Organic Chelating Research Articles

Surface n-Doped Metal Halide Perovskite for Efficient and Stable Solar Cells through Organic Chelation.

Perovskite solar cells (PSCs) have emerged as a leading photovoltaic technology due to their high efficiency and low cost. Even though they have developed rapidly since their inception, with efficiencies of over 26%, inverted PSCs face challenges such as nonradiative recombination and ion migration. Surface treatment, especially the utilization of organic compounds, has improved efficiency and stability by optimizing the perovskite-charge transport layer interface. Herein, we report a facile and effective strategy by introducing 2,2'-bipyridyl to modify the surface of perovskite, achieving a power conversion efficiency of 24.43% with increasing open-circuit voltage and fill factor and good repeatability on multiple devices. We reveal that the 2,2'-bipyridyl molecule can chelate lead ions on the surface of perovskite, effectively suppressing nonradiative recombination. Furthermore, this modification can induce surficial n-doping to refine the energy level alignment, thereby minimizing charge transport losses. Additionally, the device maintained over 92% of the initial efficiency after 1000 h of operation at the maximum power point under continuous illumination. This surface chelation and defect passivation strategy employing 2,2'-bipyridyl offers a promising avenue for exploring the details of potential long-term degradation mechanisms and the development of commercially viable high-performance p-i-n PSCs.

Leveraging multi-omics tools to comprehend responses and tolerance mechanisms of heavy metals in crop plants.

Extreme anthropogenic activities and current farming techniques exacerbate the effects of water and soil impurity by hazardous heavy metals (HMs), severely reducing agricultural output and threatening food safety. In the upcoming years, plants that undergo exposure to HM might cause a considerable decline in the development as well as production. Hence, plants have developed sophisticated defensive systems to evade or withstand the harmful consequences of HM. These mechanisms comprise the uptake as well as storage of HMs in organelles, their immobilization via chemical formation by organic chelates, and their removal using many ion channels, transporters, signaling networks, and TFs, amid other approaches. Among various cutting-edge methodologies, omics, most notably genomics, transcriptomics, proteomics, metabolomics, miRNAomics, phenomics, and epigenomics have become game-changing approaches, revealing information about the genes, proteins, critical metabolites as well as microRNAs that govern HM responses and resistance systems. With the help of integrated omics approaches, we will be able to fully understand the molecular processes behind plant defense, enabling the development of more effective crop protection techniques in the face of climate change. Therefore, this review comprehensively presented omics advancements that will allow resilient and sustainable crop plants to flourish in areas contaminated with HMs.

Development and Application of a Chelating Acid for Water Injection Wells of Chang 6 Reservoir of An-Sai Oilfield

Abstract Ansai oilfield is a typical low permeability, low pressure, low yield and serious heterogeneity oilfield. Chang 6 play of Triassic YanChang Formation is a typical ultra-low permeability reservoir. The average porosity of the reservoir is 10 % ~ 14 %, and the average permeability is (0.2 ~ 4.0) × 10−3 μm2. The absolute content of clay minerals in the reservoir is relatively high, with an average content of 18.61 %. The main components are kaolinite, chlorite, illite and illite/montmorillonite interlayer. Due to the reservoir blockage caused by scaling, water sensitivity and formation particle migration in the process of water injection, high injection pressure and under injection wells is increasing dramatically. In view of the above challenges, a fit-for-purpose acid, which contains organic acids and chelating agents, was developed for injection pressure reduction and injection enhancement. It has the characteristics of strong dissolution, good retarding and corrosion inhibition performance. Corrosion rate is 0.5632 g / (m2·h) for J55 steel in 24h, and the core permeability increases by 74.57 % after acid flooding. It has been applied in field test of 3 wells in Chang 6 layer of Ansai oilfield since March 2024. The average daily injection volume increased by 37.87 %, and the validity period was more than 180 days.

High Throughput Manufacturing of Highly Ordered Mesoporous Thin Film Oxides for Hybrid-Polymer Nanocomposite Dielectrics

Highly ordered mesoporous metal oxide thin films have potential to become integrated into widely impactful dielectric materials due to the tunable properties of the oxide and its polymer filling; however, current manufacturing techniques to form the mesoporous oxide greatly limit scalable fabrication. Sol-gel mesoporous metal oxides generated via traditional processes require multi-day aging and high temperature, prolonged curing processes to yield controlled porosity at the expense of manufacturability. Moreover, high cost and unstable alkoxide precursors require precision over the solution precursor pH and subsequent thin film aging humidity after deposition.Solution combustion synthesis (SCS) is a next-generation method of generating metal oxides at reduced process temperatures (often <300 ºC) and using green precursors compared to the sol-gel approach. The metal oxide is typically produced from a metal nitrate, which provides both the metal cation and oxidant and an organic chelator fuel. The fuel acts to stabilize the cation against hydrolysis and to participate in the exothermic redox reaction that results in the metal oxide.Here, we present porogen integrated rapid oxidation (PIRO) which utilizes the principles of SCS to fabricate large-area mesoporous thin films of AlOx in less than 1 hour and at a temperature of 230 ºC. The PIRO method uses low-cost precursors to generate micelles with a controllable open-cell porosity ranging from ~30 – 60% and with varying degrees of closed-packed cubic ordering at a nearly 95% reduction in overall processing time. We show the precursor chemistry can be deposited via ultrasonic spray or blade coating at up to 6 m/min to manufacture large area mesoporous oxides and demonstrate filling of the porous AlOx with TOPAS® polymer to generate a hybrid nanocomposite with a dielectric constant of 6.26.

Comparative assessment of pantothenic, aspartic, ascorbic and tartaric acids assisted Pb-phytoextraction by sunflower (Helianthus annuus L.).

Phytoextraction of lead (Pb) is a challenging task due to its extremely low mobility within soil and plant systems. In this study, we tested the influence of some novel chelating agents for Pb-phytoextraction using sunflower. The Pb was applied at control (0.0278mM) and 4.826mM Pb as Pb(NO3)2 through soil-spiking. After 10days of Pb addition, four different organic ligands (aspartic, ascorbic, tartaric, and pantothenic acids) were added to the soil at 1mM concentration each. respectively. In the absence of any chelate, sunflower plants grown at 4.826mM Pb level accumulated Pb concentrations up to 104µgg-1 DW in roots, whereas 64µgg-1 DW in shoot. By contrast, tartaric acid promoted significantly Pb accumulation in roots (191µgg-1 DW; + 45.5%) and shoot (131.6µgg-1 DW; + 51.3%). Pantothenic acid also resulted in a significant Pb-uptake in the sunflower shoots (123µgg-1 DW; + 47.9%) and in roots (177.3µgg-1 DW; + 41.3%). The least effective amongst the chelates tested was aspartic acid, but it still contributed to + 40.1% more Pb accumulation in the sunflower root and shoots. In addition, plant growth, biochemical, and ionomic parameters were positively regulated by the organic chelates used. Especially, an increase in leaf Ca, P, and S was evident in Pb-stressed plants in response to chelates. These results highlight that the use of biocompatible organic chelates positively alters plant physio-biochemical traits contributing to higher Pb-sequestration in sunflower plant parts.

Preparation of copper glycinate and study of its effect on the germination of winter barley seeds

We analyzed the encrustation of winter barley seeds, which includes its preliminary treatment with cuprum glycinate, with the purpose of increasing yield and biochemical indicators of grain, and also improving the ecological condition of the soil. The objective of the research was to select methods for the synthesis of cuprum glycinate, study its chemical composition and the possibility of using this compound as a chelated micro-fertilizer for pre-sowing encrustation of winter barley seed as part of a tank mixture. Two well-known synthesis methods were used to obtain cuprum glycinate. The first method was the interaction between CuO with a solution of glycine during heating, during which pink metallic copper inclusions were noticed in the mixture of reaction products. It was found that it is expedient to synthesize the glycine complex of cuprum by the reaction of a suspension of Cu2CO3(OH)2 with glycine during heating (the yield is 97%), since a complex compound Cu(NH2CH2COO)2•H2O of sufficient purity is formed. The composition of the synthesized substance and the confirmation of the formula of the compound Cu(NH2CH2COO)2•H2O were obtained by determining the infrared and the atomic absorption spectrum of the aqueous solution. Based on the obtained differences in the atomic absorption spectra of the synthesized copper sulfate and copper glycinate the formation of the latter was confirmed. The IR spectrum confirms the formula of the complex compound and the formation of strong covalent bonds between the metal cation and the ligands. The study of the effect of cuprum glycinate on the germination of winter barley Tutankhamun seeds was carried out in comparison with the similar effect of a complex compound of cuprum with ethylenediaminetetraacetate. The study of the influence of cuprum glycinate on the germination of winter barley revealed positive results in which the germination exceeded the control by 9–27%. Winter barley seeds treated with distilled water served as a control. Treatment of winter barley seeds with an aqueous solution of cuprum glycinate in the amount of 20 g of cuprum per 1 ton of grain led to better germination than pre-treatment of seeds with a twice concentrated corresponding solution. Treatment with a complex compound of copper with ethylenediaminetetraacetate had no significant effect on the germination and characteristics of sprouts. The results of laboratory studies confirmed the feasibility of using complex compounds of biometal copper with organic chelating ligands as microfertilizers for pre-sowing seed encrustation, as they have high stability and sufficient solubility in water, are non-toxic, are better absorbed by plants and are considered cost-effective and environmentally safe.

Ocean iron cycle feedbacks decouple atmospheric CO2 from meridional overturning circulation changes

The ocean’s Meridional Overturning Circulation (MOC) brings carbon- and nutrient-rich deep waters to the surface around Antarctica. Limited by light and dissolved iron, photosynthetic microbes incompletely consume these nutrients, the extent of which governs the escape of inorganic carbon into the atmosphere. Changes in MOC upwelling may have regulated Southern Ocean outgassing, resulting in glacial-interglacial atmospheric CO2 oscillations. However, numerical models that explore this positive relationship do not typically include a feedback between biological activity and abundance of organic chelating ligands that control dissolved iron availability. Here, I show that incorporating a dynamic ligand parameterization inverts the modelled MOC-atmospheric CO2 relationship: reduced MOC nutrient upwelling decreases biological activity, resulting in scant ligand production, enhanced iron limitation, incomplete nutrient usage, and ocean carbon outgassing, and vice versa. This first-order response suggests iron cycle feedbacks may be a critical driver of the ocean’s response to climate changes, independent of external iron supply.

Depollution of Polymeric Leather Waste by Applying the Most Current Methods of Chromium Extraction.

The leather industry is one of the most polluting industries in the world due to the large amounts of waste following raw hide processing but also due to the high content of chemical substances present in leather waste. The main problem with chromium-tanned leather solid waste is related to the storage, due to the ability of chromium to leach into soil or water, and also owing to the high ability of trivalent chromium to oxidize to its toxic form, hexavalent chromium. The purpose of this article is to present the most current methods of chromium extraction from solid tanned leather waste in order to obtain non-polluting leather, which can constitute secondary raw material in new industrial processes. The extraction methods identified in the present study are based on acid/basic/enzymatic hydrolysis and substitution with the help of organic chelators (organic acids and organic acid salts). In addition, this study includes a comparative analysis of the advantages and disadvantages of each identified extraction method. At the same time, this study also presents alternative chromium extraction methods based on the combination of conventional extraction methods and ultrasound-assisted extraction.

Substrate uptake patterns shape niche separation in marine prokaryotic microbiome.

Marine heterotrophic prokaryotes primarily take up ambient substrates using transporters. The patterns of transporters targeting particular substrates shape the ecological role of heterotrophic prokaryotes in marine organic matter cycles. Here, we report a size-fractionated pattern in the expression of prokaryotic transporters throughout the oceanic water column due to taxonomic variations, revealed by a multi-"omics" approach targeting ATP-binding cassette (ABC) transporters and TonB-dependent transporters (TBDTs). Substrate specificity analyses showed that marine SAR11, Rhodobacterales, and Oceanospirillales use ABC transporters to take up organic nitrogenous compounds in the free-living fraction, while Alteromonadales, Bacteroidetes, and Sphingomonadales use TBDTs for carbon-rich organic matter and metal chelates on particles. The expression of transporter proteins also supports distinct lifestyles of deep-sea prokaryotes. Our results suggest that transporter divergency in organic matter assimilation reflects a pronounced niche separation in the prokaryote-mediated organic matter cycles.

Evaluation of highly conductive cermet cathodes synthesized with organic chelating agents and sintered at low temperatures for IT-SOFCs

A novel semi-organic combustion approach using orange and lemon juice as chelating agents is employed to synthesize the perovskite Sr0.8X0.2Co0.2Fe0.8O3-δ (x = La, Ce) cathode for IT-SOFCs. This approach has been found to exhibit lower toxicity compared to chemical routes and lower impurities compared to green routes. The structural analysis validated the successful synthesis of perovskite Sr0.8X0.2Co0.2Fe0.8O3-δ (La, Ce) cathode materials with no prominent secondary phase of impurities while surface morphology revealed a porous and well-connected network of particles. EDS confirmed the composition and thermo-gravimetric analysis showed weight losses related to the creation of vacancies. The functional groups were investigated through FTIR and the conductivity measurements revealed higher electrical conductivity for Sr0.8X0.2Co0.2Fe0.8O3-δ (x = La, Ce) synthesized with orange juice as a chelating agent with Sr0.8La0.2Co0.2Fe0.8O3-δ exhibiting slightly higher value compared to Sr0.8Ce0.2Co0.2Fe0.8O3-δ. The electrochemical performance showed the highest power density of 354 and 313 mW·cm−2 at 700 °C obtained for cells having Sr0.8X0.2Co0.2Fe0.8O3-δ (x = La, Ce) cathodes synthesized with orange juice which was attributed to better crystallinity and uniform lattice. This work shows that a novel semi-organic route is successfully employed to synthesize the perovskite cathode materials for IT-SOFCs.

Siderophore-mediated iron acquisition by Klebsiella pneumoniae.

Both commensal and pathogenic bacteria produce small organic chelators, called siderophores, that avidly bind iron and increase its bioavailability. Klebsiella pneumoniae variably produces four siderophores that antagonize host iron sequestration: enterobactin, glucosylated enterobactin (also termed salmochelin), aerobactin, and yersiniabactin, which promote colonization of different host tissues. Abundant evidence links bacterial iron acquisition to virulence and infectious diseases. The data we report explain the recognition and transport of ferric catecholates and other siderophores, which are crucial to iron acquisition by K. pneumoniae.

Enhanced heavy metal leaching from volcanic muds: Synergistic effects of citric acid and EDTA composite system

The soil leaching technology is a well-established technique commonly employed for the remediation of soils contaminated with heavy metals. Volcanic muds share similar properties to those of soil. This study utilizes soil leaching technology to tackle the presence of heavy metals in volcanic muds. It examines the leaching removal effect of the synergistic system of organic acid citric acid (CA) and chelating agent EDTA on heavy metals Pb, Cd, Cr, and Ni in volcanic muds. The leaching conditions were initially selected and subsequently optimized through the application of response surface methodology (RSM). The priority of leaching conditions can be ranked as follows: leaching duration is found to be more crucial than leaching agent concentration, which is noted to be more pivotal than the solid-liquid ratio. Following an in-depth evaluation of model predictions and experimental validation, it has been established that the optimal leaching concentration of EDTA is 0.15 mol·L−1, the optimal leaching duration is 9 h, and the optimal solid-liquid ratio is 1:10. For the compound CA, the most effective leaching concentration is 0.3 mol·L−1, the optimal leaching duration is 8 h, and the optimal ratio of solid to liquid is 1:10. The significance of the leaching conditions was further explored in conjunction with RSM. Furthermore, the integration of both leaching methods, namely combined leaching and stepwise leaching, has been demonstrated to amplify the removal efficiency of heavy metals, with stepwise leaching showing the highest removal rate. The experimental findings suggest that the leaching technique involving CA and EDTA composite system is an effective approach for the remediation of heavy metals such as Pb, Cd, Cr, and Ni in volcanic muds. This study provides theoretical rationale for the adoption of soil leaching technology in the remediation of heavy metals in volcanic muds. Additionally, the heavy metal content of the remediated volcanic muds substantially meets with the standards for cosmetic raw materials.

Unveiling Innovative Approaches to Mitigate Metals/Metalloids Toxicity for Sustainable Agriculture.

Due to anthropogenic activities, environmental pollution of heavy metals/metalloids (HMs) has increased and received growing attention in recent decades. Plants growing in HM-contaminated soils have slower growth and development, resulting in lower agricultural yield. Exposure to HMs leads to the generation of free radicals (oxidative stress), which alters plant morpho-physiological and biochemical pathways at the cellular and tissue levels. Plants have evolved complex defense mechanisms to avoid or tolerate the toxic effects of HMs, including HMs absorption and accumulation in cell organelles, immobilization by forming complexes with organic chelates, extraction via numerous transporters, ion channels, signaling cascades, and transcription elements, among others. Nonetheless, these internal defensive mechanisms are insufficient to overcome HMs toxicity. Therefore, unveiling HMs adaptation and tolerance mechanisms is necessary for sustainable agriculture. Recent breakthroughs in cutting-edge approaches such as phytohormone and gasotransmitters application, nanotechnology, omics, and genetic engineering tools have identified molecular regulators linked to HMs tolerance, which may be applied to generate HMs-tolerant future plants. This review summarizes numerous systems that plants have adapted to resist HMs toxicity, such as physiological, biochemical, and molecular responses. Diverse adaptation strategies have also been comprehensively presented to advance plant resilience to HMs toxicity that could enable sustainable agricultural production.

Synthesis of Metal Complexes of Substituted Isonicotinohydrazide and their Catalytic and Biological Activities

Coordination chemistry has fascinated and inspired chemists all over the world due to an increasing academic, industrial, and biological interest in metal complexes of organic chelating ligands. Among the chelating ligands, Schiff bases have attracted the attention of chemists due to ease of preparation and complexation. Numerous reports showed that a large number of isatin and its Schiff base metal complexes have excellent catalytic activity in a variety of reactions at mild reaction conditions and are used as homogeneous catalysts. Copper-based isatin complexes have found much attention because of their biological relevance. In this study, we report the synthesis of Schiff base metal complexes of substituted isonicotinohydrazide. The Schiff base, (C14H10N4O2) is prepared by condensing isoniazid with isatin. The complexes were synthesized in good yield from easily available metal precursors and characterized by UV-visible and FTIR spectroscopy. The Cu complex shows excellent activity for the C-N coupling reaction of the amination of aryl halides. All four complexes show better antibacterial activity as compared to their corresponding [M (acac)n] complexes. In addition to this, the Co and Cu complexes such as [Co(C14H10N4O2)3] and Cu(C14H10N4O2)3] respectively show negative growth, towards Fusarium, and Aspergillus i.e. showing antifungal activity. The results were compared with the standard acetyl-acetone complexes of the same metals.

Study on the scale inhibition performance of organic chelating agent aided by surfactants on CaCO3 at high salinity condition

Abstract The salt blockage layer formed in the wellbore during the development of high salinity oil and gas fields has a serious impact on the safety of oil and gas production of the oil and gas fields. CaCO3 is the main component of scale in high salinity oil and gas fields. Herein, focusing on CaCO3 as an example, the precipitation and scaling process as well as the change of crystalline form of CaCO3 under different temperature and salinity conditions were studied. The effects of two addition methods of organic chelating agent on the solubilization and dislodgement of CaCO3 under high salinity conditions were also explored. The optimal concentration of organic chelating agent is determined to be 1 % and 5 % for solubilization and dislodgement, respectively. It was found that the solubilization is achieved by inhibiting the stable and difficult to treat calcite crystal phase to generate more irregular and more dispersed aragonite CaCO3. Organic chelating agent contains a large number of carboxyl groups in its molecules, which can be adsorbed onto the surface of CaCO3 crystals through electrostatic adsorption. By chelating Ca2+ in stable and difficult to treat calcite CaCO3, the further ordered growth of the crystals is prevented, causing lattice distortion or large crystal rupture, thereby achieving dislodgement. This study will provide theoretical and technical support for the solubilization and dislodgement of salt blockage layer in wellbore at high salinity conditions.

Unlocking the phytoremediation potential of organic acids: A study on alleviating lead toxicity in canola (Brassica napus L.)

Soil contamination with toxic heavy metals [such as lead (Pb)] is becoming a serious global problem due to the rapid development of the social economy. Organic chelating agents such as maleic acid (MA) and tartaric acid (TA) are more efficient, environmentally friendly, and biodegradable compared to inorganic chelating agents and they enhance the solubility, absorption, and stability of metals. To investigate this, we conducted a hydroponic experiment to assess the impact of MA (0.25 mM) and TA (1 mM) on enhancing the phytoremediation of Pb under its toxic concentration of 100 μM, using the oil seed crop canola (Brassica napus L.). Results from the present study showed that the Pb toxicity significantly (P < 0.05) decreased plant growth and biomass, photosynthetic pigments, gas exchange attributes and nutritional contents from the roots and shoots of the plants. In contrast, toxic concentration of Pb significantly (P < 0.05) increased oxidative stress indicators in term of malondialdehyde, hydrogen peroxide, and electrolyte leakage, increased enzymatic and non-enzymatic antixoidants and their specific gene expression and also increased organic acid exudation patter in the roots of B. napus. In addition, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that Pb toxicity significantly affected double membranous organelles while Fourier-transform infrared (FTIR) spectroscopy showed an nveiled distinct peak variations in Pb-treated plants, when compared to control. Additionally, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that Pb toxicity significantly affected double-membrane organelles, while Fourier-transform infrared (FTIR) spectroscopy unveiled distinct peak variations in Pb-treated plants compared to the control. The negative impact of Pb toxicity can overcome the application of MA and TA, which ultimately increased plant growth and biomass by capturing the reactive oxygen species, and decreased oxidative stress in B. napus. With the application of MA and TA, the values of the bioaccumulation factor (BAF) and translocation factor (TF) exceeded 1, indicating that the use of MA and TA enhances the phytoremediation potential of B. napus under Pb stress conditions. This finding could be beneficial for field environment studies, especially when explored through in-depth genetic and molecular analysis.

Stabilization of heavy metals in municipal solid waste incineration fly ash using organic chelating agents: Insight into risk assessment and function mechanism

Landfill treatment of municipal solid waste incineration fly ash (MSWI FA) after stabilization is the primary disposal technology. However, only few studies have assessed the stability of MSWI-FA-chelated products in different landfill scenarios. In this study, three commonly used dithiocarbamate (DTC)-based organic chelating agents (CAs) (TS-300, SDD, and PD) were selected to stabilize heavy metals (HMs) in MSWI FA. In addition, the leaching toxicity and environmental risks of the chelated products were assessed in different disposal environments. The results demonstrate that the HM leaching concentrations of the chelated products met the concentration limits of the sanitary landfill standard (GB16889–2008; mixed Landfill Scenario) for the three CAs at a low additive level (0.3 %). However, in the compartmentalized landfill scenario (the leaching agent was acid rain), the leaching of HMs from the chelated products met the standard when TS-300, SDD, and PD were added at 1.5 %, 6.0 %, and 8.0 %, respectively. Additionally, Pb, Zn, and Cd in the chelated products from the 1.5 %-TS-300 and 6.0 %-SDD groups met the leaching limits within the pH ranges 6–12 and 7–12, 6–12 and 7–12, and 8–12 and 8–12, respectively. This was primarily due of TS-300's multiple DTC groups forming stable chain-like macromolecular chelates with Pb. However, although the environmental risks associated with Pb, Zn, and Cd in the initial (0-d) chelated products of the 1.5 %-TS-300 and 6.0 %-SDD groups were minimized to low and negligible levels, there was a significant increase in the leaching of the three HMs after 28 d of storage. Therefore, with appropriate CA addition, although the leaching concentration of HMs in the chelated product may comply with the GB16889–2008 standards, it remains essential to consider its environmental risk, particularly in highly acidic or alkaline environments and during prolonged storage of the product.

Systems biology of chromium-plant interaction: insights from omics approaches.

Plants are frequently subjected to heavy metal (HM) stress that impedes their growth and productivity. One of the most common harmful trace metals and HM discovered is chromium (Cr). Its contamination continues to increase in the environment due to industrial or anthropogenic activities. Chromium is severely toxic to plant growth and development and acts as a human carcinogen that enters the body by inhaling or taking Cr-contaminated food items. Plants uptake Cr via various transporters, such as sulfate and phosphate transporters. In nature, Cr is found in various valence states, commonly Cr (III) and Cr (VI). Cr (VI) is soil's most hazardous and pervasive form. Cr elevates reactive oxygen species (ROS) activity, impeding various physiological and metabolic pathways. Plants have evolved various complex defense mechanisms to prevent or tolerate the toxic effects of Cr. These defense mechanisms include absorbing and accumulating Cr in cell organelles such as vacuoles, immobilizing them by forming complexes with organic chelates, and extracting them by using a variety of transporters and ion channels regulated by various signaling cascades and transcription factors. Several defense-related proteins including, metallothioneins, phytochelatins, and glutathione-S-transferases aid in the sequestration of Cr. Moreover, several genes and transcriptional factors, such as WRKY and AP2/ERF TF genes, play a crucial role in defense against Cr stress. To counter HM-mediated stress stimuli, OMICS approaches, including genomics, proteomics, transcriptomics, and metallomics, have facilitated our understanding to improve Cr stress tolerance in plants. This review discusses the Cr uptake, translocation, and accumulation in plants. Furthermore, it provides a model to unravel the complexities of the Cr-plant interaction utilizing system biology and integrated OMICS approach.

Pervaporation dehydration of an isopropanol aqueous solution using microporous TiO2-SiO2-OCL (Organic chelating Ligand) composite membranes prepared under different firing conditions

Microporous TiO2-SiO2 composite membranes intended for use in the pervaporation dehydration of a water/isopropanol mixture were prepared via the sol–gel method using acetylacetone (ACA) as an organic chelating ligand (OCL). TiO2-SiO2-ACA sols were prepared by using titanium (IV) propoxide (TiTP), an alkoxide of Ti, tetraorthoethylsilicate (TEOS), an alkoxide of Si, and ACA, as a composite of TiO2 and SiO2 with coordinating OCL to Ti. The dried gels were fired at 300 °C under N2 or at 500 °C under air, and were analyzed via FT-IR. Both powders had Ti-O-Si bonds, however, OCL in the powder fired at 500 °C in air has decomposed and removed. The TiO2-SiO2-ACA sols were applied to alumina plates and fired at either 300 °C under N2 or at 500 °C under air to check the water-contact angle, which indicated that the OCL was retained on the plates fired at 300 °C under N2 and were more hydrophobic than when fired at 500 °C under air. TiO2-SiO2-ACA composite membranes were fabricated by coating either the TiO2-SiO2-ACA sol layer fired at 300 °C under N2 or that fired at 500 °C under air onto a TiO2-SiO2 intermediate layer with an α-alumina support. The pore sizes of both membranes were estimated via the NKP method for single-gas permeance at 200 °C. The mean pore sizes of the membranes fired under N2 at 300 °C and under air at 500 °C were 0.47 nm and 0.68 nm, respectively, which suggested the possibility of pore size control via firing conditions. Pervaporation tests of the TiO2-SiO2-ACA composite membranes in a water/isopropanol mixture (IPA: 90 wt%) showed that the membranes fired under air at 500 °C and under N2 at 300 °C had values for permeation flux of 0.90 and 0.13 kg/(m2 h) and separation factors of 667 and 98 at 50 °C, respectively. The higher permeation flux of the membrane fired under air at 500 °C was due to the influence of a larger pore size as well as to a more hydrophilic surface. On the other hand, the separation factor was also higher for the membrane fired under air at 500 °C, because the hydrophilic surface facilitated water permeation. These results indicate the possibility of using firing conditions to control both the pore size and the surface properties of microporous TiO2-SiO2-ACA composite membranes for use in PV separation.

The organic–inorganic dual anchoring strategy based on organic chelators and lacunary polyoxometalates for the preparation of efficient CoWS hydrodesulfurization catalysts

Designing catalysts with bimetallic intimate synergistic effects to enhance catalytic activity has always been a focused problem for hydrodesulfurization (HDS) systems. Efficient HDS catalysts with abundant CoWS active phases were prepared through novel organic–inorganic ligand dual anchoring strategy based on the organic chelating agents and lacunary polyoxometalates (POMs). Citric acid (CA) chelating agent and Co2+ promoter are pre-coordinated in the impregnating solution, the trivacant Keggin [SiW9O34]10- (SiW9) POMs attract the promoter through the nucleophilic oxygen groups at the vacant sites to form the CA-Co@SiW9 “sandwich-like” structure, which allows the organic chelator-promoter-active center to be intimate interaction in a single molecule, thus achieving atomic-scale Co-W proximity on the precursor. In the subsequent sulfidation process, CA delayed the reduction temperature of cobalt species, enabling more Co promoter to be anchored at the edge sites of WS2 clusters to form abundant CoWS active phases, which fully exerted the bimetallic intimate synergism in the HDS reaction. Furthermore, the carbon deposits generated from CA carbonation acted as secondary support weakening the interaction of active metals with Al2O3 support and increasing the sulfidation degree as well as the dispersion of active metals. As a result, the S-Co(CA)W/Al2O3 catalyst achieves a remarkable turnover frequencies (TOF) value of 1.24 × 10-3 s−1 in HDS reaction of dibenzothiophene (DBT). This dual anchoring method based on POMs inorganic ligand and organic chelator ligand provides a new idea for designing novel HDS catalysts.