Catalytic Enantioselective Friedel-Crafts Allenylation.

The first enantioselective Friedel-Crafts (FC) allenylation reaction for the creation of central chirality is developed under cooperative Ir(I)/(phosphoramidite,olefin) and Lewis acid catalysis. This enantioconvergent reaction utilizes racemic allenylic alcohol as the electrophile and shows compatibility with a variety of electron-rich arenes and heteroarenes. The resulting highly enantioenriched (up to >99.5:0.5 e.r.) 1,1-disubstituted allenylic methanes, bearing a benzylic carbon stereocenter, are obtained with complete regiocontrol - both on (hetero)arenes as well as on the allenylic fragment. This protocol allows for the enantioselective formal introduction of a 4-carbon alkyl chain into (hetero)arenes, along with the creation of a benzylic stereocenter. Judicious synthetic elaborations not only lead to formal enantioselective FC alkylation products of less electron-rich arenes but also of substituted arenes in ortho- and even meta-selective fashion. An intramolecular version of this FC allenylation is shown to proceed with promising enantioselectivity under the same catalytic conditions. Mechanistic studies revealed the involvement of dynamic kinetic asymmetric transformation (DyKAT) of racemic allenylic alcohols in this reaction.

A comprehensive review on agricultural waste utilization through sustainable conversion techniques, with a focus on the additives effect on the fate of phosphorus and toxic elements during composting process.

The increasing trend of using agricultural wastes follows the concept of "waste to wealth" and is closely related to the themes of sustainable development goals (SDGs). Carbon-neutral technologies for waste management have not been critically reviewed yet. This paper reviews the technological trend of agricultural waste utilization, including composting, thermal conversion, and anaerobic digestion. Specifically, the effects of exogenous additives on the contents, fractionation, and fate of phosphorus (P) and potentially toxic elements (PTEs) during the composting process have been comprehensively reviewed in this article. The composting process can transform biomass-P and additive-born P into plant available forms. PTEs can be passivated during the composting process. Biochar can accelerate the passivation of PTEs in the composting process through different physiochemical interactions such as surface adsorption, precipitation, and cation exchange reactions. The addition of exogenous calcium, magnesium and phosphate in the compost can reduce the mobility of PTEs such as copper, cadmium, and zinc. Based on critical analysis, this paper recommends an eco-innovative perspective for the improvement and practical application of composting technology for the utilization of agricultural biowastes to meet the circular economy approach and achieve the SDGs.

Tricks and tracks of prevalence, occurrences, treatment technologies, and challenges of mixtures of emerging contaminants in the environment: With special emphasis on microplastic.

This paper aims to emphasize the occurrence of various emerging contaminant (EC) mixtures in natural ecosystems and highlights the primary concern arising from the unregulated release into soil and water, along with their impacts on human health. Emerging contaminant mixtures, including pharmaceuticals, personal care products, dioxins, polychlorinated biphenyls, pesticides, antibiotics, biocides, surfactants, phthalates, enteric viruses, and microplastics (MPs), are considered toxic contaminants with grave implications. MPs play a crucial role in transporting pollutants to aquatic and terrestrial ecosystems as they interact with the various components of the soil and water environments. This review summarizes that major emerging contaminants (ECs), like trimethoprim, diclofenac, sulfamethoxazole, and 17α-Ethinylestradiol, pose serious threats to public health and contribute to antimicrobial resistance. In addressing human health concerns and remediation techniques, this review critically evaluates conventional methods for removing ECs from complex matrices. The diverse physiochemical properties of surrounding environments facilitate the partitioning of ECs into sediments and other organic phases, resulting in carcinogenic, teratogenic, and estrogenic effects through active catalytic interactions and mechanisms mediated by aryl hydrocarbon receptors. The proactive toxicity of ECs mixture complexation and, in part, the yet-to-be-identified environmental mixtures of ECs represent a blind spot in current literature, necessitating conceptual frameworks for assessing the toxicity and risks with individual components and mixtures. Lastly, this review concludes with an in-depth exploration of future scopes, knowledge gaps, and challenges, emphasizing the need for a concerted effort in managing ECs and other organic pollutants.

A critical review on characterization, human health risk assessment and mitigation of malodorous gaseous emission during the composting process.

Composting has emerged as a suitable method to convert or transform organic waste including manure, green waste, and food waste into valuable products with several advantages, such as high efficiency, cost feasibility, and being environmentally friendly. However, volatile organic compounds (VOCs), mainly malodorous gases, are the major concern and challenges to overcome in facilitating composting. Ammonia (NH3) and volatile sulfur compounds (VSCs), including hydrogen sulfide (H2S), and methyl mercaptan (CH4S), primarily contributed to the malodorous gases emission during the entire composting process due to their low olfactory threshold. These compounds are mainly emitted at the thermophilic phase, accounting for over 70% of total gas emissions during the whole process, whereas methane (CH4) and nitrous oxide (N2O) are commonly detected during the mesophilic and cooling phases. Therefore, the human health risk assessment of malodorous gases using various indexes such as ECi (maximum exposure concentration for an individual volatile compound EC), HR (non-carcinogenic risk), and CR (carcinogenic risk) has been evaluated and discussed. Also, several strategies such as maintaining optimal operating conditions, and adding bulking agents and additives (e.g., biochar and zeolite) to reduce malodorous emissions have been pointed out and highlighted. Biochar has specific adsorption properties such as high surface area and high porosity and contains various functional groups that can adsorb up to 60%-70% of malodorous gases emitted from composting. Notably, biofiltration emerged as a resilient and cost-effective technique, achieving up to 90% reduction in malodorous gases at the end-of-pipe. This study offers a comprehensive insight into the characterization of malodorous emissions during composting. Additionally, it emphasizes the need to address these issues on a larger scale and provides a promising outlook for future research.

Ecological and human health risk assessment of pharmaceutical compounds in the Sirsa River of Indian Himalayas.

The Baddi-Barotiwala-Nalagarh (BBN) region of Indian Himalayas is one of the most important pharmaceutical industrial clusters in Asia. This study investigated the distribution, and ecological and human health risks of four most frequently used pharmaceuticals [ciprofloxacin (CIP), norfloxacin (NOR), cetirizine (CTZ) and citalopram oxalate (ECP)] when co-occurring with metal ions in the Sirsa river water of the BBN region. The concentration range of the selected pharmaceuticals was between 'not detected' to 50 µgL-1 with some exception for CIP (50-100 µgL-1) and CTZ (100-150 µgL-1) in locations directly receiving wastewater discharges. A significant correlation was found between the occurrences of NOR and Al (r2 = 0.65; p = 0.01), and CTZ and K (r2 = 0.50; p = 0.01) and Mg (r2 = 0.50; p = 0.01). A high-level ecological risk [risk quotient (RQ) > 1] was observed for algae from all the pharmaceuticals. A medium-level risk (RQ = 0.01-0.1) was observed for Daphnia from CIP, NOR and ECP, and a high-level risk from CTZ. A low-level risk was observed for fishes from CIP and NOR, whereas CTZ and ECP posed a high-level risk to fishes. The overall risk to ecological receptors was in the order: CTZ > CIP > ECP > NOR. Samples from the river locations receiving water from municipal drains or situated near landfill and pharmaceutical factories exhibited RQ > 1 for all pharmaceuticals. The average hazard quotient (HQ) values for the compounds followed the order: CTZ (0.18) > ECP (0.15) > NOR (0.001) > CIP (0.0003) for children (0-6 years); ECP (0.49) > CTZ (0.29) > NOR (0.005) > CIP (0.001) for children (7-17 years), and ECP (0.34) > CTZ (0.21) > NOR (0.007) > CIP (0.001) for adults (>17 years). The calculated risk values did not readily confirm the status of water as safe or unsafe because the values of predicted no-effect concentration (PNEC) would depend on various other environmental factors such as quality of the toxicity data, and species sensitivity and distribution, which warrants further research.

The distribution, fate, and environmental impacts of food additive nanomaterials in soil and aquatic ecosystems.

Nanomaterials in the food industry are used as food additives, and the main function of these food additives is to improve food qualities including texture, flavor, color, consistency, preservation, and nutrient bioavailability. This review aims to provide an overview of the distribution, fate, and environmental and health impacts of food additive nanomaterials in soil and aquatic ecosystems. Some of the major nanomaterials in food additives include titanium dioxide, silver, gold, silicon dioxide, iron oxide, and zinc oxide. Ingestion of food products containing food additive nanomaterials via dietary intake is considered to be one of the major pathways of human exposure to nanomaterials. Food additive nanomaterials reach the terrestrial and aquatic environments directly through the disposal of food wastes in landfills and the application of food waste-derived soil amendments. A significant amount of ingested food additive nanomaterials (> 90 %) is excreted, and these nanomaterials are not efficiently removed in the wastewater system, thereby reaching the environment indirectly through the disposal of recycled water and sewage sludge in agricultural land. Food additive nanomaterials undergo various transformation and reaction processes, such as adsorption, aggregation-sedimentation, desorption, degradation, dissolution, and bio-mediated reactions in the environment. These processes significantly impact the transport and bioavailability of nanomaterials as well as their behaviour and fate in the environment. These nanomaterials are toxic to soil and aquatic organisms, and reach the food chain through plant uptake and animal transfer. The environmental and health risks of food additive nanomaterials can be overcome by eliminating their emission through recycled water and sewage sludge.

Biochar modulating soil biological health: A review.

Biochar can be used for multifunctional applications including the improvement of soil health and carbon storage, remediation of contaminated soil and water resources, mitigation of greenhouse gas emissions and odorous compounds, and feed supplementation to improve animal health. A healthy soil preserves microbial biodiversity that is effective in supressing plant pathogens and pests, recycling nutrients for plant growth, promoting positive symbiotic associations with plant roots, improving soil structure to supply water and nutrients, and ultimately enhancing soil productivity and plant growth. As a soil amendment, biochar assures soil biological health through different processes. First, biochar supports habitats for microorganisms due to its porous nature and by promoting the formation of stable soil micro-aggregates. Biochar also serves as a carbon and nutrient source. Biochar alters soil physical and chemical properties, creating optimum soil conditions for microbial diversity. Biochar can also immobilize soil pollutants and reduce their bioavailability that would otherwise inhibit microbial growth. However, depending on the pyrolysis settings and feedstock resources, biochar can be comprised of contaminants including polycyclic aromatic hydrocarbons and potentially toxic elements that can inhibit microbial activity, thereby impacting soil health.

Ligand-Controlled Diastereodivergency in Propargylic Alkylation of Vinylogous Aza-Enamines: Construction of 1,3-Stereocenters.

The first diastereodivergent propargylic alkylation reaction is developed. This Cu(I)-catalyzed formal decarboxylative [4+2] cycloaddition between ethynyl benzoxazinanone and vinylogous aza-enamine delivers each diastereomer of tetrahydroquinoline derivatives, bearing 1,3-stereocenters, using either i-Pr-Pybox or BINAP as the ligand under otherwise identical reaction conditions. This is the first application of vinylogous aza-enamines in a transition metal-catalyzed transformation and the first example of the creation of 1,3-stereocenters in a propargylic substitution reaction.

Iridium-Catalyzed Enantioselective Formal α-Allylic Alkylation of Acrylonitrile.

A highly enantioselective formal α-allylic alkylation of acrylonitrile is developed using 4-cyano-3-oxotetrahydrothiophene (c-THT) as a safe and easy-to-handle surrogate of acrylonitrile. This two-step process consists of an Ir(I)/(P,olefin)-catalyzed branched-selective allylic alkylation using easily accessible branched rac-allylic alcohols as the allylic electrophile followed by retro-Dieckmann/retro-Michael fragmentation and is shown to be applicable for the enantioselective synthesis of α-allylic acrylates as well as α-allylic acrolein.

Enantioselective Synthesis of Skipped Dienes via Iridium-Catalyzed Allylic Alkylation of Phosphonates.

An enantioselective synthesis of skipped dienes has been developed based on an iridium-catalyzed allylic alkylation of phosphonates and Horner-Wadsworth-Emmons olefination. This two-step protocol uses easily accessible substrates and delivers C2-substituted skipped dienes bearing a C3 stereogenic center, generally with outstanding enantioselectivities (up to 99.5:0.5 er). This is the first catalytic enantioselective allylic alkylation of phosphonates, and the overall process represents a formal enantioselective α-C(sp2)-H allylic alkylation of α,ß-unsaturated carbonyls and acrylonitrile.

Recent analytical techniques, and potential eco-toxicological impacts of textile fibrous microplastics (FMPs) and associated contaminates: A review.

Despite of our growing understanding of microplastic's implications, research on the effects of fibrous microplastic (FMPs) on the environment is still in its infancy. Some scientists have hypothesized the possibility of natural textile fibres, which may act as one of the emerging environmental pollutants prevalent among microplastic pollutants in the environment. Therefore, this review aims to critically evaluate the toxic effects of emerging FMPs, the presence, and sources of FMPs in the environment, identification and analytical techniques, and the potential impact or toxicity of the FMPs on the environment and human health. About175 publications (2011-2023) based on FMPs were identified and critically reviewed for transportation, analysis and ecotoxicological behaviours of FMPs in the environment. Textile industries, wastewater treatment plants, and household washing of clothes are significant sources of FMPs. In addition, various characterization techniques (e.g., FTIR, SEM, RAMAN, TGA, microscope, and X-Ray Fluorescence Spectroscopy) commonly used for the identification and analysis of FMPs are also discussed, which justifies the novelty aspects of this review. FMPs are pollutants of emerging concern due to their prevalence and persistence in the environment. FMPs are also found in the food chain, which is an alarming situation for living organisms, including effects on the nervous system, digestive system, circulatory system, and genetic alteration. This review will provide readers with a comparison of different analytical techniques, which will be helpful for researchers to select the appropriate analytical techniques for their study and enhance their knowledge about the harmful effects of FMPs.

Catalytic Generation of Remote C-N Axial Chirality through Atroposelective de novo Arene Construction.

The first atroposelective desymmetrization of prochiral N-aryl maleimides through its conversion to axially chiral phthalimides is developed by applying a de novo arene construction strategy. Catalyzed by bis(3,5-dimethylphenyl)prolinol TMS-ether, this reaction proceeds through oxidative [4 + 2]-cycloaddition with α,ß-unsaturated aldehydes to generate only a chiral C-N axis remote from the reaction sites with excellent enantioselectivity (up to 97.5:2.5 er).

Hydroxy-directed iridium-catalyzed enantioselective formal ß-C(sp2)-H allylic alkylation of α,ß-unsaturated carbonyls.

Hydroxy-directed iridium-catalyzed enantioselective formal ß-C(sp2)-H allylic alkylation of kojic acid and structurally related α,ß-unsaturated carbonyl compounds is developed. This reaction, catalyzed by an Ir(i)/(P,olefin) complex, utilizes the nucleophilic character of α-hydroxy α,ß-unsaturated carbonyls, to introduce an allyl group at its ß-position in a branched-selective manner in good to excellent yield with uniformly high enantioselectivity (up to >99.9 : 0.1 er). To the best of our knowledge, this report represents the first example of the use of kojic acid in a transition metal catalyzed highly enantioselective transformation.

Mechanism and Origin of Remote Stereocontrol in the Organocatalytic Enantioselective Formal C(sp2)-H Alkylation Using Nitroalkanes as Alkylating Agents.

Experimental 13C kinetic isotope effects (KIEs) and density functional theory (DFT) calculations are used to evaluate the mechanism and origin of enantioselectivity in the formal C(sp2)-H alkylative desymmetrization of cyclopentene-1,3-diones using nitroalkanes as the alkylating agent. An unusual combination of an inverse (∼0.980) and a normal (∼1.033) KIE is observed on the bond-forming carbon atoms of the cyclopentene-1,3-dione and nitroalkane, respectively. These data provide strong support for a mechanism involving reversible carbon-carbon bond formation followed by rate- and enantioselectivity-determining nitro group elimination. The theoretical free-energy profile and the predicted KIEs indicate that this elimination event occurs via an E1cB pathway. The origin of remote stereocontrol is evaluated by distortion-interaction and SAPT0 analyses of the E1cB transition states leading to both enantiomers.

Catalytic Enantioselective de novo Construction of Chiral Arenes through Desymmetrizing Oxidative [4+2]-Cycloaddition.

Central chirality in arene derivatives arising out of unsymmetrically substituted arene ring is a fascinating yet rarely explored research topic. Here, we report a desymmetrization approach to centrally chiral unfunctionalized arenes, which is enabled by the enantioselective de novo construction of the arene ring. This operationally simple protocol is based on a [4+2]-cycloaddition between polycyclic meso-cyclohexenediones and α,ß-unsaturated aldehydes, and doesn't usually require any external oxidant. Catalyzed by a diphenylprolinol silyl ether, this reaction proceeds via dienamine intermediate and greatly simplifies the access to diversely substituted chiral arenes with outstanding enantioselectivities.

Biochar-microorganism interactions for organic pollutant remediation: Challenges and perspectives.

Numerous harmful chemicals are introduced every year in the environment through anthropogenic and geological activities raising global concerns of their ecotoxicological effects and decontamination strategies. Biochar technology has been recognized as an important pillar for recycling of biomass, contributing to the carbon capture and bioenergy industries, and remediation of contaminated soil, sediments and water. This paper aims to critically review the application potential of biochar with a special focus on the synergistic and antagonistic effects on contaminant-degrading microorganisms in single and mixed-contaminated systems. Owing to the high specific surface area, porous structure, and compatible surface chemistry, biochar can support the proliferation and activity of contaminant-degrading microorganisms. A combination of biochar and microorganisms to remove a variety of contaminants has gained popularity in recent years alongside traditional chemical and physical remediation technologies. The microbial compatibility of biochar can be improved by optimizing the surface parameters so that toxic pollutant release is minimized, biofilm formation is encouraged, and microbial populations are enhanced. Biocompatible biochar thus shows potential in the bioremediation of organic contaminants by harboring microbial populations, releasing contaminant-degrading enzymes, and protecting beneficial microorganisms from immediate toxicity of surrounding contaminants. This review recommends that biochar-microorganism co-deployment holds a great potential for the removal of contaminants thereby reducing the risk of organic contaminants to human and environmental health.

Dissipation kinetics, residue modeling and human intake of endosulfan applied to okra (Abelmoschus esculentus).

The non-judicious application of the harmful pesticide endosulfan on okra, one of India's most consumed vegetable crops, has resulted in the frequent detection of residues in food samples. This can lead to resistance and the resurgence of various pests and diseases. In this context, combined dissipation and residue dynamics of different endosulfan components or mixtures (isomers and metabolites) in crop compartments are not yet well understood. To address this research gap, the present study evaluates the dissipation and persistence behavior of different endosulfan isomers (alpha-, beta-isomers) and major metabolite (endosulfan sulfate) on okra during 2017 and 2018. The half-life of endosulfan on okra leaves was found to be between 1.79 and 3.47 days. Half of the endosulfan deposits on okra fruits at the recommended doses were dissipated after 2.39 days compared to 1.99 days at double recommended doses (mean of 2017 and 2018 residue data). Measured endosulfan residues were evaluated against the dynamic plant uptake model dynamiCROP. The better fits were observed between modeled and measured residues for fruits (R2 from 0.84 to 0.96 and residual standard error (ER) between 0.6 and 1.47) as compared to leaves (R2 from 0.57 to 0.88). We also report fractions of endosulfan components ingested by humans after crop harvest. Intake fractions range from 0.0001-7.2 gintake/kg of applied pesticide. Our results can evaluate pesticide residues in different crops grown for human consumption, including their isomers and metabolites. They can be combined with dose-response information to evaluate human exposure and/or health risk assessment.

Provenances, preponderances, and distribution of humic acids and organic pollutants in hydro-geosphere: The co-existence, interaction and isotopic biomarkers in the riverine ecosystem.

This paper aims to critically review the importance of geochemical fingerprinting and tracing using biomarkers and stable isotopes in the riverine ecosystem and depicts that isotopic ratios of δ13C, δ15N, and δ34S can be used for tracing pollution sources. Stable isotopes like carbon, hydrogen, nitrogen, oxygen, and sulfur are being used for this purpose, and their isotopic signatures are primarily used to distinguish close sources of organic matter through dual isotopes. The present review is articulated to bridge the critical research gaps of the previous and contemporary documented literature on the genesis and transport of OM between freshwater and marine systems. This review comprehensively provides methods and techniques in geochemical tracing and discusses the future directions to address the challenges of the current methods to enhance the knowledge about the source identification of organic matter in the riverine environment. Tracer geochemistry emphasizes the implications of elemental abundances and isotope ratio variations in geologic substances to track natural earth processes, anthropogenic contaminants, and geochemical signatures in the hydrologic system. The principal constituent of organic matter comprises humic substances like humic acid, fulvic acid, and humin, and these comprise 50-75% of the sediments and DOC in natural waters. Their structural and functional characterization is required to elucidate the transport and fate of organic matter, which are often influenced by several paleoenvironmental factors.

Enantioselective Total Synthesis of [3]-Ladderanol through Late-Stage Organocatalytic Desymmetrization.

Ladderane phospholipids, with their unusual ladder-like arrangement of concatenated cyclobutane rings, represent an architecturally unique class of natural products. However, despite their fascinating structure and other necessary impetus, only a few synthetic studies of these molecules have been reported so far. We have now devised a concise total synthesis of [3]-ladderanol, a component of natural ladderane phospholipids, using an organocatalytic enantioselective desymmetrizing formal C(sp2 )-H alkylation. Our synthetic strategy rests on the late-stage introduction of chirality, thus allowing facile access to both enantiomers of [3]-ladderanol as well as an analogue. This is the first time a desymmetrization strategy is applied to the synthesis of [3]-ladderanol. The scope of this desymmetrizing C(sp2 )-H alkylation of meso-cyclobutane-fused cyclohexenediones is also presented.

Iridium-Catalyzed Enantioselective and Chemodivergent Allenylic Alkylation of Vinyl Azides for the Synthesis of α-Allenylic Amides and Ketones.

The first enantioselective synthesis of α-allenylic amides and ketones through allenylic alkylation of vinyl azides is reported. In these chemodivergent reactions, cooperatively catalyzed by a IrI /(phosphoramidite,olefin) complex and Sc(OTf)3 , vinyl azides act as the surrogate for both amide enolates and ketone enolates. The desiccant (molecular sieves) plays a crucial role in controlling the chemodivergency of this enantioconvergent and regioselective reaction: Under otherwise identical reaction conditions, the presence of the desiccant led to α-allenylic amides, while its absence resulted in α-allenylic ketones. Utilizing racemic allenylic alcohols as the alkylating agent, the overall process represents a dynamic kinetic asymmetric transformation (DyKAT), where both the products are formed with the same absolute configuration. To the best of our knowledge, this is the first example of the use of vinyl azide as the ketone enolate surrogate in an enantioselective transformation.