Comprehensive analysis of spatiotemporal variability of rainfall-based extremes and their implications on agriculture in the Upper Ganga Command Area.

The agricultural sector in India primarily relies on monsoon rains, making it necessary for agricultural water managers to study variations in water availability by analyzing rainfall patterns. This information is critical for deciding cropping patterns and irrigation approaches, managing water resources, and improving crop water productivity. The long-term spatiotemporal variability over the command area, India Meteorological Department (IMD) based selection of thresholds for extremes indices, and thorough analysis of the consequences of extreme on agriculture make the study unique. These aspects collectively enhance the perception of the climate-agriculture relationship, which is essential for promoting agriculture resilience under changing rainfall patterns. This type of research is very limited in the literature. Therefore, the present study focuses on comprehensively analyzing the spatiotemporal variability of rainfall and extreme precipitation indices and their implications on agriculture. The study is carried out in the Upper Ganga Command Area (UGCA), India's oldest irrigation canal system, by using long-term (1901-2021) high-resolution (0.25 × 0.25°) daily rainfall gridded data obtained from IMD, Pune. Eight different extreme rainfall indices are used to assess spatiotemporal variations. The Mann-Whitney-Pettitt test identified 1970 as a significant change point. Rainfall trends and extreme indices for pre- and post-1970 periods were examined using the non-parametric modified Mann-Kendall test. The results show significant increases in rainfall trends for the annual, monsoon, and kharif seasons from 1901 to 1970, but significant decreases were observed during 1971-2021. This difference resulted in a noticeable decrease in average precipitation in the latter period, approximately 62 mm less than in 1901-1970. Similarly, extreme precipitation indices, including the number of rainy days (NxRainy), consecutive dry days (CWD), simple daily intensity index (SDII), and total precipitation (PRCPTOT), exhibited increasing trends in 1901-1970, but they showed significant decreasing trends in 1971-2021. In addition, there is a strong positive correlation between these indices and total precipitation. The study also found that geographical factors influence these trends, with all indices, except SDII, strongly correlated with latitude and elevation, but not with longitude. The implications of these negative rainfall and extreme rainfall trends were further analyzed, and the results indicate a significant impact on the cropping patterns in the study area. The present research findings will be beneficial for regional water resource managers and policymakers in better understanding the existing trends in rainfall distribution over the UGCA.

Cu(II) flavonoids as potential photochemotherapeutic agents.

Flavonoids, naturally derived polyphenolic compounds, have received significant attention due to their remarkable biochemical properties that offer substantial health benefits to humans. In this work, a series of six Cu(II) flavonoid complexes of the formulation [Cu(L1)(L2)](ClO4) where L1 is 3-hydroxy flavone (HF1, 1 and 4), 4-fluoro-3-hydroxy flavone (HF2, 2 and 5), and 2,6-difluoro-3-hydroxy flavone (HF3, 3 and 6); L2 is 1,10-phenanthroline (phen, 1-3) and 2-(anthracen-1-yl)-1H-imidazo[4,5-f][1,10]phenanthroline (aip, 4-6) were successfully synthesized, fully characterized and also evaluated for their in vitro photo-triggered cytotoxicity in cancer cells. The single-crystal X-ray diffraction structure of complex 2 shows square pyramidal geometry around the Cu(II) center. The complexes 1-6 showed quasi-reversible cyclic voltammetric responses for the Cu(II)/Cu(I) couple at ∼-0.230 V with a very large ΔEp value of ∼350-480 mV against the Ag/AgCl reference electrode in DMF-0.1 M tetrabutylammonium perchlorate (TBAP) at a scan rate of 50 mV s-1. The complexes were found to have considerable binding propensity for human serum albumin (HSA) and calf thymus DNA (ct-DNA). The complexes displayed remarkable dose-dependent photocytotoxicity in visible light (400-700 nm) in both A549 (human lung cancer) and MCF-7 (human breast cancer) cell lines while remaining significantly less toxic in darkness. They were found to be much less toxic to HPL1D (immortalized human peripheral lung epithelial) normal cells compared to A549 and MCF-7 cancer cells. Upon exposure to visible light, they generate reactive oxygen species, which are thought to be the main contributors to the death of cancer cells. In the presence of visible light, the complexes predominantly elicit an apoptotic mode of cell death. Complex 6 preferentially localizes in the mitochondria of A549 cells.

Co(II) complexes of curcumin and a ferrocene-based curcuminoid: a study on photo-induced antitumor activity.

Co(II) complexes having a ferrocene-based curcuminoid (Fc-curH) ligand viz. [Co(L)2(Fc-cur)]ClO4 (1, 2), where L is phenanthroline base, namely, 1,10-phenanthroline (phen in 1) and dipyrido[3,2-a:2',3'-c]phenazine (dppz in 2) have been synthesized, characterized and evaluated as photochemotherapeutic agents in vitro. The corresponding Co(II) complexes of the naturally occurring polyphenol curcumin (curH), namely, [Co(L)2(cur)]ClO4 (3, 4), where L is phen (in 3) and dppz (in 4) were synthesized and their photo-induced anticancer activities compared with their ferrocene containing counterparts 1 and 2. The Co(II) acetylacetonato complex viz. [Co(phen)2(acac)]ClO4 (5) was structurally characterized through X-ray crystallography and used as control for cellular experiments. The Co(II) complexes having ferrocene-based curcuminoid are remarkably stable at physiological condition with higher lipophilicity compared to their curcumin analogues. The complexes display significant binding propensity to calf thymus (ct) DNA and human serum albumin (HSA). The complexes 1-4 display remarkable visible light induced cytotoxicity with the ferrocenyl analogues showing more phototoxic index (PI). The Co(II) curcumin complexes localize in the nucleus and mitochondria of A549 cells. The primary cell death mechanism is believed to be apoptotic in nature induced by light assisted generation of reactive oxygen species (ROS).Graphic abstract.

Visible light-induced cytotoxicity studies on Co(ii) complexes having an anthracene-based curcuminoid ligand.

Herein, two ternary cobalt(ii) complexes, namely [Co(9-accm)(phen)2](OAc) (1) and [Co(9-accm)(dppz)2](OAc) (2), where 9-accmH is 1,7-(di-9-anthracene-1,6-heptadiene-3,5-dione), phen is 1,10-phenanthroline and dppz is dipyrido[3,2-a:2',3'-c]phenazine, having an anthracene-based curcuminoid and phenanthroline bases were synthesized and fully characterized, and their in vitro photocytotoxicities were studied in cancer cells. To understand the role of the curcuminoid ligand 9-accm in photo-activated cytotoxicity, two control complexes, viz. [Co(dbm)(phen)2](OAc) (3) and [Co(dbm)(dppz)2](OAc) (4), where dbmH is 1,3-diphenyl-1,3-propanedione (dibenzoylmethane), were prepared and used for the control experiments. Complex 3 was structurally characterized by X-ray crystallography. The complexes displayed a quasi-reversible Co(i)/Co(ii) redox couple at ∼-1.1 V and an irreversible Co(ii)/Co(iii) couple at ∼1.3 V vs. Ag/AgCl in DMF-0.1 M [Bun4N](ClO4). Highly intense 9-accm ligand-centred bands were observed at ∼250-450 nm, which masked the Co(ii)-based weak d-d bands in the DMF-Tris-HCl buffer (1 : 9 v/v). The complexes displayed a significant binding propensity for calf-thymus (ct) DNA with binding constants in the range from (2.42 ± 0.10) × 105 to (3.24 ± 0.13) × 106 M-1. They also showed a moderate binding affinity for human serum albumin (HSA), displaying Kb values in the order of ∼104-105 M-1. The complexes 1 and 2 showed prodigious photoenhanced cytotoxicity in human cervical cancer (HeLa) and breast cancer (MCF-7 and MDA-MB-231) cells with low dark toxicity, whereas they were non-toxic to immortalized lung epithelial normal cells (HPL1D). Flow cytometric studies showed a time-dependent uptake of the complexes 1 and 2 in HeLa cells. The complexes generated reactive oxygen species (ROS) upon excitation with low energy visible light, thereby killing the cancer cells. The results from DAPI staining, AO/EB dual staining and Annexin-V-FITC experiments suggested that the complexes induce cell death primarily via an apoptotic mechanism in HeLa cells.

Photocytotoxic copper(II) complexes of N-salicylyl-l-tryptophan and phenanthroline bases.

Four ternary copper(II) complexes of N-salicylyl-l-Tryptophan (Sal-TrpH) and phenanthroline bases of general formula [Cu(Sal-Trp)(L)], where L is 1,10-phenanthroline (phen, 1), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 2), dipyrido[3,2-a:2',3'-c]phenazine (dppz, 3) and 2-(anthracen-1-yl)-1H-imidazo[4,5-f][1,10]phenanthroline (aip, 4), were synthesized and fully characterized. The complexes were evaluated for their affinity for biomolecules and photocytotoxic activities. Single crystal X-ray diffraction studies of complex 1 revealed that it has a square pyramidal CuN3O2 core with the phenolate oxygen of salicylaldehyde occupying the axial coordination site in the solid state. Complexes 1-4 displayed the Cu(II)-Cu(I) redox couples at ~-0.3 V vs. Ag/AgCl reference electrode in DMF-0.1 M [Bun4N](ClO4). A Cu(II)-based weak d-d band ~650 nm and a moderately strong ligand to metal charge transfer band at ~430 nm were observed in DMF-Tris-HCl buffer (pH 7.2) (1:4 v/v). The complexes are efficient binders to calf thymus DNA and model proteins such as bovine serum albumin and lysozyme. They cleave supercoiled plasmid DNA efficiently when exposed to 446 and 660 nm laser radiation. They are cytotoxic to HeLa (human cervical cancer) and MCF-7 (human breast cancer) cells showing significant enhancement of cytotoxicity upon photo-excitation with low energy visible light. The complexes are found to kill cancer cells through generation of reactive oxygen species (ROS) as confirmed by DCFDA (2',7'-dichlorofluorescin diacetate) assay. The apoptotic cell death induced by complex 4 was confirmed by Annexin V-Fluorescein isothiocyanate-Propidium iodide assay. Confocal microscopic images using 4 showed its primary cytosolic localization in the HeLa and MCF-7 cells.