Unlocking growth potential: Synergistic potassium fertilization for enhanced yield, nutrient uptake, and energy fractions in Chinese cabbage.

The implementation of integrated potassium management presents a viable approach for augmenting plant growth, yield, and nutrient uptake while enhancing soil nutrient availability. A field experiment was executed during the rabi season of 2020, employing a randomized complete block design encompassing eight treatments involving standard (100%) and reduced (75% and 50%) rates of the recommended dose of potassium (RDK) administered through muriate of potash (MOP). Treatments included variations in the incorporation/exclusion of plant growth-promoting rhizobacteria (PGPR), farmyard manure (FYM) at 25% of potassium recommendation, and foliar application of nano potash. The use of 100% RDK +25% K augmentation through FYM + PGPR and nano K fertilizer spray at 25 and 40 DAS (T8) exhibited significant enhancements in green fodder yield (64.0 ± 2.2 t ha-1) over control with no potassium application (47.3 ± 3.7 t ha-1) and found at par with and 75% RDK + 25% K augmentation through FYM + PGPR and nano K fertilizer spray at 25 and 40 DAS (T7). These treatments yielded maximum percent increase for plant height (34.9%), leaf count (38.5%), leaf dimensions (28.8-31.5%), stem girth (25.84%), root volume (27.0%), and root length (37.64%), observed at the harvest stage compared to control (T1-no potassium application). The treatment T8 was on par with T7 and recorded highest uptake of macro (N, P, and K) and micro (Zn, Fe, Cu, and Mn) nutrients. While soil parameters such as available nitrogen and potassium levels were notably increased through the application of treatment T7 across various treatment combinations and found significantly superiority over treatment T8. Multivariate analysis also highlighted treatment T7 is more efficient in maintaining sustainability. Hence, based on the present findings it can be concluded that application of 75% RDK +25% K augmentation through FYM + PGPR and nano K fertilizer spray at 25 and 40 DAS (T7) can be recommended for achieving enhanced productivity and soil fertility improvement within agricultural systems.

Heptanuclear Mixed-Valence Co4IIICo3II Molecular Wheel─A Molecular Analogue of Layered Double Hydroxides with Single-Molecule Magnet Behavior and Electrocatalytic Activity for Hydrogen Evolution Reactions.

We present a bifunctional heptanuclear cobalt(II)/cobalt(III) molecular complex formulated as [Co7(µ3-OH)4(H2L1)2(HL2)2](NO3)6·6H2O (1) (where H5L1 is 2,2'-(((1E,1'E)-((2-hydroxy-5-methyl-1,3-phenylene)bis(methanylylidene))bis(azanylylidene))bis(propane-1,3-diol)) and H2L2 is 2-amino-1,3-propanediol). Compound 1 has been characterized by single-crystal X-ray diffraction analysis along with other spectral and magnetic measurements. Structural analysis indicates that 1 contains a mixed-valence Co7 cluster where a central Co(II) ion is connected to six different Co centers (four CoIII and two CoII ions) by four µ3-OH groups, giving rise to a planar heptanuclear cluster that resembles a molecular fragment of a layered double hydroxide (LDH). Two triply deprotonated (H2L1)3- ligands form the outer side of the cluster while two singly deprotonated (HL2)- ligands are located at the top and bottom of the central heptanuclear core. Variable temperature magnetic measurements indicate the presence of weak ferromagnetic CoII···CoII interactions (J = 3.53(6) cm-1) within the linear trinuclear CoII cluster. AC susceptibility measurements show that 1 is a field-induced single-molecule magnet (SMM) with τ0 = 8.2(7) × 10-7 s and Ueff = 11.3(4) K. The electrocatalytic hydrogen evolution reaction (HER) activity of 1 in homogeneous phase shows an overpotential of 455 mV, with a Faradaic efficiency of 81% and a TOF of 8.97 × 104 µmol H2 h-1 mol-1.

Co-N-C/C Bifunctional Electrocatalyst for Dual Applications in Seawater Electrolysis and Catalyst in Hydrazine Fuel Cells.

The convergence of water electrolysis and alkaline fuel cells offers captivating solutions for sustainably harvesting energy. The research explores both hydrazine-assisted seawater electrolysis (hydrazine oxidation reaction (HzOR) and hydrogen production reaction (HER)), as well as alkaline hydrazine fuel cell reactions (HzOR and Oxygen reduction reaction (ORR)) by using a bifunctional cobalt polyaniline derived (Co PANI/C) catalyst. The catalyst shows excellent performance for hydrazine-assisted seawater electrolysis in harsh seawater environments to produce H2 as fuel with nearly 85% Faradaic efficiency and during alkaline HzOR, the bifunctional catalyst generates H2 with 95% Faradaic efficiency by acting as both anode and cathode side catalyst. Also, the same catalyst requires only a potential of 0.34 V versus RHE and 0.906 V versus RHE for HzOR and ORR, respectively, in 1 m KOH, which makes this overall process useful for a Hz/O2 fuel cell.

Reducing the environmental impact of rice production in subtropical India by minimising reactive nitrogen loss.

The future of reactive nitrogen (N) for subtropical lowland rice to be characterised under diverse N-management to develop adequate sustainable practices. It is a challenge to increase the efficiency of N use in lowland rice, as N can be lost in various ways, e.g., through nitrous oxide (N2O) or dinitrogen (N2) emissions, ammonia (NH3) volatilization and nitrate (NO3-) leaching. A field study was carried out in the subsequent wet (2021) and dry (2022) seasons to assess the impacts of different N management strategies on yield, N use efficiency and different N losses in a double-cropped rice system. Seven different N-management practices including application of chemical fertilisers, liquid organic fertiliser, nitrification inhibitors, organic nutrient management and integrated nutrient management (INM) were studied. The application of soil test-based neem-coated urea (NCU) during the wet season resulted in the highest economic yield, while integrated nutrient management showed the highest economic yield during the dry season. Total N losses by volatilization of NH3, N2O loss and leaching were 0.06-4.73, 0.32-2.14 and 0.25-1.93 kg ha-1, corresponding to 0.06-5.84%, 0.11-2.20% and 0.09-1.81% of total applied N, respectively. The total N-uptake in grain and straw was highest in INM (87-89% over control) followed by the soil test-based NCU (77-82% over control). In comparison, recovery efficiency of N was maximum from application of NCU + dicyandiamide during both the seasons. The N footprint of paddy rice ranged 0.46-2.01 kg N-eq. t-1 during both seasons under various N management. Ammonia volatilization was the process responsible for the largest N loss, followed by N2O emissions, and NO3- leaching in these subtropical lowland rice fields. After ranking the different N management practices on a scale of 1-7, soil test-based NCU was considered the best N management approach in the wet year 2021, while INM scored the best in the dry year 2022.

Chemistry of a series of heterobimetallic complexes MnIII2(CaII/SrII)X2 (X = Cl-, Br-).

This manuscript describes the syntheses, structures and magnetism of MnIII-CaII/SrII complexes which are compositionally relevant in the context of the oxygen evolving complex (OEC) of photosystem II (PS II). A series of trimetallic tetraoxo complexes containing redox-inactive metal ions CaII or SrII were synthesized using a tetranucleating ligand framework. The structural characteristics of these complexes, with the oxido ligands bridging the redox-inactive metals and the manganese centres, make them particularly relevant to biological and heterogeneous metal-oxido clusters. Electrochemical studies of these compounds show that the reduction potentials are highly dependent upon the Lewis acidity of the redox-inactive metal, identifying the chemical basis for the observed differences in electrochemistry. This correlation provides insights into the role of the CaII/SrII ion in modulating the redox potential of the OEC and of other redox-inactive ions in tuning the redox potentials of other metal-oxide electrocatalysts. Temperature dependent magnetic measurements have also been performed for the complexes.

The synergy between electrochemical substrate oxidation and the oxygen reduction reaction to enable aerobic oxidation.

Aerobic substrate oxidation reactions catalyzed by a heterogeneous catalyst can be looked upon as two independent half-cell reactions, viz. anodic substrate oxidation and the cathodic oxygen reduction reaction (ORR). In this context, Fe PANI/C, a well-known catalyst for the ORR, is chosen to validate this hypothesis, wherein the anodic reaction is hydrazine oxidation. Fe PANI/C shows excellent activity in terms of the electrochemical ORR and hydrazine oxidation in both alkaline aqueous and non-aqueous media and taken together the aerobic oxidation efficacy of hydrazine-like small organic molecules is correlated with the electrochemical outcomes.

The Implications of Coupling an Electron Transfer Mediated Oxidation with a Proton Coupled Electron Transfer Reduction in Hybrid Water Electrolysis.

Invited for this month's cover are the groups of Menny Shalom at the Ben-Gurion University of the Negev, Israel and Dr. Biswajit Mondal at Indian Institute of Technology Gandhinagar, India. The image shows the connection between two half-cells: an electron transfer-mediated [(2,2,6,6-tetramethyl-1-piperidin-1-yl)oxyl] (TEMPO)-catalyzed benzylamine oxidation at the anode and a proton-coupled electron transfer at the cathode for hydrogen generation. The difference in pH dependence of the anodic and cathodic processes enables hybrid water electrolysis at low cell potential (∼1.0 V) by adjusting only the pH value of the electrolytic medium. The Research Article itself is available at 10.1002/cssc.202202271.

Dissociative reactions of [Au25(SR)18]- at copper oxide nanoparticles and formation of aggregated nanostructures.

Reactions between nanoclusters (NCs) have been studied widely in the recent past, but such processes between NCs and metal-oxide nanoparticles (NPs), belonging to two different size ranges, have not been explored earlier. For the first time, we demonstrate the spontaneous reactions between an atomically precise NC, [Au25(PET)18]- (PET = 2-phenylethanethiolate), and polydispersed copper oxide nanoparticles with an average diameter of 50 nm under ambient conditions. These interparticle reactions result in the formation of alloy NCs and copper-doped NC fragments, which assemble to form nanospheres at the end of the reaction. High-resolution electrospray ionization mass spectrometry (ESI MS), transmission electron microscopy (HR-TEM), electron tomography, and X-ray photoelectron spectroscopy (XPS) studies were performed to understand the structures formed. The results from our study show that interparticle reactions can be extended to a range of chemical systems, leading to diverse alloy NCs and self-assembled colloidal superstructures.

Molecular identification of Culicoides oxystoma and Culicoides actoni vectors of bluetongue virus.

Bluetongue is a non-contagious viral disease causing significant economic losses throughout the world. The bluetongue vectors Culicoides oxystoma and Culicoides actoni, which play a significant role in the transmission of various pathogens, are distributed across different geographical realms. Adults are minute in size with wide phenotypic variation, so morphology-based species identification is severely constrained by preparatory time and shortage of taxonomic expertise. To make the identification process rapid and effective, a specific primer was designed for the identification of C. actoni based on the multiple sequence alignment of ITS1 sequences of 11 Culicoides species. Along with this, a refined version of existing C. oxystoma specific primer was proposed. The primer sets distinguished C. oxystoma and C. actoni from a pooled sample consisting of other Culicoides species as well as closely related genera such as Forcipomyia and Alluaudomyia. Our findings suggest that the primers were species specific, sensitive and have potential to discriminate vector species C. oxystoma and C. actoni from pooled samples. To the best of our knowledge, these are the first ITS1 sequences generated and submitted in GenBank for Culicoides innoxius, Culicoides shortti, Culicoides palpifer and Culicoides anophelis and the first for Culicoides peregrinus, Culicoides fulvus and C. actoni from India.

Evaluation of crop research institutes under data and resource constraints: An alternative approach.

The evaluation of crop research institutes in the developing world under limited data availability has not been assessed in the past due to resource constraints. The paper assesses the social benefits of rice research taking the case of a research institute from India following a new approach. The area coverage of the varieties was estimated to be 3.4 million ha and the gain in production was 6.2 million tonnes per year in India. The additional return obtained due to the adoption of these varieties was about ₹ 14,621 million (US$ 232 million) per year at constant 2014-5 prices. The return per rupee investment in the institute's research and extension was ₹ 17. This approach is recommended for the impact evaluation of other crop research institutes in India and the developing world under resource constraints.

Tunable reactivity of silver nanoclusters: a facile route to synthesize a range of bimetallic nanostructures.

Quantized energy levels and unique optoelectronic properties of atomically precise noble metal nanoclusters (NCs) have made them important in materials science, catalysis, sensors, and biomedicine. Recent studies on the profound chemical interactions of such NCs within themselves and with ultrasmall plasmonic nanoparticles (NPs) indicate that depending on the size, shape, and composition of the second reactant, NCs can either take part in colloidal assembly without any chemical modifications or lead to products with atoms exchanged. Anisotropic NPs are a unique class of plasmonic nanomaterials as their sharp edges and protrusions show higher chemical reactivity compared to flat surfaces, often leading to site-specific growth of foreign metals and metal oxide shells. Here, using chemical interactions between gold nanotriangles (AuNTs) and Ag NCs of different compositions, we show for the first time that metal atom etching, alloying/atom exchange, and colloidal assembly can all happen at a particular length scale. Specifically, Ag25(DMBT)18 NCs (denoted as 1), upon reacting with AuNTs of ∼57 nm edge length, etch gold atoms from their sharp tips and edges. Simultaneously, the two nanosystems exchange metal atoms, resulting in Ag-doped AuNTs and AuxAg24-x(DMBT)18 (x = 1, 2). However, another Ag NC with the same metallic core, but a different ligand shell, namely, Ag25H22(DPPE)8 (denoted as 2), creates dendritic shells made of Ag, surrounding these AuNTs under the same reaction conditions. Furthermore, we show that in the case of a more reactive thiol-protected Ag NC, namely, Ag44(pMBA)30 (denoted as 3), gold etching is faster from the edges and tips, which drastically alters the identities of both the reactants. Interestingly, when the AuNTs are protected by pMBA, 3 systematically assembles on AuNTs through H-bonding, resulting in an AuNT core-Ag NC shell nanocomposite. Thus, while shedding light on various factors affecting the reactivity of Ag NCs towards AuNTs, the present study proposes a single strategy to obtain a number of bimetallic nanosystems of targeted morphology and functionality.

The Implications of Coupling an Electron Transfer Mediated Oxidation with a Proton Coupled Electron Transfer Reduction in Hybrid Water Electrolysis.

Electrolysis of water is a sustainable route to produce clean hydrogen. Full water-splitting requires a high applied potential, in part because of the pH-dependency of the H2 and O2 evolution reactions (HER and OER), which are proton-coupled electron transfer (PCET) reactions. Therefore, the minimum required potential will not change at different pHs. TEMPO [(2,2,6,6-tetramethyl-1-piperidin-1-yl)oxyl], a stable free-radical that undergoes fast electro-oxidation by a single-electron transfer (ET) process, is pH-independent. Here, we show that the combination of PCET and ET processes enables hydrogen production from water at low cell potentials below the theoretical value for full water-splitting by simple pH adjustment. As a case study, we combined the HER with the oxidation of benzylamine by anodically oxidized TEMPO. The pH-independent electrocatalytic oxidation of TEMPO permits the operation of a hybrid water-splitting cell that shows promise to perform at a low cell potential (≈1 V) and neutral pH conditions.

Spatial reorganization of analytes in charged aqueous microdroplets.

Imprinted charged aqueous droplets of micrometer dimensions containing spherical gold and silver nanoparticles, gold nanorods, proteins and simple molecules were visualized using dark-field and transmission electron microscopies. With such studies, we hoped to understand the unusual chemistry exhibited by microdroplets. These droplets with sizes in the range of 1-100 µm were formed using a home-built electrospray source with nitrogen as the nebulization gas. Several remarkable features such as mass/size-selective segregation and spatial localization of solutes in nanometer-thin regions of microdroplets were visualized, along with the formation of micro-nano vacuoles. Electrospray parameters such as distance between the spray tip and surface, voltage and nebulization gas pressure influenced particle distribution within the droplets. We relate these features to unusual phenomena such as the enhancement of rates of chemical reactions in microdroplets.

Photoelectrochemical alcohols oxidation over polymeric carbon nitride photoanodes with simultaneous H2 production.

The photoelectrochemical oxidation of organic molecules into valuable chemicals is a promising technology, but its development is hampered by the poor stability of photoanodic materials in aqueous solutions, low faradaic efficiency, low product selectivity, and a narrow working pH range. Here, we demonstrate the synthesis of value-added aldehydes and carboxylic acids with clean hydrogen (H2) production in water using a photoelectrochemical cell based solely on polymeric carbon nitride (CN) as the photoanode. Isotope labeling measurements and DFT calculations reveal a preferential adsorption of benzyl alcohol and molecular oxygen to the CN layer, enabling fast proton abstraction and oxygen reduction, which leads to the synthesis of an aldehyde at the first step. Further oxidation affords the corresponding acid. The CN photoanode exhibits excellent stability (>40 h) and activity for the oxidation of a wide range of substituted benzyl alcohols with high yield, selectivity (up to 99%), and faradaic efficiency (>90%).

Host preference of bluetongue virus vectors, Culicoides species associated with livestock in West Bengal, India: Potential relevance on bluetongue epidemiology.

Determination of host choice of Culicoides species (Diptera: Ceratopogonidae), the vectors of bluetongue virus (BTV), is pivotal to ascertain the role of each species in the transmission of pathogens, pest management and enumeration of disease prediction models. Host preference of livestock associated Culicoides midges was investigated in West Bengal, India with four replicates of a 3 × 3 Latin square design during August and September 2021. Adult Culicoides were mouth aspirated from three BTV hosts viz., cattle, sheep and goats. Mouth aspirating was validated by the sweep net collections. The host-baited collections recorded seven Culicoides species; with the highest landing rate on cattle (n = 5,667; 92.9%) followed by sheep (n = 365; 6.0%) and goat (n = 67; 1.1%). Based on the Jacob's selectivity index, all midge species, except for Culicoides fulvus Sen & Das Gupta, encountered, preferred cattle over other mammalian hosts. Culicoides oxystoma Kieffer, the subgenus Trithecoides Wirth & Hubert and Culicoides actoni Smith, predominated on the ventral region (belly/flank) of the cattle. However, Culicoides peregrinus Kieffer and C. actoni were observed to be prevalent in the leg region of sheep. A significantly higher percentage of female (99.9%) with only 0.3% of male were trapped in aspiration based animal baited collections. On the other hand sweep net and light trap catch comprises of 50.7%, 89.7% female and 49.2%, 10.2% male respectively. Surprisingly, DNA based blood meal analysis revealed human blood from the midges trapped in UV-LED light traps. Supplying the first evidence that Culicoides similis Carter, Ingram & Macfie, C. fulvus and Culicoides palpifer Das Gupta & Ghosh, feed on humans.

Strong and Elastic Membranes via Hydrogen Bonding Directed Self-Assembly of Atomically Precise Nanoclusters.

2D nanomaterials have provided an extraordinary palette of mechanical, electrical, optical, and catalytic properties. Ultrathin 2D nanomaterials are classically produced via exfoliation, delamination, deposition, or advanced synthesis methods using a handful of starting materials. Thus, there is a need to explore more generic avenues to expand the feasibility to the next generation 2D materials beyond atomic and molecular-level covalent networks. In this context, self-assembly of atomically precise noble nanoclusters can, in principle, suggest modular approaches for new generation 2D materials, provided that the ligand engineering allows symmetry breaking and directional internanoparticle interactions. Here the self-assembly of silver nanoclusters (NCs) capped with p-mercaptobenzoic acid ligands (Na4 Ag44 -pMBA30 ) into large-area freestanding membranes by trapping the NCs in a transient solvent layer at air-solvent interfaces is demonstrated. The patchy distribution of ligand bundles facilitates symmetry breaking and preferential intralayer hydrogen bondings resulting in strong and elastic membranes. The membranes with Young's modulus of 14.5 ± 0.2 GPa can readily be transferred to different substrates. The assemblies allow detection of Raman active antibiotic molecules with high reproducibility without any need for substrate pretreatment.

Evaluation of resting traps: An approach to understand resting biology of Culicoides spp. in backyard cattle shed.

Worldwide Culicoides biting midges transmit disease-causing agents that have significant economic impact on livestock industries. The aim of this study was to evaluate the sticky resting box traps to elucidate the resting behaviour of adult Culicoides in backyard cattle shed. Four different experiments were conducted over a six-month period based on types of resting box traps (material, colour, texture & height). During the study period 8870 individuals comprising 4046 (45.61%) males and 4824 (54.39%) females were collected. During the study period no significant preference was observed for the choice of resting box material (plywood & carton). For the colour experiment: adult Culicoides were retrieved from black box trap the most (21.15%) followed by blue (19.93%), red (17.84%), pink (14.06%), green (13.31%), yellow (7.21%) and the white (6.51%). Differential catch in the trap with surface texture (rough & smooth) was statistically significant (χ2 = 4.09, df = 1, P < 0.05). The highest proportion of males (n=987, 0.64) was recovered in the lower sticky resting box while the highest proportion of females (n=1318, 0.64) was collected in the upper sticky resting box during the study period. Sticky Resting Box (SRB) seems to be an effective tool for passive monitoring of resting adult vectors of Culicoides spp. prevalent in backyard sheds of West Bengal, India.

Blood meal analysis of Culicoides species associated with livestock in West Bengal, India.

Knowledge gaps exist on the feeding pattern and host range of bluetongue virus vectors, Culicoides species, associated with livestock in India. Adult midges were trapped with ultraviolet light traps at 13 household farms adjacent to human biotope. Host DNA was isolated from individual females (n = 101; blood engorged-82, gravid-4 and parous-15) and subjected to PCR amplification targeting CytB and 16S rRNA gene fragments followed by sequencing of amplified DNA samples. However, DNA sequences from only 71 individuals (70.3%) comprising of 10 Culicoides species were obtained. Blood meal analysis revealed at least 10 species that fed on five mammalian hosts including humans, but surprisingly none tested positive for birds. Results revealed that Culicoides innoxius tested positive for four not previously recognized species indicating a potential role as a vector species. Likewise, Culicoides shortti and Culicoides hegneri preferred goat and cattle respectively as hosts, whereas Culicoides palpifer preferred cattle along with buffalo as hosts, which is being reported for the first time. This is the first document on DNA-based blood meal identification and feeding preference of Culicoides midges associated with livestock in India.

Shell-Isolated Assembly of Atomically Precise Nanoclusters on Gold Nanorods for Integrated Plasmonic-Luminescent Nanocomposites.

In this work, we integrate atomically precise noble metal nanoclusters (NCs) on gold nanorods (AuNRs) to create hybrid plasmonic-luminescent nanomaterials. Initially, we assemble luminescent Ag29(LA)12 NC (LA = lipoic acid) to silica shell-encapsulated AuNRs. The resulting nanostructure shows plasmon-enhanced luminescence in aqueous medium as well as in the solid state. Atomic precision of the fluorophores used in this case allows detailed characterization of individual nanocomposites by diverse techniques, including transmission electron microscopy (TEM) and 3D electron tomographic reconstruction. We extend this strategy to prepare similar structures with gold NC protected with bovine serum albumin (Au30BSA). These two examples demonstrate the generic nature of the present strategy in preparing plasmonic-luminescent hybrid nanostructures using atomically precise NCs.

Chemical and Electrochemical O2 Reduction on Earth-Abundant M-N-C Catalysts and Implications for Mediated Electrolysis.

M-N-C catalysts, incorporating non-precious-metal ions (e.g. M = Fe, Co) within a nitrogen-doped carbon support, have been the focus of broad interest for electrochemical O2 reduction and aerobic oxidation reactions. The present study explores the mechanistic relationship between the O2 reduction mechanism under electrochemical and chemical conditions. Chemical O2 reduction is investigated via the aerobic oxidation of a hydroquinone, in which the O-H bonds supply the protons and electrons needed for O2 reduction to water. Mechanistic studies have been conducted to elucidate whether the M-N-C catalyst couples two independent half-reactions (IHR), similar to electrode-mediated processes, or mediates a direct inner-sphere reaction (ISR) between O2 and the organic molecule. Kinetic data support the latter ISR pathway. This conclusion is reinforced by rate/potential correlations that reveal significantly different Tafel slopes, implicating different mechanisms for chemical and electrochemical O2 reduction.