1,1'-Bis-(diphenylphosphino)ferrocene appended d8- and d10-configuration based thiosquarates: the molecular and electronic configurational insights into their sensitization and co-sensitization properties for dye sensitized solar cells.

Three new d8- and d10-configuration based 1,1'-bis-(diphenylphosphino)ferrocene (dppf) appended thiosquarates complexes with general composition [M(mtsq)2dppf] (M = Ni2+ (NiL2); Zn2+ (ZnL2) and Cd2+ (CdL2)) (mtsq = 3-ethoxycyclobutenedione-4-thiolate) have been synthesized and characterized spectroscopically as well as in case of NiL2 by single crystal X-ray diffraction technique. The single crystal X-ray analysis reveals square planar geometry around Ni(II) in NiL2, where Ni(II) coordinates with two sulfur centres of two mtsq ligands in monodentate fashion and two phosphorus of a dppf ligand in chelating mode. The supramolecular architecture of NiL2 is sustained by intermolecular C-H⋯O interactions to form one-dimensional chain. Further, the application of these newly synthesized complexes as sensitizers and co-sensitizers/co-absorbents with ruthenium based N719 sensitizer in dye-sensitized solar cells (DSSCs) have been explored. The DSSC set-up based on NiL2 offers best photovoltaic performance with photovoltaic efficiency (η) 5.12%, short-circuit current (Jsc) 11.60 mA cm-2, open circuit potential (Voc) 0.690 V and incident photon to current conversion efficiency (IPCE) 63%. In co-sensitized DSSC set-up, ZnL2 along with state-of-the-art N719 dye displays best photovoltaic performance with η 6.65%, Jsc 14.47 mA cm-2, Voc 0.729 V and IPCE 69%, thereby showing an improvement by 15.25% in photovoltaic efficiency in comparison to the photovoltaic efficiency of N719 sensitized DSSC set-up. Variation in co-sensitization behaviour have been ascribed to the differences in the excited state energy level of co-sensitizers. The ZnL2 and CdL2 have a higher energy level position than N719 dye, allowing efficient electron transfer to N719 during light irradiation, while excited state of NiL2 is lower than N719 dye, preventing photoexcited electron transfer to N719, resulting in its lowest overall efficiency among the three co-sensitized DSSC setups.

Mycorrhizal fungus Serendipita indica-associated acid phosphatase rescues the phosphate nutrition with reduced arsenic uptake in the host plant under arsenic stress.

Symbiotic interactions play a vital role in maintaining the phosphate (Pi) nutrient status of host plants and providing resilience during biotic and abiotic stresses. Serendipita indica, a mycorrhiza-like fungus, supports plant growth by transporting Pi to the plant. Despite the competitive behaviour of arsenate (AsV) with Pi, the association with S. indica promotes plant growth under arsenic (As) stress by reducing As bioavailability through adsorption, accumulation, and precipitation within the fungus. However, the capacity of S. indica to enhance Pi accumulation and utilization under As stress remains unexplored. Axenic studies revealed that As supply significantly reduces intracellular ACPase activity in S. indica, while extracellular ACPase remains unaffected. Further investigations using Native PAGE and gene expression studies confirmed that intracellular ACPase (isoform2) is sensitive to As, whereas extracellular ACPase (isoform1) is As-insensitive. Biochemical analysis showed that ACPase (isoform1) has a Km of 0.5977 µM and Vmax of 0.1945 Unit/min. In hydroponically cultured tomato seedlings, simultaneous inoculation of S. indica with As on the 14thday after seed germination led to hyper-colonization, increased root/shoot length, biomass, and induction of ACPase expression and secretion under As stress. Arsenic-treated S. indica colonized groups (13.33 µM As+Si and 26.67 µM As+Si) exhibited 8.28-19.14 and 1.71-3.45-fold activation of ACPase in both rhizospheric media and root samples, respectively, thereby enhancing Pi availability in the surrounding medium under As stress. Moreover, S. indica (13.33 µM As+Si and 26.67 µM As+Si) significantly improved Pi accumulation in roots by 7.26 and 9.46 times and in shoots by 4.36 and 8.85 times compared to the control. Additionally, S. indica induced the expression of SiPT under As stress, further improving Pi mobilization. Notably, fungal colonization also restricted As mobilization from the hydroponic medium to the shoot, with a higher amount of As (191.01 ppm As in the 26.67 µM As+Si group) accumulating in the plant's roots. The study demonstrates the performance of S. indica under As stress in enhancing Pi mobilization while limiting As uptake in the host plant. These findings provide the first evidence of the As-Pi interaction in the AM-like fungus S. indica, indicating reduced As uptake and regulation of PHO genes (ACPase and SiPT genes) to increase Pi acquisition. These data also lay the foundation for the rational use of S. indica in agricultural practices.

Impact of arsenic on phosphate solubilization, acquisition and poly-phosphate accumulation in endophytic fungus Serendipita indica.

Symbiotic interactions play a crucial role in the phosphate (Pi) nutrient status of the host plant and offer resilience during biotic and abiotic stresses. Despite a competitive behavior of arsenic (AsV) with Pi, Serendipita indica association promotes plant growth by reducing arsenic bioavailability in the rhizosphere. Reduced arsenic availability is due to the adsorption, accumulation, and precipitation of arsenic in the fungus. The present investigation focused on the fitness and performance of Pi acquisition and utilization in S. indica for growth and metabolism under arsenic stress. The fungus accumulates a massive amount of arsenic up to 2459.3 ppm at a tolerable limit of arsenic supply (1 mM) with a bioaccumulation factor (BAF) 32. Arsenic induces Pi transporter expression to stimulate the arsenic acquisition in the fungus. At the same time, Pi accumulation was also enhanced by 112.2 times higher than the control with an increase in poly-P (polyphosphate) content (6.69 times) of the cell. This result suggests arsenic does not hamper poly-P storage in the cell but shows a marked delocalization of stored poly-P from the vacuoles. Furthermore, an enhanced exopolyphosphatase activity and poly-P storage during arsenic stress suggest induction of cellular machinery for the utilization of Pi is required to deal with arsenic toxicity and competition. However, at high arsenic supply (2.5 and 5 mM), 14.55 and 22.07 times reduced Pi utilization, respectively, was observed during the Pi uptake by the fungus. The reduction of Pi uptake reduces the cell growth and biomass due to competition between arsenic and phosphate. The study suggests no negative impact of arsenic on the Pi acquisition, storage, and metabolism in symbiotic fungus, S. indica, under environmental arsenic contamination.

Endophytic fungus Serendipita indica reduces arsenic mobilization from root to fruit in colonized tomato plant.

The accumulation of arsenic in crop plants has become a worldwide concern that affects millions of people. The major source of arsenic in crop plants is irrigation water and soil. In this study, Serendipita indica, an endophytic fungus, was used to investigate the protection against arsenic and its accumulation in the tomato plant. We found that inoculation of S. indica recovers seed germination, plant growth and improves overall plant health under arsenic stress. A hyper-colonization of fungus in the plant root was observed under arsenic stress, which results in reduced oxidative stress via modulation of antioxidative enzymes, glutathione, and proline levels. Furthermore, fungal colonization restricts arsenic mobilization from root to shoot and fruit by accumulating it exclusively in the root. We observed that fungal colonization enhances the arsenic bioaccumulation factor 1.48 times in root and reduces the arsenic translocation factor by 2.96 times from root to shoot and 13.6 times from root to fruit compared to non colonized plants. Further, investigation suggests that S. indica can tolerate arsenic by immobilizing it on the cell wall and accumulating it in the vacuole. This study shows that S. indica may be helpful for the reduction of arsenic accumulation in crops grown in arsenic-contaminated agriculture fields.

An effective in-gel assay protocol for the assessment of acid phosphatase (ACPase) isoform expression in the fungus Serendipita indica.

The induction of acid phosphatase (ACPase) in the mycorrhizal fungi is an adaptive survival mechanism to cope in a low-phosphate environment. A mycorrhizal fungi Serendipita indica can induce the ACPase enzyme and enhance the phosphate (Pi) level to the host plant through Pi-solubilization mechanism, both intracellular and extracellular (media) levels. The spectrophotometer technique has been widely and commonly used to measure the ACPase enzyme activity in all microorganisms and plants using pNPP as a substrate. However, this technique cannot be useful when studying the involvement of ACPase isoforms in Pi-solubilization. In this article, we developed a single method to identify and express the ACPase isoforms of S. indica that contribute to the Pi-nutrition in the plant. This is native-PAGE electrophoresis with the in-gel assay and staining to detect the isoforms of the ACPase enzyme. The dark red-brown color developed after staining indicates the non-denatured (native) ACPase enzyme. This method utilized a modified minimal media for the de-repression of P-responsive genes such as ACPases with minimum salt contamination in the samples. This method will be helpful for the characterization of secretory and intracellular ACPases in fungi.

Fungal mediated biotransformation reduces toxicity of arsenic to soil dwelling microorganism and plant.

Rhizospheric and plant root associated microbes generally play a protective role against arsenic toxicity in rhizosphere. Rhizospheric microbial interaction influences arsenic (As) detoxification/mobilization into crop plants and its level of toxicity and burden. In the present investigation, we have reported a rhizospheric fungi Aspergillus flavus from an As contaminated rice field, which has capability to grow at high As concentration and convert soluble As into As particles. These As particles showed a reduced toxicity to soil dwelling bacteria, fungi, plant and slime mold. It does not disrupt membrane potential, inner/outer membrane integrity and survival of the free N2 fixating bacteria. In arbuscular mycorrhiza like endophytic fungi Piriformospora indica, these As particles does not influence mycelial growth and plant beneficial parameters such as phosphate solubilizing enzyme rAPase secretion and plant root colonization. Similarly, it does not affect plant growth and chlorophyll content negatively in rice plant. However, these As particles showed a poor absorption and mobilization in plant. These As particle also does not affect attachment process and survival of amoeboid cells in slime mold, Dictyostelium discoideum. This study suggests that the process of conversion of physical and chemical properties of arsenic during transformation, decides the toxicity of arsenic particles in the rhizospheric environment. This phenomenon is of environmental significance, not only in reducing arsenic toxicity but also in the survival of healthy living organism in arsenic-contaminated rhizospheric environment.

Endophytic Fungi Piriformospora indica Mediated Protection of Host from Arsenic Toxicity.

Complex intercellular interaction is a common theme in plant-pathogen/symbiont relationship. Cellular physiology of both the partners is affected by abiotic stress. However, little is known about the degree of protection each offers to the other from different types of environmental stress. Our current study focused on the changes in response to toxic arsenic in the presence of an endophytic fungus Piriformospora indica that colonizes the paddy roots. The primary impact of arsenic was observed in the form of hyper-colonization of fungus in the host root and resulted in the recovery of its overall biomass, root damage, and chlorophyll due to arsenic toxicity. Further, fungal colonization leads to balance the redox status of the cell by adjusting the antioxidative enzyme system which in turn protects photosynthetic machinery of the plant from arsenic stress. We observed that fungus has ability to immobilize soluble arsenic and interestingly, it was also observed that fungal colonization restricts most of arsenic in the colonized root while a small fraction of it translocated to shoot of colonized plants. Our study suggests that P. indica protects the paddy (Oryza sativa) from arsenic toxicity by three different mechanisms viz. reducing the availability of free arsenic in the plant environment, bio-transformation of the toxic arsenic salts into insoluble particulate matter and modulating the antioxidative system of the host cell.