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Hexavalent chromium (CrVI) poses a serious risk to both human and environment health. Hence, a simple, robust, and efficient analytical method must be developed to monitor the presence of Cr(VI) in the environment. The current investigation concentrated on the colorimetric detection of Cr(VI) using TMB as indicator in the presence of H2O2. The study found that Cr(VI) reacts with H2O2 to generate hydroxyl radicals which oxidize TMB in a concentration dependent manner. Under optimized conditions, the method obtained a good linearity range (0.025-0.5 mg/L, r2 = 0.9944) with LOD and LOQ of 0.009 mg/L and 0.029 mg/L, respectively. The technique was further improved by the addition of EDTA in the sample preparation protocol to reduce the false positive result by the presence of ions like Cu2+, Fe3+, etc. The study recorded improved Cr(VI) recoveries (81.73-111.40 %) at different fortification levels (0.1-0.5 mg/L). Under optimized conditions, the EDTA added method obtained a good linear response (r2 = 0.9952) with a detection limit of 0.023 mg/L which is less than the prescribed limits by WHO (0.05 mg/L) and US EPA (0.1 mg/L) for drinking water. The developed analytical method is very simple without use of any nanomaterial and the results with natural water samples show that it has the potential for real-time detection of Cr(VI) in the environment.

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A general approach to Sceletium alkaloids of the family Aizoaceace following a key Johnson (orthoester)-Claisen rearrangement of an enantioenriched allylic alcohol has been disclosed. The tricyclic core (1c) of cis-3a-octahydroindoline skeleton was achieved via an ester-aminolysis followed by an intramolecular aza-Michael reaction with amine under elevated temperature. Utilizing aforementioned strategy, a collective total syntheses of Sceletium alkaloids, such as (-)-2-oxo-epimesembranol (1d) [the first total synthesis], (-)-6-epimesembranol (1b), and (-)-mesembrine (1a) were shown. Further this strategy was applied for total synthesis of (+)-dihydromaritidine (2c) sharing [5,11b]-ethanophenanthridine skeleton.

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Application of an aqueous Zn-ion battery is plagued by a water-induced hydrogen evolution reaction (HER), resulting in local pH variations and an unstable electrode-electrolyte interface (EEI) with uncontrolled Zn plating and side reactions. Here, 4-methyl pyridine N-oxide (PNO) is introduced as a redox non-innocent additive that comprises a hydrophilic bipolar N+-O- ion pair as a coordinating ligand for Zn and a hydrophobic ─CH3 group at the para position of the pyridine ring that reduces water activity at the EEI, thereby enhancing stability. The N+-O- moiety of PNO possesses the unique functionality of an efficient push electron donor and pull electron acceptor, thus maintaining the desired pH during charging/discharging. Intriguingly, replacing ─CH3 (electron pushing +I effect) by ─CF3 group (electron pulling ─I effect), however, does not improve the reversibility; instead, it degrades the cell performance. The electrolyte with 2 m ZnSO4 + 15 mm PNO enables symmetric cell Zn plating/stripping for a remarkable > 10 000 h at 0.5 mA cm-2 and exhibits coulombic efficiency (CE) ≈99.61% at 0.8 mA cm-2 in Zn/Cu asymmetric cell. This work showcases the immense interplay of the electron push-pull of the additives on the cycling.

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We report the asymmetric total synthesis of dixiamycin C (1) through the shrewd alliance of the naturally occurring monomer xiamycin A methyl ester (5) and its bromo derivative (31) following a late-stage Buchwald-Macmillan's C-N bond formation via a photoredox electron transfer approach with a less reactive carbazole nitrogen. The key step in the synthesis of monomer xiamycin A methyl ester (5) involves Buchwald's Pd(II)-mediated aerobic dehydrogenative C-N bond formation, Beckmann rearrangement, and ipso-acetylation of an electron-rich aromatic ring of an abietane core.

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Codeine and morphine are among the few natural products that are used directly as drugs for medical treatment. However, the availability of these is widely dependent on natural resources. Herein, we report an efficient enantioselective seven-step synthesis of (-)-codeine starting from simpler starting materials. The key steps involve microwave-assisted intramolecular cascade double heck cyclization to access the ABCE ring of opium alkaloids with the required stereocenters in one pot. A photoinduced intramolecular hydroamination of carboxamide forms the D ring and completes the pentacyclic core of the morphinans. Following that, an oxidation followed by global reduction leads to the formation of (-)-codeine. Our synthesis relies on simple and classical reactions to address the opium alkaloids and will serve as an efficient route to access the other morphinans.

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We have accomplished a unified strategy to achieve the structurally intriguing indolosesquiterpene alkaloids with diverse biological activity, xiamycin A (1a), xiamycin A methyl ester (1b) and oridamycins A (2a), and B (2b), which possesses a complex 6/6/6/5/6-fused pentacyclic skeleton bearing a carbazole moiety fused with a highly functionalized trans-decalin motif. Lewis acid-mediated epoxy-ene cyclization establishes the required pentacyclic scaffold with the installation of the four contiguous stereogenic centers. Further oxidative cleavage of the vinyl functionality, followed by successive functional group interconversions, completed the total synthesis of the indolosesquiterpene alkaloids.

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Biomass, an organic matter, has gained worldwide attention due to the overconsumption of fossil fuels. Biomass has emerged as a new alternative resource with implications for efficient energy production, environmental benefits and socio-economic impacts. According to the World Bioenergy Association, biomass has accounted for 14% of the energy supply in 2016 and is expected to provide 44% of the energy demand by 2030. This literary endeavour comprises insights into past developments, including biomass types, characterization methods and conversion technologies. This review article aims to facilitate a deeper understanding of agriculture biomass utilization and its significance in achieving sustainable development goals by analysing the latest research findings. Moreover, the emerging role of biosensors in optimizing biomass utilization and monitoring environmental impacts has been documented. The scope embraces the vast realm of bioenergy production, environmental mitigation and the generation of valuable by-products. In conclusion, portraying biomass conversion technologies as the transition towards cleaner, renewable energy, the potential benefits and challenges extend beyond energy production, encompassing effective agricultural residue management and the creation of valuable by-products. This review will guide the researchers and stakeholders towards a deeper understanding of the transformative potential embedded in biomass conversion processes for a sustainable and cleaner energy future.

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Due to the increase in urbanization and industrialization, the load of toxicants in the environment is alarming. The most common toxicants, including heavy metals and metalloids such as hexavalent Chromium, have severe pathophysiological impacts on humans and other aquatic biotas. Therefore, developing a portable rapid detection device for such toxicants in the aquatic environment is necessary. This work portrays the development of a field-portable image analysis device coupled with 3,3',5,5'-tetramethylbenzidine (TMB) as a sensing probe for chromium (VI) detection in the aquatic ecosystem. Sensor parameters, such as reagent concentration, reaction time, etc., were optimized for the sensor development and validation using a commercial UV-Vis spectrophotometer. The chemoreceptor integrated with a uniform illumination imaging system (UIIS) revealed the system's applicability toward Cr(VI) detection. The calibration curve using the R-value of image parameters allows Cr(VI) detection in the linear range of 25 to 600 ppb, which covers the prescribed permissible limit by various regulatory authorities. Furthermore, the adjusted R2 = 0.992 of the linear fit and correlation coefficients of 0.99018 against the spectrophotometric method signifies the suitability of the developed system. This TMB-coupled field-portable sensing system is the first-ever reported image analysis-based technology for detecting a wide range of Cr(VI) in aquatic ecosystems to our knowledge.

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Chemical and biological contaminants are of primary concern in ensuring seafood safety. Rapid detection of such contaminants is needed to keep us safe from being affected. For over three decades, immunoassay (IA) technology has been used for the detection of contaminants in seafood products. However, limitations inherent to antibody generation against small molecular targets that cannot elicit an immune response, along with the instability of antibodies under ambient conditions greatly limit their wider application for developing robust detection and monitoring tools, particularly for non-biomedical applications. As an alternative, aptamer-based biosensors (aptasensors) have emerged as a powerful yet robust analytical tool for the detection of a wide range of analytes. Due to the high specificity of aptamers in recognising targets ranging from small molecules to large proteins and even whole cells, these have been suggested to be viable molecular recognition elements (MREs) in the development of new diagnostic and biosensing tools for detecting a wide range of contaminants including heavy metals, antibiotics, pesticides, pathogens and biotoxins. In this review, we discuss the recent progress made in the field of aptasensors for detection of contaminants in seafood products with a view of effectively managing their potential human health hazards. A critical outlook is also provided to facilitate translation of aptasensors from academic laboratories to the mainstream seafood industry and consumer applications.

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A concise asymmetric total synthesis of naturally occurring Amaryllidaceae alkaloids sharing dihydrobenzofuran scaffolds, (-)-galanthamine (1a), (-)-lycoramine (1b), (-)-narwedine (2a), and (-)-lycoraminone (2b), is reported. Orthoester Johnson-Claisen rearrangement of allyl alcohol (+)-9 (98% ee) in diisopropylethylamine furnished enantioenriched cyclohexene (+)-8 (97.4% ee) with a quaternary stereogenic center.

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Soft ionotronics are emerging materials as wearable sensors for monitoring physiological signals, sensing environmental hazards, and bridging the human-machine interface. However, the next generation of wearable sensors requires multiple sensing capabilities, mechanical toughness, and 3D printability. In this study, a metal-organic framework (MOF) and three-dimensional (3D) printing were integrated for the synthesis of a tough MOF-based ionogel (MIG) for colorimetric and mechanical sensing. The ink for 3D printing contained deep eutectic solvents (DESs), cellulose nanocrystals (CNCs), MOF crystals, and acrylamide. After printing, further photopolymerization resulted in a second covalently cross-linked poly(acrylamide) network and solidification of MIG. As a porphyrinic Zr-based MOF, MOF-525 served as a functional filler to provide sharp color changes when exposed to acidic compounds. Notably, MOF-525 crystals also provided another design space to tune the printability and mechanical strength of MIG. In addition, the printed MIG exhibited high stability in the air because of the low volatility of DESs. Thereafter, wearable auxetic materials comprising MIG with negative Poisson's ratios were prepared by 3D printing for the detection of mechanical deformation. The resulting auxetic sensor exhibited high sensitivity via the change in resistance upon mechanical deformation and a conformal contact with skins to monitor various human body movements. These results demonstrate a facile strategy for the construction of multifunctional sensors and the shaping of MOF-based composite materials.

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Naturally occurring bis(cyclotryptamine) alkaloids feature vicinal all-carbon quaternary stereocenters with an elongated labile C-3a-C-3a' Sigma bond with impressive biological activities. In this report, we have developed a thio-urea catalyzed one-pot sequential Michael addition of bis-oxindole onto selenone to access enantioenriched dimeric 2-oxindoles with vicinal quaternary stereogenic centers at the pseudobenzylic position (up to 96% ee and >20 : 1 dr). This strategy has been successfully applied for the total syntheses of either enantiomers of chimonanthine, folicanthine, and calycanthine.

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The catalytic asymmetric synthesis of 3-allyl-3'-aryl 2-oxindoles has been shown via the Pd(0)-catalyzed decarboxylative allylation of allylenol carbonates. This methodology provides access to a variety of 2-oxindole substrates (5a-v) with all-carbon quaternary stereocenters (up to 94% ee) at the pseudobenzylic position under additive-free and mild conditions. The synthetic potential of this method was shown by the asymmetric synthesis of the tetracyclic core of the diketopiparazine-based alkaloid azonazine (11).

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We report on the development of a simple and cost-effective potentiometric sensor array that is based on manual "drawing" on the polymeric support with the pencils composed of graphite and different types of zeolites. The sensor array demonstrates distinct sensitivity towards a variety of inorganic ions in aqueous media. This multisensor system has been successfully applied to quantitative analysis of 100 real-life surface waters sampled in Mahananda and Hooghly rivers in the West Bengal state (India). Partial least squares regression has been utilized to relate responses of the sensors to the values of different water quality parameters. It has been found that the developed sensor array, or electronic tongue, is capable of quantifying total hardness, total alkalinity, and calcium content in the samples, with the mean relative errors below 18%.

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To fight against the present pandemic scenario of COVID-19 outbreak, medication with drugs and vaccines is extremely essential other than ventilation support. In this paper, we present a list of ligands which are expected to have the highest binding affinity with the S-glycoprotein of 2019-nCoV and thus can be used to make the drug for the novel coronavirus. Here, we implemented an architecture using 1D convolutional networks to predict drug-target interaction (DTI) values. The network was trained on the KIBA (Kinase Inhibitor Bioactivity) dataset. With this network, we predicted the KIBA scores (which gives a measure of binding affinity) of a list of ligands against the S-glycoprotein of 2019-nCoV. Based on these KIBA scores, we are proposing a list of ligands (33 top ligands based on best interactions) which have a high binding affinity with the S-glycoprotein of 2019-nCoV and thus can be used for the formation of drugs.

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Nitrogen-doped porous carbon (NPC) materials were successfully synthesized via a Zn-containing metal-organic framework (Zn-MOF). The resulting NPC materials are characterized using various physicochemical techniques which indicated that the NPC materials obtained at different carbonization temperatures exhibited different properties. Pristine MOF morphology and pore size are retained after carbonization at particular temperatures (600 °C-NPC600 and 800 °C-NPC800). NPC800 material shows an excellent surface area 1192 m2/g, total pore volume 0.92 cm3/g and displays a higher CO2 uptake 4.71 mmol/g at 273 k and 1 bar. Furthermore, NPC600 material displays good electrochemical sensing towards H2O2. Under optimized conditions, our sensor exhibited a wide linearity range between 100 µM and 10 mM with a detection limit of 27.5 µM.

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Catalytic cross-coupling of ketones and secondary alcohols with primary alcohols is reported. An abundant manganese-based pincer catalyst catalyzes the reactions. Low loading of catalyst (2 mol %) and catalytic use of a mild base (5-10 mol %) are sufficient for efficient cross-coupling. Various aryl and heteroaryl ketones are catalytically cross-coupled with primary alcohols to provide the selective α-alkylated products. Challenging α-ethylation of ketones is also attained using ethanol as an alkylating reagent. Further, direct use of secondary alcohols in the reaction results in in situ oxidation to provide the ketone intermediates, which undergo selective α-alkylation. The reaction proceeds via the borrowing hydrogen pathway. The catalyst oxidizes the primary alcohols to aldehydes, which undergo subsequent aldol condensation with ketones, promoted by catalytic amount of Cs2CO3, to provide the α,ß-unsaturated ketone intermediates. The hydrogen liberated from oxidation of alcohols is used for hydrogenation of α,ß-unsaturated ketone intermediates. Notably either water or water and dihydrogen are the only byproducts in these environmentally benign catalytic processes. Mechanistic studies allowed inferring all of the intermediates involved. Dearomatization-aromatization metal-ligand cooperation in the catalyst facilitates the facile O-H bond activation of both primary and secondary alcohols, and the resultant manganese alkoxide complexes produce corresponding carbonyl compounds, perhaps via ß-hydride elimination. The manganese(I) hydride intermediate plays dual role as it hydrogenates α,ß-unsaturated ketones and liberates molecular hydrogen to regenerate the catalytically active dearomatized intermediate. Metal-ligand cooperation allows all of the manganese intermediates to exist in same oxidation state (+1) and plays an important role in these catalytic cross-coupling reactions.

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Aluminium-based metal-organic framework (MOF) coatings on polystyrene bead surfaces were easily synthesized by reacting an intermediate metal hydroxide coating with an organic linker. Several different sizes of polystyrene beads were coated with aluminium metal hydroxide to construct Al@PS core-shell bead materials. The activated Al@PS core-shell beads were involved to make a homogenous MOF-based layer in the presence of the organic linker. By using different sizes of the PS support the size of MOFs on the PS composites could be fine-tuned under specific reaction conditions. MOF-coated core-shell bead materials (Al-1,4-NDC@PS and MIL-53(Al)@PS) were characterized using various analytical techniques. Al-1,4-NDC@PS and MIL-53(Al)@PS were evaluated for solid-phase microextraction (SPME) of hydrophobic polycyclic aromatic hydrocarbons (PAHs) and hydrophilic non-steroidal anti-inflammatory drugs (NSAIDs), respectively. Al-1,4-NDC@PS-1000 displayed high extraction recoveries ranging from 79.2 % to 99.8 % in the SPME of PAHs. Meanwhile, MIL-53(Al)@PS-1000 showed 85.9-99.0 % extraction recoveries in the SPME of NSAIDs. These results show that the proposed approach holds potential to extract organic analytes on an industrial scale.

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The colorimetric sensing technology has evolved into an essential tool for high-throughput analysis including portability and cost-effectiveness among available biomedical and agricultural screening approach. In this endeavor, the objective of work is to focus on the development of a field-portable instrument based on an Uniform Illumination Imaging System (UIIS), which will facilitate the colorimetric biochemical sensing. The developed field-portable, wavelength independent UIIS has been exploited for (a) rotavirus detection using commercial enzymatic immunoassay based microplate kit; (b) pesticide residue detection and quantification; The proposed system exhibited a good correlation in comparison to another two conventional techniques, i.e., multi-plate reader (r = 0.9991938) and LC-MS/MS (r = 0.998877399) with a short analysis time of 5 min for 95 test samples. Moreover, the feasibility of UIIS system has also been explored as field-portable enzyme-linked immunosorbent assay (ELISA) plate reader. By incorporating the Mahalanobis distance calculation, the advanced algorithm has been investigated and developed to analyze the data. The overall dataset was transformed into a matrix format to give a good correlation with a conventional plate reader, i.e., r = 0.915389612. Internet of things (IoT) enabled decision support system can be exploited by using big data analytics. Finally, test results can be shared with concerned stakeholders and the remote users. Thus, the developed UIIS will help to identify potential public health threats expeditiosly compared to conventional time consuming process of sample submission to the laboratory for analysis.

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Development of tamarind seed gum (TSG)-hydrolyzed polymethacrylamide-g-gellan (h-Pmaa-g-GG) composite beads for extended release of diclofenac sodium using 32 full factorial design is the main purpose of this study. The ratio of h-Pmaa-g-GG and TSG and concentration of cross-linker CaCl2 were taken as independent factors with three different levels of each. Effects of polymer ratio and CaCl2 on drug entrapment efficiency (DEE), drug release, bead size and swelling were investigated. Responses such as DEE and different drug release parameters were statistically analyzed by 32 full factorial design using Design-Expert software and finally the formulation factors were optimized to obtain USP-reference release profile. Drug release rate was found to decrease with decrease in the ratio of h-Pmaa-g-GG:TSG and increase in the concentration of Ca2+ ions in cross-linking medium. The optimized formulation showed DEE of 93.25% and an extended drug release profile over a period of 10h with f2=80.13. Kinetic modeling unveiled case-I-Fickian diffusion based drug release mechanism.

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