Meso‐β fused porphyrins with tunable optoelectronic properties are attractive candidates for applications in light‐harvesting, sensing, and catalysis, yet their synthesis often requires harsh conditions or tedious synthetic routes. Herein, a mild, operationally simple, and Cu(OTf) 2 ‐catalyzed protocol is reported to access meso‐N ‐aryliminonaphtho‐fused and N‐ arylcarboxamide porphyrins from readily available β ‐cyanoporphyrins and diaryliodonium salts. Reaction selectivity is controlled by the water content present in the reaction mixture, affording either fused imines or carboxamides in high yields. The protocol tolerates different symmetrical diaryliodonium salts and enables the preparation of free‐base, Zn (II), and Cu (II) porphyrin derivatives, all fully characterized by NMR, UV–visible spectroscopy, high resolution mass spectrometry, electrochemistry, and single crystal X‐ray diffraction. The π‐extended systems exhibit distinct bathochromic shifts (≈42 nm in Soret and ≈80–90 nm in Q‐bands) and narrowed highest molecular orbital‐lowest unoccupied molecular orbital (HOMO‐LUMO) gaps up to 1.54 eV. Electrochemical studies reveal that fused porphyrins exhibited anodically shifted reduction potentials, while Density functional theory calculations attribute the gap reduction to LUMO stabilization and HOMO destabilization induced by fusion. Overall, this strategy provides rapid access to structurally diverse π‐extended porphyrins with tailored photophysical and redox properties.

A diverse range of N-heterocycle-fused porphyrins were efficiently prepared via unprecedented cascade annulation of readily accessible benzotriazolyl-appended porphyrins in diglyme. The present protocol provides metal-free and direct access to structurally diverse N-heterocycle-fused (meso-β, β-β) and carbazolyl-appended porphyrinoids in good yields. In addition, the prepared N-heterocycle-fused porphyrinoids displayed drastic changes in absorption spectra (red-shifted), higher singlet oxygen generation ability (ΦΔ ≈ 0.73), and narrow band gap (∼1.84 eV) and responded to protonation and deprotonation processes to produce a switchable pH-sensitive near-IR chromophore.

A series of twelve (E)-α-cyano indolylenones 6a-l were synthesized exclusively in good to excellent yields (79-93%) using a green protocol, from 2-cyano acetylindoles 4 and substituted aldehydes 5 using l-proline as the catalyst. The use of readily available precursors, easy product isolation, benign reaction conditions and wider substrate scope are the advantages of the developed protocol. X-Ray analysis unambiguously confirmed that, 6e exists in E-conformation. DFT calculations also support the exclusive formation E-isomer of 6e over the Z-isomer by an energy difference of 4.68 eV. Six compounds showed selective cytotoxicity (IC50 = 0.048–1.1 μM), against prostate and breast cancer cell lines, i.e., MDA-MB-231, PC3, C4-2, and 22Rv1. Among them, 6b and 6g showed selective cytotoxic activity against the prostate cancer (IC50 = 48 nM and 0.26 μM respectively, C4-2) cell line. Furthermore, 6j and 6k were selective against the highly aggressive, triple-negative breast cancer cell line (IC50 = 0.73-0.78 μM, MDA-MB-231). Additionally, in MDA-MB-231 cells, 6j causes cell toxicity, at least partially due to increased tubulin-depolymerizing activity, which could be ROS-mediated. Compound 6j showed crucial interactions with Cysβ241 and Alaβ317, Leuβ255 in Colchicine Binding Site (CBS).

A facile, high-yielding synthetic protocol has been developed to access azepino-fused porphyrins via iodine(III)-mediated oxidative intramolecular cyclization of β-imidazole or benzimidazole substituted porphyrins. The absorption of the synthesized compounds showed the characteristic features of meso-β-fused porphyrins, with intense Soret bands centered between 440 and 460 nm and two weak bands ranging from 550 to 750 nm (Q-bands) Among the synthesized compounds, the free-base imidazo-azepino-fused porphyrin was found to be an efficient 1O2 producer with a higher singlet oxygen quantum yield (ΦΔ ∼0.78 in DMF) as compared to H2TPP (ΦΔ = 0.64 in DMF). It was observed that the protonated form of 4aH2 exhibits a significant red shift of ∼24 nm in Soret and ∼150 nm in Q-bands. Fitting of the titration data of 4aH2 with TFA yielded an apparent pKa of ∼3.58, demonstrating that imidazole fusion enhances the basicity of the porphyrin system.

Pyropheophorbide are recognized as potential photosensitizers due to their capacity to generate singlet oxygen in presence of light, which can selectively induce cytotoxicity in tumor cells. This study focuses on the synthesis and photophysical properties of pyropheophorbide-a (PP) and tryptophan conjugated pyropheophorbide-a (TCPP) and examines their noncovalent interactions with sulphobutylether beta-cyclodextrin (SBE7beta CD) or SBE7beta CD-stabilized Au nanoparticles (SBE7beta CDAuNP). The tryptophan substitution in PP decreases the self-assembly formation, increases the singlet oxygen yield and photostability and reduces the intrinsic toxicity of PP significantly. The 1:1 complex formation between PP/TCPP and SBE7beta CD as revealed by Jobs plot leads to substantial changes in the absorption and fluorescence behaviour including fluorescence lifetime as well as the singlet oxygen yield of both the pyropheophorbide derivatives. Furthermore, SBE7beta CD-stabilized Au nanoparticles containing very low concentration of SBE7beta CD shows efficient interaction with PP/TCPP. SBE7beta CDAuNP:PP exhibits moderate dark toxicity towards both A549 cancer cells and WI38 normal cells and very high phototoxicity towards A549 cells upon light exposure. However, following the supra-nanomolecular approach, SBE7beta CDAuNP:TCPP shows selective and moderate phototoxicity with IC50 value of 3.7 +/- 0.2 M towards A549 cancer cells while preserving the viability of WI38 normal cells under white light irradiation as well as dark conditions. These findings underscore the enhanced photophysical properties of the synthesized pyropheophorbide, highlighting their potential as improved photosensitizers for targeted cancer therapy.

Rapeseed-mustard, a key oilseed crop in India, faces significant yield losses due to insect pests, particularly the mustard aphid (Lipaphis erysimi). This study evaluated the resistance of 79 rapeseed-mustard genotypes to aphid infestation across three growth stages (aphid appearance, full flowering, and full siliqua formation) during the 2022-23 Rabi season. Results revealed significant variability in aphid resistance among genotypes and across growth stages. At the aphid appearance stage, 41 genotypes exhibited resistance (Aphid Resistance Index = 1), while 38 were moderately resistant. As the crop matured, aphid populations increased, and resistance levels declined. At the full flowering stage, 31 genotypes remained resistant, with 46 moderately resistant. At the full siliqua formation stage, only six genotypes were resistant, with 69 moderately resistant and four tolerant. No genotypes were categorized as susceptible or highly susceptible throughout the study, indicating a baseline level of resistance in the evaluated germplasm. Aphid populations ranged from 1.2 to 24.6 (aphid appearance), 3.2 to 59.0 (full flowering), and 2.6 to 173.4 (full siliqua formation) aphids per 10 cm twig. These findings emphasize the dynamic nature of host-aphid interactions and the crucial need for growth-stage-specific resistance evaluations in breeding programs. Identifying and utilizing resistant genotypes can significantly reduce reliance on chemical insecticides, promoting sustainable and eco-friendly aphid management strategies in rapeseed-mustard production.

Preparation of diverse meso-functionalized porphyrins involves iodine(III)- and copper triflate-promoted dehydrogenative coupling of meso-free porphyrins and appropriate NH-free heterocycles. Reaction conditions involving the stable and recyclable iodobenzene diacetate reagent are compatible with a range of NH-free heterocycles (acridone, phenoxazine and phenothiazine, carbazole, β-carbolin triazoles, imidazole, pyrazole, indazole, and tetrazole) and porphyrins to access diversely functionalized A3B, A2BC, and A2B2 porphyrins in moderate to good yields. The prepared heterocycle-appended porphyrins exhibit modestly red-shifted Soret and Q bands in the absorption spectra.

A diverse range of alpha-cyano bis(indolyl)chalcones (21a-r) were synthesized in high yields (90-95%) through the l-proline catalysed reaction of appropriate aldehydes and 3-cyanoacetylindoles. Formation of alpha-cyano bis(indolyl)chalcones involves readily available starting materials, catalytic l-proline, environmentally benign and metal-free conditions. The prepared eighteen alpha-cyano bis(indolyl)chalcones 21a-r were screened against prostate, breast, epithelial cancer cells and found to be non-cytotoxic to normal HEK293 cells. The alpha-cyano bis(indolyl)chalcones 21a (3.9 mu M), 21c (7.5 mu M), 21i (2.2 mu M) and 21o (5.9 mu M) displayed good cytotoxicity against C4-2 cells, whereas, derivatives 21c (1.23 mu M), 21h (5.23 mu M), and 21l (2.5 mu M) showed selective cytotoxicity against 22Rv1 cells. With broad spectrum of activity (0.98-5.6 mu M), the compound 21j was found to increase the endogenous level of ROS, upregulate the level of p-53 and c-jun besides mitochondrial dysfunction, cause apoptosis.

Transgenic Bt cotton is effective to a high degree of, with respect to target lepidoptran bollworms, however sucking pests especially whitefly posed a serious issues in absence of bollworm in genetically modified (GM) crops. Therefore, to understand the efficacy of various biorational compounds against whitefly under non-weedy as well as weedy field conditions, studies on whitefly carried out during kharif 2018, to know the changes in number of whitefly adults as well as nymphs. Transgenic hybrid cotton variety RCH 650 was sown with a spacing of 100×45 cm and replicated four times in both non-weedy and weedy habitat. Although, standard check Dimethoate 30 EC proved it’s efficacy after first and second spray in cotton crop against whitefly. Not with standing, after the application of biorational first time as spray in 29th Standard Meteoroloical Week (SMW), Nimbecidine 300 ppm was admitted as most effective in non-weedy (66.76 and 60.65% mean mortality in whitefly adult and nymph, respectively) as well as in weedy habitat that caused 56.77 and 55.54% mean mortality in adult and nymph, respectively over a period of seven days after application. Entomopathogenic fungi Verticillium lecanii found better to control whitefly adults (42.06 and 40.63%), while Metarhizium anisopliae (42.39 and 36.01%) found more effective for nymphal mortality in non-weedy as well as in weedy habitat. One and same pattern of efficacy of biorational was reconstructed against whitefly again after second application of biorational in all the treatment selected to test against whitefly.

A facile and ratiometric BODIPY-based fluorescent probe 4 was developed for the selective detection of hydrazine in solution phase. The BODIPY-based fluorophores 3 and 4 were easily prepared in high yields from the L-proline catalyzed reaction between α/β-formyl BODIPY 1 a/1 b and 3-cyanoacetylindole 2. Use of easily accessible substrates, benign solvent, catalytic amount of L-proline and high product yields are the advantageous features of the developed protocol. Prepared BODIPYs 3 (536 nm) and 4 (567 nm) showed bathochromic shifts (36-67 nm) in UV-Visible absorption maxima when compared to parent BODIPY (500 nm) in dichloromethane (DCM). The stable and economical BODIPY-based probe 4 exhibited rapid response and remarkable selectivity towards hydrazine when compared to other commonly occurring analytes. At low concentration, the BODIPY probe 4 (10 μΜ) is non-fluorescent, however, a significant enhancement in fluorescent (turn-on) was observed with the increasing concentration of hydrazine (0-100 μΜ). This change in fluorescent behaviour may be ascribed to intramolecular charge transfer (ICT) effect as supported by density functional theory (DFT) calculations. With a 4.3 μM detection limit, the BODIPY probe 4 was also found to be useful in detecting hydrazine in real environmental samples.

Using readily available BODIPY and iodoarenes various BODIPY(aryl)iodonium salts were prepared and successfully utilized for the direct syntheses of functionalized BODIPYs, bis-BODIPYs and for the selective detection of serum protein.

A regioselective manganese-catalyzed ortho-hydroalkyla-tion of aryl-substituted N-heteroaromatic compounds with a range of maleimides is described. The developed C-H bond functionalization protocol allowed the introduction of the succinimide motif at the ortho- position of the aryl ring of N-heteroaromatic compounds, such as 2-arylimidazo[1,2-a]pyridines, 2-arylindazoles, 2-phenylpyridine, 2-phenyl-pyrimidine, 2-phenylimidazo[1,2-a]pyrimidine, 2-phenylimidazo[2,1-b]-thiazole, 2-phenylbenzo[d]imidazo[2,1-b]thiazole, 1-phenylindazole and 1-phenylpyrazole, to produce 3-(2-(N-heteroaryl)aryl)pyrrolidine-2,5-diones in good yields. The protocol exhibited broad substrate scope, good functional group tolerance and excellent regioselectivity under mild and additive-free reaction conditions.

A facile and efficient approach utilizing copper-mediated cross-coupling reaction of N-boc-3-indolylsulfoximines with aryl iodides was developed to synthesize a diverse range of N-arylated indolylsulfoximines 11a-m in excellent yields (up to 91%). The key precursors, free NH sulfoximines 9 were readily prepared by the treatment of N-boc-3-methylthioindoles 8 with a combination of IBD and ammonium carbamate. Under similar conditions NH-free indolylsulfoximine 9a was successfully prepared in gram-scale quantities. The reaction is highly chemoselective and tolerant of a wide range of functional groups. The process is environmentally friendly and is amenable to scale-up. Among the prepared N-arylated indolylsulfoximines 11a-m, compounds 11i-j (2.68-2.76 & mu;M), 11f-g (1.9-3.7 & mu;M) and 11k (1.28 & mu;M) showed potent and selective cytotoxicity against 22Rv1, C4-2 and MCF7 cells, respectively. Indolylsulfoximine derivative 11l displayed a broad spectrum of activity (1.7-8.2 & mu;M) against the tested cancer cell lines. These compounds were found to be non-cytotoxic to normal HEK293 cells, indicating their potential selectivity for cancer cells. We analysed the impact of 11l on various cellular assays to uncover its mechanism of action. Cellular assay shows that 11l increases the endogenous level of ROS, leading to the increased level of p-53 and c-jun inducing apoptosis. 11l also induced mitochondrial dysfunction, further promoting apoptotic pathways. Besides, 11l also restricts cell invasiveness, indicating that it could serve as an effective anti-metastatic agent. As oxidative stress severe F actin causing tubulin depolymerization, we examined the impact of 11l on tubulin dynamics. Accordingly, 11l treatment decreased the levels of polymerized tubulin in 22Rv1 and C4-2 cells. Although future studies are needed to determine their exact molecular target(s), our data shows that N-aryl indolylsulfoximines could serve as effective anti-cancer agents.

To investigate and compare the pharmacokinetic profile and anti-cancer activity of fluorinated and iodinated photosensitizers (PSs), the 3-(1′-(o-fluorobenzyloxy)ethyl pyropheophorbide and the corresponding meta-(m-) and para (p-) fluorinated analogs (methyl esters and carboxylic acids) were synthesized. Replacing iodine with fluorine in PSs did not make any significant difference in fluorescence and singlet oxygen (a key cytotoxic agent) production. The nature of the delivery vehicle and tumor types showed a significant difference in uptake and long-term cure by photodynamic therapy (PDT), especially in the iodinated PS. An unexpected difference in the pharmacokinetic profiles of fluorinated vs. iodinated PSs was observed. At the same imaging parameters, the fluorinated PSs showed maximal tumor uptake at 2 h post injection of the PS, whereas the iodinated PS gave the highest uptake at 24 h post injection. Among all isomers, the m-fluoro PS showed the best in vivo anti-cancer activity in mice bearing U87 (brain) or bladder (UMUC3) tumors. A direct correlation between the tumor uptake and PDT efficacy was observed. The higher tumor uptake of m-fluoro PS at two hours post injection provides a solid rationale for developing the corresponding 18F-agent (half-life 110 min only) for positron imaging tomography (PET) of those cancers (e.g., bladder, prostate, kidney, pancreas, and brain) where 18F-FDG-PET shows limitations.

A simple sequential one-pot protocol has been developed to prepare oxadiazolyl and triazolopyridyl-BODIPY derivatives 4-6 by employing iodine (III)-promoted oxidative cyclization of BODIPY hydrazide-hydrazones which are readily accessible from the reaction of formyl BODIPYs with arylhy-drazides. Photophysical studies of the prepared compounds 4-6 showed a significant red shift in ab-sorption and emission maxima when compared to that of the parent BODIPY. Presence of triazolopyridyl substituent in 6a has affected its binding ability with metal ions and has rendered unique photophysical response by 6a selectively in presence of Hg2+ ions. Compound 6a showed high affinity towards Hg2+ (Ka = 1.8 x 104 M-1) with 2.1 mM limit of detection. The binding stoichiometry between 6a and Hg2+ was determined to be 2:1 by Job's plot analysis. Under acidic conditions, compounds 4c, 5c, 6a and 6b bearing dimethylamino-and triazolopyridyl moieties at a/b-positions of BODIPY unit exhibit blue shifted ab-sorption (10-15 nm) and emission spectra (7-34 nm). Photophysical response of the compounds 4c, 5c, 6a and 6b on changing pH was validated by DFT calculations.(c) 2023 Elsevier Ltd. All rights reserved.

Six methyl pheophorbide-a derivatives were prepared by linking a tryptamine side chain at the C-131 , C-152 and C-173 positions of pheophorbide-a. Prepared conjugates were characterized and evaluated for their photocytotoxicity against A549 cells. The conjugate 6 a with strong absorption at 413 nm (Soret band), 663-671 nm (Q bands) and comparable fluorescence quantum yield (0.26) was found to exhibit significant cytotoxicity (659 nM). Molecular integration of pheophorbide-a and tryptamines showed synergistic effects as the most potent conjugate 6 a was identified with enhanced photocytotoxicity when compared to methyl pheophorbide-a. The conjugate 6 a was smoothly taken up by A549 cells and exhibited intracellular localization predominantly to lysosome in the cytoplasm. Upon photoirradiation 6 a generated singlet oxygen to show potent cytotoxicity toward A549 cells.

Effect of different management modules on Encarsia spp. at different intervals during Kharif, 2015 was studied. Maximum parasitization 32.28 and 31.50% was recorded in T12 [Control (without water spray)] in both the intervals (5- and 10-days interval) followed by 30.30 and 29.85% in T2 nimbecidine (six sprays at 5 days interval) + Yellow sticky trap in both the intervals, respectively. While minimum parasitization (15.02 and 14.91%) was recorded in T5 [First spray of dimethoate followed by imidacloprid, thiamethoxam, triazophos, imidacloprid and thiamethoxam (at 5 days interval)] and T8 [first spray of nimbecidine followed by dimethoate, triazophos, novaluron (at 10 days interval)], respectively. It is concluded that high whitefly pupae parasitization was found in neem treated plots than insecticide treated plots. So, nimbecidine was found relatively less toxic and much safer to natural enemy.

Various β-triazolyl tethered BODIPYs were efficiently prepared in a sequential one-pot protocol involving the initial reaction of BODIPY with iodobenzene diacetate (IBD) and sodium azide to in situ generate BODIPY azides followed by a copper-catalyzed azide-alkyne cycloaddition reaction. Under the optimized reaction conditions, various β-triazolyl BODIPYs 5a-i were successfully prepared in good yields and adequately characterized by using UV, NMR, mass spectral data and XRD analyses. The UV-Visible spectra of the prepared β-triazolyl BODIPYs 5a-i showed intense absorption bands (514-545 nm) with a 13-44 nm red shift when compared with those of the parent BODIPY. The selective recognition of compound 5d towards Ni2+ ions (detection limit 0.26 nM) led to significant quenching in the fluorescence intensity over other selected bivalent metal ions. The complex formed between 5d and Ni2+ in a stoichiometry of 2 : 1 was found to have a binding constant of 7.5 × 105 M-1. The fluorescence of compound 5i gets enhanced gradually upon interaction with bovine serum albumin due to its selective and high binding affinity (1.25 × 105 M-1) with protein and a concomitant decrease in the total non-radiative decay rate.