Estuarine mangrove niches select cultivable heterotrophic diazotrophs with diverse metabolic potentials-a prospective cross-dialog for functional diazotrophy.

Introduction: Biological nitrogen fixation (BNF), an unparalleled metabolic novelty among living microorganisms on earth, globally contributes ~88-101 Tg N year-1 to natural ecosystems, ~56% sourced from symbiotic BNF while ~22-45% derived from free-living nitrogen fixers (FLNF). The success of symbiotic BNF is largely dependent on its interaction with host-plant, however ubiquitous environmental heterotrophic FLNFs face many limitations in their immediate ecological niches to sustain unhindered BNF. The autotrophic FLNFs like cyanobacteria and oceanic heterotrophic diazotrophs have been well studied about their contrivances acclimated/adapted by these organisms to outwit the environmental constraints for functional diazotrophy. However, FLNF heterotrophs face more adversity in executing BNF under stressful estuarine/marine/aquatic habitats. Methods: In this study a large-scale cultivation-dependent investigation was accomplished with 190 NCBI accessioned and 45 non-accessioned heterotrophic FLNF cultivable bacterial isolates (total 235) from halophilic estuarine intertidal mangrove niches of Indian Sundarbans, a Ramsar site and UNESCO proclaimed World Heritage Site. Assuming ~1% culturability of the microbial community, the respective niches were also studied for representing actual bacterial diversity via cultivation-independent next-generation sequencing of V3-V4 rRNA regions. Results: Both the studies revealed a higher abundance of culturable Gammaproteobacteria followed by Firmicutes, the majority of 235 FLNFs studied belonging to these two classes. The FLNFs displayed comparable selection potential in media for free nitrogen fixers and iron-oxidizing bacteria, linking diazotrophy with iron oxidation, siderophore production, phosphorus solubilization, phosphorus uptake and accumulation as well as denitrification. Discussion: This observation validated the hypothesis that under extreme estuarine mangrove niches, diazotrophs are naturally selected as a specialized multidimensional entity, to expedite BNF and survive. Earlier metagenome data from mangrove niches demonstrated a microbial metabolic coupling among C, N, P, S, and Fe cycling in mangrove sediments, as an adaptive trait, evident with the co-abundant respective functional genes, which corroborates our findings in cultivation mode for multiple interrelated metabolic potential facilitating BNF in a challenging intertidal mangrove environment.

Ecological restoration at pilot-scale employing site-specific rationales for small-patch degraded mangroves in Indian Sundarbans.

To date, degraded mangrove ecosystem restoration accomplished worldwide primarily aligns towards rehabilitation with monotypic plantations, while ecological restoration principles are rarely followed in these interventions. However, researchers admit that most of these initiatives' success rate is not appreciable often. An integrative framework of ecological restoration for degraded mangroves where site-specific observations could be scientifically rationalized, with co-located reference pristine mangroves as the target ecosystem to achieve is currently distinctively lacking. Through this experimental scale study, we studied the suitability of site-specific strategies to ecologically restore degraded mangrove patches vis-à-vis the conventional mono-species plantations in a highly vulnerable mangrove ecosystem in Indian Sundarbans. This comprehensive restoration framework was trialed in small discrete degraded mangrove patches spanning ~ 65 ha. Site-specific key restoration components applied are statistically validated through RDA analyses and Bayesian t-tests. 25 quantifiable metrics evaluate the restoration success of a ~ 3 ha degraded mangrove patch with Ridgeline distribution, Kolmogorov-Smirnov (K-S) tests, and Mahalanobis Distance (D2) measure to prove the site's near-equivalence to pristine reference in multiple ecosystem attributes. This restoration intervention irrevocably establishes the greater potential of this framework in the recovery of ecosystem functions and self-sustenance compared to that of predominant monoculture practices for vulnerable mangroves.

Palladium-Catalyzed Electrooxidative Hydrofluorination of Aryl-Substituted Alkenes with a Nucleophilic Fluorine Source.

Herein, we report an electrocatalytic hydrofluorination of aryl-substituted alkenes with a nucleophilic fluorine source. The merger of palladium catalysis with electrooxidation enables the transformation of various substrates ranging from styrenes to more challenging α,ß-unsaturated carbonyl derivatives to the corresponding benzylic fluorides. This method can also be applied to the late-stage modification of pharmaceutical derivatives. Mechanistic studies suggest that the generation of a high-valent palladium intermediate via anodic oxidation is the crucial step in this electrocatalytic hydrofluorination.

Detection of a bibenzyl core scaffold in 28 common mangrove and associate species of the Indian Sundarbans: potential signature molecule for mangrove salinity stress acclimation.

Bibenzyl derivatives comprising two benzene rings are secondary plant metabolites with significant therapeutic value. To date, bibenzyl derivatives in the Plant kingdom have been primarily identified in bryophytes, orchids, and Cannabis sativa. The metabolic cost investment by plant species for the synthesis of these bioactive secondary metabolites is rationalized as a mechanism of plant defense in response to oxidative stress induced by biotic/abiotic factors. Bibenzyl derivatives are synthesized from core phenylpropanoid biosynthetic pathway offshoots in plant species. Mangrove and mangrove associate species thrive under extreme ecological niches such as a hypersaline intertidal environment through unique adaptive and acclimative characteristics, primarily involving osmotic adjustments followed by oxidative stress abatement. Several primary/secondary bioactive metabolites in mangrove species have been identified as components of salinity stress adaptation/acclimation/mitigation; however, the existence of a bibenzyl scaffold in mangrove species functioning in this context remains unknown. We here report the confirmed detection of a core bibenzyl scaffold from extensive gas chromatography-mass spectrometry and gas chromatography-flame ionization detection analyses of 28 mangrove and mangrove associate species from the Indian Sundarbans. We speculate that the common presence of this bibenzyl core molecule in 28 mangrove and associate species may be related to its synthesis via branches of the phenylpropanoid biosynthetic pathway induced under high salinity, which functions to detoxify reactive oxygen species as a protection for the maintenance of plant metabolic processes. This finding reveals a new eco-physiological functional role of bibenzyls in unique mangrove ecosystem.

Wave induced coastal flooding along the southwest coast of India during tropical cyclone Tauktae.

The coastal flood during the tropical cyclone Tauktae, 2021, at Chellanam coast, Kerala, India, has invited wide attention as the wave overtopping severely affected coastal properties and livelihood. We used a combination of WAVEWATCHIII and XBeach to study the coastal inundation during high waves. The effect of low-frequency waves and the rise in the coastal water level due to wave setup caused the inundation at Chellanam, even during low tide with negligible surge height. Wave setup raised the water level at the coast with steep slopes to more than 0.6 m and peaked during low tide, facilitating wave breaking at the nearshore region. The coastal regions adjacent to these steep slopes were subjected to severe inundation. The combined effect of long and short waves over wave setup formed extreme wave runups that flooded inland areas. At gently sloping beaches, the longwave component dominated and overtopped the seawalls and damaged households along the shoreline. The study emphasizes the importance of longwave and wave setup and its interaction with nearshore bathymetry during the high wave. The present study shall lead to the development of a coastal inundation prediction system for the low-lying hot spots using the combination of WAVEWATCHIII and XBeach models.

Prospects and challenges of yellow flesh pangasius in international markets: secondary and primary evidence from Bangladesh.

The projected increase in aquaculture production by 2030 will mostly occur in countries of Asia and Africa, including Bangladesh. The pangasius (Pangasianodon hypophthalmus) produced in Bangladesh, the second-largest producer globally, is mainly consumed by low-income domestic consumers and is poorly demanded in international markets. One reason for this is the yellow flesh of fish; consumers generally in mainstream international markets prefer to fish with white flesh. Reviewing secondary evidence and analyzing primary data, this article assesses the underlying reasons for the discolored pangasius flesh in Bangladesh and synthesizes strategies for avoiding discoloration to induce exports. The findings indicate that farming practices with high stocking density, infrequent water exchange, high organic matter in pond water, and the growth of carotenoid-containing cyanobacteria contribute to the discoloration of pangasius flesh. Artificial and natural pigments in feed and poor post-harvest handling of fish are also contributing factors. Furthermore, a positive correlation between water exchange, price, and yield at the farm is found, which indicates that farm-gate price and yield per hectare can increase with more frequent water exchange. The findings of this study provide strong evidence that improved aquaculture practices can solve the problem of discolored pangasius flesh and establish an export-oriented pangasius industry in Bangladesh.

Genetic Identification of all Four Mangrove Mud Crab Species (genus Scylla) Using Multiple Molecular Markers.

Misleading identification and subsequent publications on biological, molecular, and aquaculture data of mangrove mud crab (genus Scylla de Hann 1833) is a major concern in many countries. In this study, multiple molecular markers were used for genetic identification of all four known mud crab species under genus Scylla collected from India, Philippines, Myanmar, Malaysia and Indonesia. Internal Transcribed Spacer (ITS-1), Polymerase chain reaction (PCR)-Restriction Fragment Length Polymorphism (PCR-RFLP) and PCR-based species-specific markers were used to resolve taxonomic ambiguity. PCR-RFLP techniques using NlaIV and BsaJI restriction endonucleases were efficient to differentiate four different mud crab species under genus Scylla with specific fragment profile. The results also justified the use of ITS-1 and PCR-based species-specific markers to identify mud crab species available in many countries quite rapidly and effectively. Several new molecular markers generated during the study are reported here to resolve the taxonomic ambiguity of Scylla species and the results reconfirmed that India is only having two commonly available mud crab species which was reported by the authors earlier.

Surveillance of disease incidence in shrimp farms located in the east coastal region of India and in vitro antibacterial efficacy of probiotics against Vibrio parahaemolyticus.

We surveyed 130 shrimp farms located on the eastern coast of India to determine the prevalence of emerging diseases in Litopenaeus vannamei and Penaeus monodon. Live shrimps were collected from the farms based on external symptoms. The biochemical, molecular, and histopathology results confirmed infection with Enterocytozoon hepatopenaei (32.4%), Vibrio parahaemolyticus (27.7%), White Spot Syndrome Virus (25.4%), Vibrio alginolyticus (16.1%), Vibrio harveyi (13.1%), Monodon-type baculovirus (4.61%), and infectious Hematopoietic Necrosis Virus (2.3%) in the collected shrimps. Enterocytozoon hepatopenaei (EHP) occurred more frequently in L. vannamei than P. monodon, with the microsporidian spores in the hepatopancreas. In P. monodon, Monodon-type Baculovirus infection (33.3%) was dominant and small percentages of WSSV, IHHNV, V. alginolyticus, and V. harveyi were observed. A few ponds were observed with co-infection of EHP and WSSV (7.6%), V. parahaemolyticus and WSSV (4.6%) and also V. parahaemolyticus and EHP (6.1%). Among the Vibrio spp, V. parahaemolyticus showed the highest percentage of infection in L. vannamei. Overall, we found that shrimp were chiefly infected with EHP and V. parahaemolyticus. The impact of water quality parameters on shrimp diseases was not addressed in this study. In an antibiotic susceptibility study, V. parahaemolyticus isolated from L. vannamei ponds was susceptible to nitrofurantoin, chloramphenicol, oxytetracycline and tetracycline, but resistant to erythromycin and nalidixic acid. In a preliminary in vitro antibacterial activity assay, probiotics against V. parahaemolyticus showed high inhibitory activity and the results encourage further in-depth studies on the efficacy of probiotics for disease control and prevention in shrimp farms.

Regioselective C-H Alkenylation and Unsymmetrical Bis-olefination of Heteroarene Carboxylic Acids with Ruthenium Catalysis in Water.

An efficient weak carboxylate-assisted oxidative cross-dehydrogenative C-H/C-H coupling (CDC) of heteroarenes with readily available olefins has been devised employing water as green solvent under ruthenium(II) catalysis. The reaction is operationally simple, accommodates a large variety of heteroaromatic carboxylic acids as well as olefins, and facilitates a diverse array of high-value olefin-tethered heteroarenes in high yields (up to 87%). The potential of this ortho-C-H bond activation strategy has also been exploited toward tunable synthesis of densely functionalized heteroarenes through challenging unsymmetrical bis-olefination process in a one-pot sequential fashion. Mechanistic investigation demonstrates a reversible ruthenation process and C-H metalation step might not be involved in the rate-determining step.

Cross-Dehydrogenative Coupling/Annulation of Arene Carboxylic Acids and Alkenes in Water with Ruthenium(II) Catalyst and Air.

A cross-dehydrogenative coupling of arene carboxylic acids with olefins is reported with ruthenium(II) catalyst employing air and water as green oxidant and solvent, respectively. It offers a robust synthesis of valuable phthalide molecules. A one-pot sequential strategy is also disclosed to access Heck-type products that are apparently difficult to make directly from arene carboxylic acids.

Copper-Catalyzed 8-Aminoquinoline-Directed Oxidative C-H/N-H Coupling for N-Arylation of Sulfoximines.

A copper-catalyzed cross-dehydrogenative C-H/N-H coupling has been devised to access a series of N-arylated sulfoximines in high yield from 8-aminoquinoline-derived benzamides and sulfoximines. The reaction is scalable, and mechanistic studies favor the involvement of an organometallic pathway, where C-H bond cleavage is presumed to be the kinetically relevant step. The utility of sulfoximine-coupled benzamides was displayed through the nickel-catalyzed acceptorless dehydrogenative olefination of benzyl alcohols.

Recent Advancements in Transition-Metal-Catalyzed One-Pot Twofold Unsymmetrical Difunctionalization of Arenes.

Transition-metal-catalyzed direct C-H bond activation reactions have been embraced as a powerful synthetic tool to access diverse functionalized arenes. However, site-selective incorporation of multiple distinct functionalities in an arene has always been a formidable challenge. Recent efforts from the synthetic community have disclosed a few dynamic synthetic approaches to fabricate multifunctionalized arenes in one-pot using a single catalytic system. These reports manifested the immense potential of such approaches to expedite contemporary organic synthesis towards building molecular complexity. In this minireview, we have illustrated the recent progress in this area, highlighting the contribution from several synthetic chemists including our group.

A ruthenium-catalyzed free amine directed (5+1) annulation of anilines with olefins: diverse synthesis of phenanthridine derivatives.

A ruthenium(ii)-catalyzed cross-ring (5+1) annulation between 2-aminobiphenyls and activated olefins is disclosed for succinct synthesis of valuable phenanthridine scaffolds. The protocol avails a common organic functional group, free amine, as a directing group and represents a unique combination of C-H activation/annulation/C-C bond cleavage cascade that bodes well in the production of bioactive alkaloids including trisphaeridine and bicolorine.

Streamlined Ruthenium(II) Catalysis for One-Pot 2-fold Unsymmetrical C-H Olefination of (Hetero)Arenes.

The potential of carboxylate-directed Ru(II)-catalyzed C-H bond activation has been exploited in the first example of challenging 2-fold unsymmetrical cross-dehydrogenative olefination of (hetero)aromatic carboxylic acids. This highly regioselective protocol operates in one pot under a single catalytic system and tolerates a wide spectrum of carboxylic acids as well as activated olefins. A rare example of an unsymmetrical meta-bis-olefination approach has also been successfully engineered via a tailored unsymmetrical double C-H functionalization and concomitant decarboxylation process.

Atom Transfer Oxidative Radical Cascade of Aryl Alkynoates towards 1,1-Dichalcogenide Olefins.

An oxidative trifunctionalization of aryl alkynoates has been devised via the chalcogenide radical triggered intramolecular 1,4-aryl migration/decarboxylation cascade to prepare 1,1-dichalcogenide tetrasubstituted alkenes in high yields (up to 98 %). This operationally simple reaction proceeds under metal-free conditions, can be executed on gram scale, and highlights formal 1,1-difunctionalization of alkynes. Synthetic potential of this protocol was demonstrated through a twofold cascade rearrangement to access highly conjugated tetra-selenylated alkenes along with a cross-dehydrogenative annulation to prepare fluorene derivative.

Ru(II)-Catalyzed Oxidative Heck-Type Olefination of Aromatic Carboxylic Acids with Styrenes through Carboxylate-Assisted C-H Bond Activation.

A straightforward synthesis of 2-styrylbenzoic acids from aryl carboxylic acids is disclosed through a carboxylate-assisted coupling under Ru(II) catalysis. This protocol is simple and exhibits broad scope with high tolerance of common organic functional groups, providing good to excellent yields of diverse olefinated products. The efficacy of this protocol has been showcased through sequential syntheses of isochromanone, isocoumarin, and formal synthesis of anacardic acid derivative in good yields.

A Cross-Dehydrogenative Annulation Strategy towards Synthesis of Polyfluorinated Phenanthridinones with Copper.

The first cross-dehydrogenative annulation of (hetero)aromatic amides with polyfluoro(hetero)arenes is presented. This operationally simple oxidative annulation process is mediated by inexpensive copper salt, accommodates a wide range of substrates with exquisite chemo- and regioselectivity profile, and produces demanding polyfluorinated phenanthridinones in high yields (up to 92 %). Using alkenyl amides under identical conditions, the synthesis of polyfluorinated 2-quinolones has also been accomplished. Given the importance of fluorinated heterocycles in the pharmaceutical industry and drug discovery, this work is highly significant.

Ruthenium(II)-Catalyzed Hydroarylation of Maleimides Using Carboxylic Acids as a Traceless Directing Group.

An efficient Ru(II)-catalyzed hydroarylation of maleimides with ready-stock aryl carboxylic acids has been developed based on weak carboxylate-directed ortho-C-H alkylation and concomitant decarboxylation processes, fabricating 3-aryl succinimides, a recurrent scaffold in drug molecules, in high yields (up to 97%). The protocol features operational simplicity, avoids the need for precious metal additives/oxidants, and offers broad substrate scope with formal meta- and para-selectivities. It represents the first example of Ru(II)-catalyzed direct arylation of maleimides with unbiased benzoic acids.

Ruthenium(II)-Catalyzed ortho-C-H Chalcogenation of Benzoic Acids via Weak O-Coordination: Synthesis of Chalcogenoxanthones.

A general protocol for direct chalcogenation of inert C-H bonds of (hetero)aromatic carboxylic acids is developed with a ruthenium(II) catalyst using readily available starting materials, offering densely substituted ortho-chalcogenyl aromatic acids in high yields (up to 96%). The strategy avoids the installation of an external directing group, use of metallic oxidants, and features operational simplicity with ample substrate scope. Synthetic application en route to biologically important chalcogenoxanthones is also demonstrated. This work represents the first example of ruthenium(II)-catalyzed direct C-H chalcogenation of benzoic acids.

Ru(II)-Catalyzed C-H Functionalization on Maleimides with Electrophiles: A Demonstration of Umpolung Strategy.

The unconventional nucleophilic reactivity of maleimides, innate electrophiles, has been realized under Ru(II)-catalysis such that exposure to electrophiles delivered products of C-H chalcogenation and amidation in good yields (up to 94%). This protocol features mild conditions and operational simplicity with broad substrate scope, uses an inexpensive and air-stable catalyst, and also represents the first example of Ru(II) catalyzed C-H selenylation of alkenes.