido-oxy isobutyrate (NPIB) as a novel activating group for alcohols. Essentially, it is a more chemically robust alternative to Overman's N-phthalimidoyl oxalate group. The utility of the NPIB group is showcased in the conversion of tertiary alcohols to nitriles under Ir/Cu dual catalysts and in the presence of TMSCN upon blue LED irradiation. With our newly developed NPIB handle, the reactivities of N-hydroxyphthalimide esters derived from carboxylic acids would be achievable with naturally and commercially more abundant alcohol substrates.

NIR-II emissive anionic copper nanoclusters with intrinsic photoredox activity in single-electron transfer

Ultrasmall copper nanoclusters have recently emerged as promising photocatalysts for organic synthesis, owing to their exceptional light absorption ability and large surface areas for efficient interactions with substrates. Despite significant advances in cluster-based visible-light photocatalysis, the types of organic transformations that copper nanoclusters can catalyze remain limited to date. Herein, we report a structurally well-defined anionic Cu40 nanocluster that emits in the second near-infrared region (NIR-II, 1000−1700 nm) after photoexcitation and can conduct single-electron transfer with fluoroalkyl iodides without the need for external ligand activation. This photoredox-active copper nanocluster efficiently catalyzes the three-component radical couplings of alkenes, fluoroalkyl iodides, and trimethylsilyl cyanide under blue-LED irradiation at room temperature. A variety of fluorine-containing electrophiles and a cyanide nucleophile can be added onto an array of alkenes, including styrenes and aliphatic olefins. Our current work demonstrates the viability of using readily accessible metal nanoclusters to establish photocatalytic systems with a high degree of practicality and reaction complexity.

Blue light irradiation inhibits the M2 polarization of the cancer-associated macrophages in colon cancer

Recent studies have shown that blue light-emitting diode (LED) light has anti-tumor effects, suggesting the possibility of using visible light in cancer therapy. However, the effects of blue light irradiation on cells in the tumor microenvironment, including tumor-associated macrophages (TAMs), are unknown. Here, THP-1 cells were cultured in the conditioned medium (CM) of HCT-116 cells to prepare TAMs. TAMs were divided into LED-irradiated and control groups. Then, the effects of blue LED irradiation on TAM activation were examined. Expression levels of M2 macrophage markers CD163 and CD206 expression were significantly decreased in LED-irradiated TAMs compared with the control group. While control TAM-CM could induce HCT-116 cell migration, these effects were not observed in cells cultured in TAM-CM with LED irradiation. Vascular endothelial growth factor (VEGF) secretion was significantly suppressed in LED-exposed TAMs. PD-L1 expression was upregulated in HCT-116 cells cultured with TAM-CM but attenuated in cells cultured with LED-irradiated TAM-CM. In an in vivo model, protein expression levels of F4/80 and CD163, which are TAM markers, were reduced in the LED-exposed group. These results indicate that blue LED light may have an inhibitory effect on TAMs, as well as anti-tumor effects on colon cancer cells.

Photocatalytic (V2O5/TiO2) Blue LED Mediated Selective Oxidation of Alcohols, Styrene to Aldehydes, and Oxygenation of Alkyl‐Benzene to Ketones

AbstractThe development of a low‐cost, reusable, and sustainable approach is a difficult and emerging demand in the coming arena. Here, we demonstrate the selective oxidation of primary alcohol, styrene to aldehyde, and alkyl benzene to appropriate ketone, under Blue LED irradiation. The developed approaches employ reusable catalysts (V2O5/TIO2) and green solvents (ACN, H2O) at room temperature. The substrate scope is widely investigated for various compounds of different functionalities. Organic transformations are supported by reaction mechanistic studies. The gram scale reaction and catalytic recyclability were also carried out to maximize the protocol's synthetic utility.

Visible-Light-Induced Radical Sulfonylative-Cyclization Cascade of 1,6-Enynol Derivatives with Sulfinic Acids: A Sustainable Approach for the Synthesis of 2,3-Disubstituted Benzoheteroles.

Benzoheteroles are promising structural scaffolds in the realm of medicinal chemistry, but sustainable synthesis of 2,3-difunctionalized benzoheterole derivatives is still in high demand. Indeed, we have conceptually rationalized the intrinsic reactivity of propargylic-enyne systems for the flexible construction of 2,3-disubstituted benzoheteroles through radical sulfonylative-cyclization cascade under organophotoredox catalysis. We hereby report an efficient visible-light-induced sulfonyl radical-triggered cyclization of 1,6-enynols with sulfinic acids under the dual catalytic influence of 4CzIPN and NiBr2⋅DME, which led to the formation of 2,3-disubstituted benzoheteroles in good to high yields. Additionally, the Rose Bengal (RB)-catalyzed radical sulfonylative-cycloannulation of acetyl-derived 1,6-enynols with sulfinic acids under blue LED irradiation allowed to access 3-(E-styryl)-derived benzofurans and benzothiophenes in moderate to good yields. The scope and limitations of the present strategies were successfully established using different classes of 1,6-enynols and sulfinic acids bearing various sensitive functional groups, yielding the desired products in a highly stereoselective fashion. Plausible mechanistic pathways were also proposed based on the current experimental and control experiments.

Single-crystal oxygen-rich bismuth oxybromide nanosheets with highly exposed defective {10–1} facets for the selective oxidation of toluene under blue LED irradiation

Reactive radicals are crucial for activating inert and low-polarity C(sp3)-H bonds for the fabrication of high value-added products. Herein, novel single-crystal oxygen-rich bismuth oxybromide nanosheets (Bi4O5Br2 SCNs) with more than 85 % {10–1} facets exposure and oxygen defects were synthesized via a facile solvothermal route. The Bi4O5Br2 SCNs demonstrated excellent photocatalytic performance in the selective oxidation of toluene under blue light. The yield of benzaldehyde was 1876.66 μmol g−1 h−1, with a selectivity of approximately 90 %. Compared to that of polycrystalline Bi4O5Br2 nanosheets (Bi4O5Br2 PCNs), the activity of Bi4O5Br2 SCNs exhibit a 21-fold increase. Experimental studies and density functional theory (DFT) calculations have demonstrated that the defect Bi4O5Br2 (10–1) facets exhibits exceptional adsorption properties for O2 molecules. In addition, the single-crystal structure in the presence of surface defects significantly increases the separation and transport of photogenerated carriers, resulting in the effective activation of adsorbed O2 into superoxide radicals (•O2–). Subsequently, the positively charged phenylmethyl H is readily linked to the negatively charged superoxide radical anion, thereby activating the CH bond. This study offers a fresh perspective and valuable insights into the development of efficient molecular oxygen-activated photocatalysts and their application in the selective catalytic conversion of aromatic C(sp3)-H bonds.

Continuous microalgal culture module and method of culturing microalgae containing macular pigment

This study established and investigated continuous macular pigment (MP) production with a lutein (L):zeaxanthin (Z) ratio of 4–5:1 by an MP-rich Chlorella sp. CN6 mutant strain in a continuous microalgal culture module. Chlorella sp. CN6 was cultured in a four-stage module for 10 days. The microalgal culture volume increased to 200 L in the first stage (6 days). Biomass productivity increased to 0.931 g/L/day with continuous indoor white light irradiation during the second stage (3 days). MP content effectively increased to 8.29 mg/g upon continuous, indoor white light and blue light-emitting diode irradiation in the third stage (1 day), and the microalgal biomass and MP concentrations were 8.88 g/L and 73.6 mg/L in the fourth stage, respectively. Using a two-step MP extraction process, 80 % of the MP was recovered with a high purity of 93 %, and its L:Z ratio was 4–5:1.