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ABSTRACT Heterometallic d‐4f coordination complexes are of paramount interest in modern coordination chemistry because of their potential applications in organic light‐emitting devices and spintronic materials. Here we report the synthesis and thorough investigation of Ln and MLn (M = Zn, Cd; Ln = Sm, Eu, Gd, Tb) molecular complexes based on 2‐furancarboxylic acid anion (Hfur): [Ln2(NO3)2(fur)4(DME)2] (Ln = Eu, Gd, Tb; DME is dimethoxyethane) and [M2Ln2(NO3)2(fur)8(bpy)2] (M = Zn, Cd; Ln = Eu, Gd, Tb, Sm; bpy is 2,2′‐bipyridyl). The structure and isostructural nature of compounds were determined based on the single‐crystal and powder X‐ray diffraction data. The photophysical properties of the obtained compounds were studied in detail: The energies of the triplet levels of the furoate anion and d‐blocks {M(fur)2(bpy)} (M = Zn, Cd), the relaxation times of the excited states, and the quantum yields were determined. Critical step from Ln complexes to ZnLn and CdLn (Ln = Eu, Tb) is accompanied by an increase in quantum yields, which correlates with a change in the energy of the triplet level of the aromatic part of the complexes and with the results of quantum chemical calculations indicating different schemes for the origination of triplet levels in MLn compounds. [ABSTRACT FROM AUTHOR]

Soil phosphorus (P) availability is a crucial factor determining primary productivity in terrestrial ecosystem. Plant functional traits and microbes under P‐deficient conditions can respond positively to increase soil P bioavailability. Whether and/or how the fine‐root traits (FRTs) of deep‐rooted desert species affect the rhizosphere and bulk soil community of phoD‐harbouring bacteria and thus improve the availability of soil P, however, remains unclear.We conducted a three‐year artificial outdoor pot experiment of P supply using Alhagi sparsifolia Shap. (hereafter Alhagi) to address this gap. Fine‐root samples from 1‐ and 3‐year‐old Alhagi seedlings and samples of the rhizospheres and bulk soil were collected. High‐throughput sequencing, sequential extraction and root system scanning were used to determine soil phoD‐harbouring bacteria community, Hedley‐P fractions and the FRTs.Fine‐root surface area (RSA), specific root length, foliar Mn concentration (indicating the quantities of root carboxylates that are released) and acid phosphatase (APase) activity were significantly higher in the no‐P supply compared with the high‐P supply conditions. APase activity was significantly higher by 27%, but the foliar Mn concentration was remarkably lower by 26%, in the 3‐ than the 1‐year‐old seedlings. The rhizospheric concentrations of labile P, moderately labile P, inorganic P and organic P in the no‐P supply condition were 5%, 11%, 10% and 21% higher, respectively, in the 3‐ than the 1‐year‐old seedlings. RSA and the foliar Mn concentration were dominated root predictors for the rhizospheric phoD‐harbouring bacteria community for the 1‐year‐old seedlings, whereas fine‐root P concentration was the dominated root predictor for the rhizospheric and bulk soil phoD‐harbouring bacteria communities for the 3‐year‐old seedlings. Soil water content, as the most dominant soil factor driving the variation of phoD‐harbouring bacteria community, notably could not be ignored. FRTs were the main factors that directly and positively determined rhizospheric phoD‐harbouring bacteria community and thus influenced soil P availability, but bulk soil phoD‐harbouring bacteria community were dominated by inorganic P concentration. The importance of fine‐root morphological traits to soil P availability gradually increased as the plants grew.Overall, our results emphasize the significance of rhizospheric phoD‐harbouring bacteria determined by the effect of FRTs on the bioavailability of soil P. Read the free Plain Language Summary for this article on the Journal blog. Read the free Plain Language Summary for this article on the Journal blog. [ABSTRACT FROM AUTHOR]

Reversible cycling of sodium metal batteries (SMBs) is limited by Na dendrite growth, unstable solid‐electrolyte interphase (SEI) formation, and poor Na+ transport/de‐solvation kinetics, especially under the conditions of low‐temperature and fast‐charging. Here, a series of electrolytes for low‐temperature and fast‐charging SMBs by regulating the molecular structure of solvents is presented, in which ethyl acetate (EA) is selected as a baseline solvent, ethyl difluoroacetate (EDFA) and 2,2‐difluoroethyl acetate (DFEA) solvents are obtained by introducing difluorination group into EA molecule at different positions. It is found that the difluorination at the space‐position of oxygen in DFEA causes the lowest binding energy with Na+, which brings faster Na+ transport/de‐solvation ability in DFEA‐based electrolytes. In addition, more ionic aggregates (AGGs) structures are also observed in DFEA‐based electrolytes, leading to a stable inorganic‐rich SEI layer formed on the Na‐metal surface. Therefore, the optimal DFEA‐based electrolyte shows prolonged cycle life (>1500 h) in Na||Na cell and evidently improves cycle performance in the Na3V2(PO4)3 (NVP)||Na cell at −20 °C, achieving high discharge capacity (93.64 mAh g−1 at 0.5C) and ultra‐stable capacity retention (99.27% after 400 cycles). Furthermore, the NVP||Na cell also reveals outstanding fast‐charging ability at room temperature, showing capacity retention of 81.84% at 10C over 1000 cycles. [ABSTRACT FROM AUTHOR]

A novel 3D luminescent metal–organic framework (MOF) denoted as [Eu(BTA)0.5(H2BTA)0.5(H2O)]n (Cj-2) has been constructed from a π-conjugated ligand with a tetracarboxylate group, 1,2,4,5-benzenetetracarboxylic acid (BTA), via solvothermal synthesis. Structural analysis reveals that the Cj-2 framework is composed of tetranuclear secondary building units (SBUs) containing uncoordinated carbonyl groups which provide feasible recognition sites to interact with analytes. Cj-2 shows a trinodal (4,6,10)-connected 3D topological network consisting of tetranuclear SBUs. Cj-2 displays outstanding potential as a luminescent sensor for detecting o-NP and Cd2+ in DMF suspension, with remarkable sensitivity and selectivity through the luminescence quenching effect. Cj-2 displays excellent luminescence quenching behaviour in the presence of other competing interfering analytes and can be recycled at least four times for sensing o-NP and Cd2+. For Cd2+ ions, it is the host–guest interactions and for the nitroaromatic compounds, it is the competitive absorption of excitation energy and the electron transfer mechanism that are the probable mechanisms for such sensing processes. Moreover, visual fluorescent test papers based on Cj-2 were assembled and employed to selectively detect nitroaromatic compounds and metal ions. Based on the aforementioned results, Cj-2 can be considered as a potential luminescence sensor for detecting Cd2+ and o-NP. [ABSTRACT FROM AUTHOR]

In this study, we report the fabrication and characteristics of a self-healing polymer forming an ionically bonded network based on carboxylic acids and alkyl amines. The self-healing polymer forming an ionically bonded network is prepared from acrylic acid-containing carboxylic groups in the main chain and ammonium carboxylate salts derived from alkyl amines of varying lengths. The nature of the ion bonding between alkyl amines and carboxylic acids within the polymer matrix was analyzed using Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared Spectroscopy (FT-IR). The self-healing polymer, incorporating ionically bound entities like ammonium carboxylate salts, demonstrated 100% self-healing efficiency at room temperature overnight, in contrast to the reference polymer without ion bonding. Various lengths of alkyl amines used to form ammonium carboxylate salts exhibited remarkable properties such as over 500% elongation at break, adhesive strength exceeding 300 gf, and light transmittance of over 90%, all dependent on the length of the alkyl chain. [ABSTRACT FROM AUTHOR]

Quasi-2D nanomaterials such as semiconducting nanoplatelets (NPLs) have drawn considerable interest due to their tunable optical properties and large surface to volume ratios. Cadmium selenide (CdSe) NPLs are of particular fundamental interest since their thicknesses can be controlled with atomic precision using well-established solution-phase synthetic techniques. Additionally, their large surface area makes them especially susceptible to changes in the identity of the capping ligands and, therefore, good model systems for understanding surface chemistry. In the current work, we explore the role of these ligands in altering the lattice parameters and optical properties of CdSe NPLs. We build on prior research that has employed varying binding groups, including thiols, phosphonic acids, and halides, to demonstrate ligand-dependent optical bandgap changes and concomitant lattice distortions as determined by powder x-ray diffraction (PXRD). Our work investigates the correlations between ligand-induced optical and structural changes with a series of ligands that maintain a consistent carboxylic acid binding group, thus allowing us to probe secondary ligand effects. We perform ligand exchanges on oleic acid-capped CdSe NPLs with benzoic acids, cinnamic acids, and cyclohexanecarboxylic acid. In all cases, the optical bandgap decreases upon ligand exchange, and a correlated expansion in the thickness of the NPLs is observed via PXRD. We also observe that the benzoic acids produce larger optical and structural distortions than the cinnamic acids. We show that the optical and structural correlation is nearly quantitatively described by quantum confinement effects, with the thicker quantum wells exhibiting smaller energy gaps. [ABSTRACT FROM AUTHOR]

This work presents an extension of the projector operator embedding scheme of Manby et al. [J. Chem. Theory Comput. 8, 2564 (2012)] in a multicomponent (MC) framework. Here, a molecular system containing electrons and other types of quantum species is divided into a wavefunction (WF) subsystem of interest and a density functional theory (DFT) environment. The WF-in-DFT partition decreases computational costs by partially truncating the WF subsystem basis set at the cost of introducing a controllable embedding error. To explore the applicability of the MC extension, third-order propagator-in-DFT calculations were performed for positron–anion complexes for alkoxides and carboxylates with carbon chains of different sizes. For these systems, it was found that selecting a WF subsystem with the positron and only the oxygen atoms caused an error of 0.1 eV or lower in positron-binding energies, while reducing between 33% and 55% the basis set size. The reduction of computational costs achieved with the embedding scheme allowed us to improve molecular positron-binding energy predictions by performing complete basis set limit extrapolations. Combining the WF-in-DFT embedding and the complete basis set extrapolation, positronium aliphatic alkoxides were predicted to be energetically stable by 0.3 eV with respect to Ps emission. Similarly, positronium carboxylates, both aromatic and aliphatic, were predicted to be stable by 1.3 eV. [ABSTRACT FROM AUTHOR]

Abstract Converting waste into high-value products promotes sustainability by reducing waste and creating new revenue streams. This study investigates the potential of diverse yeasts for microbial oil production by utilizing short-chain fatty acids (SCFAs) that can be produced from organic waste and focuses on identifying strains with the best SCFA utilisation, tolerance and lipid production. A collection of 1434 yeast strains was cultivated with SCFAs as the sole carbon source. Eleven strains emerged as candidates with promising growth rates and high lipid accumulation. Subsequent fermentation experiments in liquid SCFA-rich media, which focused on optimizing lipid accumulation by adjusting the carbon to nitrogen (C/N) ratio, showed an increase in lipid content at a C/N ratio of 200:1, but with a concurrent reduction in biomass. Two strains were characterized by their superior ability to produce lipids compared to the reference strain Yarrowia lipolytica CECT124: Y. lipolytica EXF-17398 and Pichia manshurica EXF-7849. Characterization of these two strains indicated that they exhibit a biotechnologically relevant balance between maximizing lipid yield and maintaining growth at high SCFA concentrations. These results emphasize the potential of using SCFAs as a sustainable feedstock for oleochemical production, offering a dual benefit of waste valorisation and microbial oil production.

Two solvent-controlled Cd(II) compounds, formulated as {[Cd2(Htdc)4(µ-imyp)(H2O)4]} (1), [Cd2(µ2-tdc)2(µ-imyp)(DMF)2(H2O)2]n (2) (H2tdc= 2,5-thiophenedicarboxylic acid, imyp = 4-imidazol-1-yl-pyridine and DMF = N,N-dimethylformamide) have been synthesized by reactions of Cd(NO3)2·4H2O and H2tdc with imyp in different solvents, respectively. Both compounds were then characterized by single-crystal X-ray diffraction and other physicochemical methods. In 1, partially deprotonated Htdc− anion as terminal ligand and µ-imyp ligand connect Cd2+ ions to generate a discrete structure. In 2, completely deprotonated µ2 – tdc2− anions and µ-imyp ligand link Cd2+ ions into a 1D double chain structure. Both compounds display 3D supramolecular structures through hydrogen bonding interactions. The results provided interesting insights into solvent effects on the structural formation of compounds 1 and 2. In addition, the solid-state photoluminescent properties of compounds 1 and 2 were also investigated. Two solvent-controlled Cd(II) compounds have been synthesized by reactions of Cd(NO3)2·4H2O and 2,5-thiophenedicarboxylic acid with 4-imidazol-1-yl-pyridine in the different solvents. One compound is a discrete structure, while the other compound has a 1D double chain structure. The results provided interesting insights into solvent effects on the structural formation of compounds. [ABSTRACT FROM AUTHOR]

Once considered a metabolic waste product, today it is considered an important signaling molecule continuously forming under aerobic conditions. Lactate, a molecule primarily known as a byproduct of glycolysis, has gained importance in recent years due to its multifaceted role in various biological processes. Misconceptions surrounding lactate have persisted for centuries, especially the belief that elevated lactate levels were solely a result of low oxygen levels shaped early understanding. However, current research challenges this view and expands our comprehension of lactate's various roles. Unfortunately, despite all of the mentioned above lactate is rooted in modern society as a deterrent word and many people do not know its value in the human body, let alone clinical implementations or physical performance. The main goal of this review is to refresh current knowledge regarding lactate research and spread the overall information among a professional society. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal CrystEngComm, which focuses on the design and understanding of solid-state and crystalline materials. It includes a range of papers on various topics, such as photon upconversion, catalytic activity, structural diversity, and crystal stability. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document provides a list of papers and their authors, allowing library patrons to quickly identify articles of interest for their research. [Extracted from the article]

Halogen(I) complexes are widely used as halogenation reagents and traditionally feature homoleptic stabilising Lewis bases, though the recent revitalisation of iodine(I) carboxylate chemistry has provided isolable examples of heteroleptic iodine(I) complexes. This work reports iodine(I) pnictogenate complexes stabilised by a Lewis base (L), Ph2P(O)O─I─L, synthesised via cation exchange from the silver(I) precursor, (Ph2P(O)OAg)n. The complexes were characterised in both solution (1H, 1H-15N HMBC, 31P) and the solid state, and supplemented computationally by DFT studies. Interestingly, these iodine(I) pnictogenates demonstrate a range of stabilities, and have been found to excel as iodination reagents in comparison to carbonyl hypoiodites, with comparable reactivity to the eponymous Barluenga's reagent in the iodination of antipyrine. Iodine(I) carboxylates have been explored as iodination reagents, but the role of the carbonyl group in promoting such reactivity remains poorly understood. Here, the authors prepare iodine(I) pnictogenates and find that they excel as iodination reagents in comparison to iodine(I) carboxylates. [ABSTRACT FROM AUTHOR]

Phosphonate, as an effective flame‐retardant group, has a dynamic phosphonate exchange behavior similar to the transesterification of carboxylate; and introducing it into the network of epoxy resin (EP) is beneficial for solving the fire risk and waste disposal problems of EP in the meantime. Herein, a reprocessable and flame‐retardant epoxy vitrimer (EV) with dual dynamic covalent reactions of phosphonate and carboxylate transesterifications is constructed by introducing a phosphonate‐containing diol named GHPP into an epoxy‐anhydride curing system. The presence of the phosphonate makes the EV intrinsically flame‐retardant; meanwhile, both of the dynamic phosphonate and carboxylate transesterifications are accelerated by the abundant primary hydroxyl groups, which show much higher activity than the as‐generated β‐hydroxyls during curing, leading to enhanced dynamic properties of the EV. As a result, on the one hand, the EV achieves the UL‐94 V‐0 rating with a high limiting oxygen index value of 37.3%; and it shows a 41% reduction for the peak heat release rate and a 39% reduction for the total heat release in the cone calorimetry test. On the other hand, such EV exhibits rapid stress relaxation and is reprocessed easily to maintain its mechanical properties, thermal properties and flame retardancy to the hilt. [ABSTRACT FROM AUTHOR]

The coordination of anionic donors is involved at various stages of catalytic cycles in transition‐metal catalysis, but control over the spatial positioning of anions around a metal center is a challenge in coordination chemistry. Here we show that regioisomeric phosphine‐carboxylate ligands provide spatial anion control on palladium(II) centers by favoring either κ2, cis‐κ1, or trans‐κ1 coordination of the carboxylate donor. Additionally, the palladium(II) carboxylates, which contain a methyl donor, upon protonation, deliver metal‐alkyl complexes that feature a coordinated carboxylic acid. Such complexes can be considered as models for the minima that follow the concerted metalation‐deprotonation transition state for C−H activation. The predictability of the coordination modes is further demonstrated on silver(I) and copper(I) centers, for which less common structures of mononuclear and dinuclear complexes can be obtained by using spatial anion control. Our results demonstrate the potential for spatial control over carboxylate anions in coordination chemistry. [ABSTRACT FROM AUTHOR]

Based on the prior observation of the trifluoroacetate hypoiodite, CF3C(O)OI, demonstrating the largest σ‐hole of a neutral halogen bond donor, a series of mono‐ and bis‐carbonyl hypoiodites utilising trifluoromethyl or fluorine substituents at various positions of a parent benzoyl skeleton have been synthesised. The carbonyl hypoiodite complexes were prepared via cation exchange of the silver(I) cations with iodine(I) from the respective silver(I) carboxylates and dicarboxylates as the synthetic precursors. A range of pyridinic Lewis bases of varying nucleophilicities were used to stabilise the carbonyl hypoiodites to further probe their properties. The silver(I) intermediates with these Lewis bases were also isolated for silver(I) pentafluorobenzoate, providing additional insight into the cation exchange reaction. All complexes were characterised both in solution (1H, 1H‐15N HMBC, 19F) and in the solid state (SCXRD), permitting insights into the formation of the elusive pyridine‐iodine(I) cation. [ABSTRACT FROM AUTHOR]

Lanthanoid carboxylates were synthesized and in situ self‐assembled to illustrate temperature‐driven evolution in chromaticity. Evolution in structure (crystallinity), composition, luminosity, and chromaticity were investigated revealing the coupled role of divergence in order/structure (spatial organization), and composition in tuning observed color. Loss of crystallinity or increase in residual carbon leads to decrease in luminosity even with increase in hue. Comparing Ho and Er congeners shows that the density of accessible transition states relates to shifts in low and high wavelength components of color. This work demonstrates that, just as interface dipoles can lead to change in semiconductor band gap, structure and composition can analogously alter observed color. [ABSTRACT FROM AUTHOR]

The research of molecular capsules offers high application potential and numerous benefits in various fields. With the aim of forming supramolecular capsules which can be reversibly assembled and dissociated by simple external stimuli, we studied interactions between calixarenes containing urea and carboxylate moieties. To this end two ureido‐derivatives of p‐tert‐butylcalix[4]arene comprising phenylureido‐moieties and diacetate‐calix[4]arenes were prepared. The binding of acetate by ureido‐derivatives of calixarene in acetonitrile was characterized, revealing high affinity of ureido‐calixarenes for carboxylates. This suggested high potential for uniting the complementary calix[4]arenes via H‐bonds between carboxylic groups and urea moieties. The assembly of calixarenes was examined in detail by means of UV, 1H NMR, ITC, DOSY, MS, and conductometry providing insight in the structure‐stability relationship. The tetraureido‐calixarene derivative formed the most stable heterodimers with diacetate‐calix[4]arenes featuring practically quantitative association upon mixing the two calixarene counterparts. The possibility of controlling the formation of the heterodimer by protonating the carboxylates, thereby hindering the interactions critical for capsule assembly, was investigated. Indeed, the reversibility of breaking and re‐forming the heterodimer by addition of an acid and base to the solution containing urea‐ and carboxylate‐derivative calix[4]arene was demonstrated using NMR spectroscopy. [ABSTRACT FROM AUTHOR]

Compounds of three types, [LnL3(C2H5OH)] (Ln = Nd (I), Sm (II), Eu (III)), [LnL3(H2O)] (Ln = Gd (IV), Tb (V)), and [DyL2(NO3)(C2H5OH)2] (VI), were obtained by reactions of lanthanide nitrate with NaL (L– = 2,4-dichlorophenoxyacetate anion) in ethanol. The composition and structure of complexes I–VI were investigated by elemental and thermogravimetric analysis, IR spectroscopy, and X-ray diffraction (nos. 2311578 (I), 2311579 (II), 2311580 (III), 2311581 (IV), 2311582 (VI)). All compounds have a one-dimensional polymer structure in which metal atoms are connected by bridging carboxylate groups. The π–π interactions and intermolecular contacts between the chains give rise to a three-dimensional supramolecular structure. [ABSTRACT FROM AUTHOR]

A variety of 3-hydroxy-isoindolin-1-one derivatives were synthesized using the photodecarboxylative addition of carboxylates to phthalimide derivatives in aqueous media. Subsequent acid-catalyzed dehydration furnished 3-(alkyl and aryl)methyleneisoindolin-1-ones with variable E-diastereoselectivity in good to excellent overall yields. Noteworthy, the parent 3-phenylmethyleneisoindolin-1-one underwent isomerization and oxidative decomposition when exposed to light and air. Selected 3-hydroxy-isoindolin-1-one and 3-(alkyl and aryl)methyleneisoindolin-1-one derivatives showed moderate antibacterial activity that justifies future elaboration and study of these important bioactive scaffolds. [ABSTRACT FROM AUTHOR]

Carboxylates are ideal directing groups because they are widely available, readily cleavable and excellent linchpins for diverse follow-up reactions. However, their use in meta-selective C−H functionalizations remains a substantial unmet catalytic challenge. Herein, we report the ruthenium-catalyzed meta-C–H alkylation of aromatic carboxylic acids with various functionalized alkyl halides. A bidentate N-ligand increases the electron density at the metal center of ortho-benzoate ruthenacycles to the extent that single-electron reductions of alkyl halides can take place. The subsequent addition of alkyl radicals is exclusively directed to the position para to the CAr–Ru bond, i.e., meta to the carboxylate group. The resulting catalytic meta-C−H alkylation extends to a wide range of (hetero)aromatic carboxylic acids including benzofused five-membered ring heteroarenes but no pyridine derivatives in combination with secondary/tertiary alkyl halides, including fluorinated derivatives. It also allows site-selective C5−H alkylation of 1-naphthoic acids. The products are shown to be synthetic hubs en route to meta-alkylated aryl ketones, nitriles, amides, esters and other functionalized products. Carboxylates are ideal directing groups for aryl C–H functionalizations, given their wide availability and relative ease of functional group interconversion; however, their potential in meta-selective functionalizations has not been fully realized. Here, the authors use carboxylates for meta-selective alkylations via ruthenium catalysis. [ABSTRACT FROM AUTHOR]

A binuclear Co(II) complex, [Co2(PhBIMP)(μ‐O2CPh)(MeCN)]2+ (1) (PhBIMP is the anion of 2,6‐bis[(bis((N‐1‐methyl‐4,5‐diphenylimidazoylmethyl) amino)methyl]‐4‐methylphenol) catalyzes the hydrolysis of thiolates to the corresponding alcohols/phenols at room temperature. Hydrolysis of 11 different thiolates has been investigated with a catalyst loading of 4–6.7 mol% and with the highest TON values reaching 22. Furthermore, the effects of electron donating and electron withdrawing groups on the bridging benzoate of 1 have been investigated. The intermediates, products, and fate of the catalyst have been identified by mass spectrometric, gas chromatographic and gravimetric methods, and based on that, a mechanism for the catalytic cycle has been proposed. [ABSTRACT FROM AUTHOR]

A water oxidation catalyst Ru-bcs (bcs = 2,2′-bipyridine-6′-carboxylate-6-sulfonate) with a hybrid ligand was reported. Ru-bcs utilizes the electron-donating properties of carboxylate ligands and the on-demand coordination feature of sulfonate ligands to enable a low onset potential of 1.21 V vs. NHE and a high TOF over 1000 s−1 at pH 7. The adaptive chemistry uncovered in this work provides new perspectives for developing molecular catalysts with high efficiency under low driving forces. [ABSTRACT FROM AUTHOR]

A series of 4-ferrcenylbutyl carboxylate esters with different alkyl chain length (C2-C4) of carboxylic acids were synthesized using Fe3O4@SiO2@(CH2)3-Im-bisEthylFc[I] nanoparticles as catalyst and have been characterized with FT-IR, 1H NMR, and 13C NMR. Ferrocenyl-based esters were used as corrosion inhibitors of mild steel in the 1M HCl solution as corrosive media. The corrosion inhibition efficiency of the synthesized ferrocenyl-based esters has been assessed by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The 4-ferrocenylbutyl propionate showed a more effective corrosion inhibition behavior among the studied esters with 96% efficiency after immersion in the corrosive media for 2 weeks. The corrosion inhibition mechanism is dominated by formation of passive layer of inhibitor on the surface of the mild steel by adsorption. Moreover, the adsorption characteristics of 4-butylferrcenyl carboxylate esters on mild steel were thoroughly explored using density functional theory calculations. It was found that the Fe atoms located around the C impurity in the mild steel are the most efficient and active sites to adsorb 4-butylferrcenyl carboxylate esters. [ABSTRACT FROM AUTHOR]

Background: The need for addition of external electron donors such as ethanol or lactate impairs the economic viability of chain elongation (CE) processes for the production of medium-chain carboxylates (MCC). However, using feedstocks with inherent electron donors such as silages of waste biomass can improve the economics. Moreover, the use of an appropriate inoculum is critical to the overall efficiency of the CE process, as the production of a desired MCC can significantly be influenced by the presence or absence of specific microorganisms and their metabolic interactions. Beyond, it is necessary to generate data that can be used for reactor design, simulation and optimization of a given CE process. Such data can be obtained using appropriate mathematical models to predict the dynamics of the CE process. Results: In batch experiments using silages of sugar beet leaves, cassava leaves, and Elodea/wheat straw as substrates, caproate was the only MCC produced with maximum yields of 1.97, 3.48, and 0.88 g/kgVS, respectively. The MCC concentrations were accurately predicted with the modified Gompertz model. In a semi-continuous fermentation with ensiled sugar beet leaves as substrate and digestate from a biogas reactor as the sole inoculum, a prolonged lag phase of 7 days was observed for the production of MCC (C6–C8). The lag phase was significantly shortened by at least 4 days when an enriched inoculum was added to the system. With the enriched inoculum, an MCC yield of 93.67 g/kgVS and a productivity of 2.05 gMCC/L/d were achieved. Without the enriched inoculum, MCC yield and productivity were 43.30 g/kgVS and 0.95 gMCC/L/d, respectively. The higher MCC production was accompanied by higher relative abundances of Lachnospiraceae and Eubacteriaceae. Conclusions: Ensiled waste biomass is a suitable substrate for MCC production using CE. For an enhanced production of MCC from ensiled sugar beet leaves, the use of an enriched inoculum is recommended for a fast process start and high production performance. [ABSTRACT FROM AUTHOR]

A method for the synthesis of 1,4-dihydroquinoline-3-carbonyl compounds from 2-benzoyl-3-[2-(dialkylamino)aryl]acrylates via the sequence of 1,5-hydride shift, dealkylation, and cyclization processes was proposed. The reaction products contained a push-pull enamine fragment. [ABSTRACT FROM AUTHOR]

An innovative green procedure has been devised to prepare derivatives of 1,4‐dihydropyridine (1,4‐DHP). This method works with a catalyst process using ethanol as solvent under microwave irradiation conditions, enabling swift reactions (<30 min) with impressive yields (90%–96%). It contributes to an environmentally friendly and easily executable process by using the energy efficiency method. Within 30 min, this method underscores ecologically conscious practices and offers simple purification, streamlining the process by omitting column chromatography. This method highlights the efficacy and eco‐friendly nature of synthesizing 1,4‐DHPs. This method combines four component reactions, utilizing EtOH as the solvent and triethylamine as the catalyst. Furthermore, the product was characterized by diverse spectroscopic analysis. [ABSTRACT FROM AUTHOR]

A dinuclear copper (II) complex, Cu2 (RCOO)4(L)2 (1) while [RCOO = benzoate, L = 2-amino-3-chloro-5-trifluoro methyl pyridine], with square pyramidal geometry with four carboxylate bridged groups has been reported. This dinuclear copper (II) unit (with the most robust, frequently occurring paddle wheel structure) was characterized by single crystal X-ray diffraction, IR, UV, CV, TGA, and EPR studies. It exhibits catechol oxidase activity in methanol medium and the catecholase activity was monitored by the UV–Vis spectroscopy. The kinetic parameters have been determined by using Michaelis–Menten equation which shows that the complex is an efficient catalyst with very high turnover number. Preliminary mechanistic investigation of the catalytic behavior was established with the help of ESI–MS spectra. [ABSTRACT FROM AUTHOR]

The oxidation of tetra‐n‐butylammonium acetate, propionate, and pivalate was studied in rigorously anhydrous acetonitrile by conventional linear sweep and convolution voltammetry (LSV and ConV, respectively). The results suggest oxidation occurs via a concerted dissociative electron transfer pathway (RCO2−→R⋅+CO2+e−). The addition of water lowers the intrinsic barrier, signaling a possible change in mechanism to stepwise dissociative electron transfer. In rigorously dry acetonitrile, the oxidation potentials of CH3CO2− (0.60±0.09), CH3CH2CO2−, (0.47±0.05) and (CH3)3CCO2− (0.40±0.04 V vs. Ag/AgNO3 (CH3CN, 0.1 M)) are reported. These values parallel the stabilities of the resulting free radicals, consistent with a possible concerted pathway, although differential solvation of the carboxylate anions cannot be completely excluded as a contributor to this trend. [ABSTRACT FROM AUTHOR]

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Paired redox‐neutral electrolysis offers an attractive green platform for organic synthesis by avoiding sacrificial oxidants and reductants. Carboxylates are non‐toxic, stable, inexpensive, and widely available, making them ideal nucleophiles for C−C cross‐coupling reactions. Here, we report the electro/Ni dual‐catalyzed redox‐neutral decarboxylative C(sp3)−C(sp2) cross‐coupling reactions of pristine carboxylates with aryl bromides. At a cathode, a NiII(Ar)(Br) intermediate is formed through the activation of Ar−Br bond by a NiI‐bipyridine catalyst and subsequent reduction. At an anode, the carboxylates, including amino acid, benzyl carboxylic acid, and 2‐phenoxy propionic acid, undergo oxidative decarboxylation to form carbon‐based free radicals. The combination of NiII(Ar)(Br) intermediate and carbon radical results in the formation of C(sp3)−C(sp2) cross‐coupling products. The adaptation of this electrosynthesis method to flow synthesis and valuable molecule synthesis was demonstrated. The reaction mechanism was systematically studied through electrochemical voltammetry and density functional theory (DFT) computational studies. The relationships between the electrochemical properties of carboxylates and the reaction selectivity were revealed. The electro/Ni dual‐catalyzed cross‐coupling reactions described herein expand the chemical space of paired electrochemical C(sp3)−C(sp2) cross‐coupling and represent a promising method for the construction of the C(sp3)−C(sp2) bonds because of the ubiquitous carboxylate nucleophiles and the innate scalability and flexibility of electrochemical flow‐synthesis technology. [ABSTRACT FROM AUTHOR]

This review presents an overview of the biological applications of coordinative compounds based on unsaturated carboxylates accompanied by other ligands, usually N-based heterocyclic species. The interest in these compounds arises from the valuable antimicrobial and antitumor activities evidenced by some species, as well as from their ability to generate metal-containing polymers suitable for various medical purposes. Therefore, we describe the recently discovered aspects related to the synthesis, structure, and biological activity of a wide range of unsaturated carboxylate-containing species and metal ions, originating mostly from 3d series. The unsaturated carboxylates encountered in coordinative compounds are acrylate, methacrylate, fumarate, maleate, cinnamate, ferulate, coumarate, and itaconate. Regarding the properties of the investigated compounds, it is worth mentioning the good ability of some to inhibit the development of resistant strains or microbial biofilms on inert surfaces or, even more, exert antitumor activity against resistant cells. The ability of some species to intercalate into DNA strands as well as to scavenge ROS species is also addressed. [ABSTRACT FROM AUTHOR]

Interaction of the pre-organized complex of iron(II) trimethylacetate and 1,10-phenanthroline (phen) [Fe2(piv)4(phen)2] (1) (piv = (Me)3CCO2−)) with 1,6-diaminohexane (dahx) in anhydrous acetonitrile yielded a 1D coordination polymer [Fe3O(piv)6(dahx)1.5]n (2) and an organic salt of pivalic acid (H2dahx)(piv)2 (3). The structure of the obtained compounds was determined by single-crystal X-ray diffraction analysis. The phase purity of the complexes was determined by powder X-ray diffraction analysis. According to the single-crystal X-ray analysis, coordination polymer 2 is formed due to the binding of a triangular carboxylate core {Fe3(μ3-O)(μ-piv)6} with an aliphatic diamine ligand. Thermal behavior was investigated for compounds 1 and 2 in an argon atmosphere. [ABSTRACT FROM AUTHOR]

3D coordination polymers of Zn(II) with 2,5-diiodoterephthalate linkers (DMA)2[Zn(2,5-I-bdc)2]·1.5DMF (1) and K2[Zn(2,5-I-bdc)2]·2DMF (2) (2,5-I-bdc = 2,5-diiodoterephthalate) are prepared; their structure is established by XRD. [ABSTRACT FROM AUTHOR]

Metalloproteins are ubiquitous in all living organisms and take part in a very wide range of biological processes. For this reason, their experimental characterization is crucial to obtain improved knowledge of their structure and biological functions. The three‐dimensional structure represents highly relevant information since it provides insight into the interaction between the metal ion(s) and the protein fold. Such interactions determine the chemical reactivity of the bound metal. The available PDB structures can contain errors due to experimental factors such as poor resolution and radiation damage. A lack of use of distance restraints during the refinement and validation process also impacts the structure quality. Here, the aim was to obtain a thorough overview of the distribution of the distances between metal ions and their donor atoms through the statistical analysis of a data set based on more than 115 000 metal‐binding sites in proteins. This analysis not only produced reference data that can be used by experimentalists to support the structure‐determination process, for example as refinement restraints, but also resulted in an improved insight into how protein coordination occurs for different metals and the nature of their binding interactions. In particular, the features of carboxylate coordination were inspected, which is the only type of interaction that is commonly present for nearly all metals. [ABSTRACT FROM AUTHOR]

Investigating the reversible structural transformation of stimuli‐responsive metal–organic frameworks (MOFs) through single‐crystal diffraction and establishing a structure–property relationship pose a significant challenge. Herein, the controllable synthesis of Co‐MOF‐1 and Co‐MOF‐2 by incorporating water into the solvothermal synthesis process is presented. In comparison to the trinuclear [Co3(COO)8]2− clusters found in Co‐MOF‐1, Co‐MOF‐2 presents a variable dinuclear [Co2(COO)4(H2O)5] cluster. Single crystal diffraction studies, utilizing synchrotron radiation, confirm the reversible two‐step transformation. The presence of various organic solvents induces the single‐crystal‐to‐single‐crystal (SC‐to‐SC) transformation of Co‐MOF‐2. This transformation is initiated by the cleavage of three coordinated water molecules and subsequent coordination of carboxylates in the ligand, resulting in solvatochromic behavior. Further, the reversible stimuli‐responsive behavior can also be rapidly induced under the stimuli of heat, vacuum, and X‐rays. This study successfully demonstrates the crystallographic and spectroscopic snapshots of dynamic coordination bonds in MOFs and contributes to a deeper understanding of the structure–property relationship. [ABSTRACT FROM AUTHOR]

Layered double hydroxides (LDHs) are fascinating clay-like materials that display versatile properties, making them an extremely fertile playground for diverse applications, ranging from bio-compatible materials to the pharmaceutical industry to catalysis and photocatalysis. When intercalating organic and bio-organic species between the inorganic layers, such materials are named hybrid LDHs. The structure–property relation in these systems is particularly relevant, since most of the properties of the materials may be fine-tuned if a comprehensive understanding of the microscopic structure in the interlamellar space is achieved, especially with respect to the reorganization under water uptake (swelling). In this work, we combined experiments and simulations to rationalize the behavior of LDHs intercalating three carboxylates, the general structure of which can be given as [ Mg 4 Al 2 (OH) 12 ] A 2 − · XH 2 O (with A 2 − = succinate, aspartate, or glutamate and X representing increasing water content). Following this strategy, we were able to provide an interpretation of the different shapes observed for the experimental water adsorption isotherms and for the evolution of the infrared carboxylate band of the anions. Apart from small differences, due to the different reorganization of the conformational space under confinement, the behavior of the two amino acids is very similar. However, such behavior is quite different in the case of succinate. We were able to describe the different response of the anions, which has a significant impact on the isotherm and on the size of the interlamellar region, in terms of a different interaction mechanism with the inorganic layer. [ABSTRACT FROM AUTHOR]

In this work, a novel strategy for the straightforward synthesis of quinoline and quinazoline‐substituted carboxylates is described. The reaction between substituted (4‐oxo‐3‐phenyl‐1,3‐thiazolidin‐2‐ylidene)acetates and substituted α,α‐dicyanoolefins is explored, with a focus on the effects of substituents. The process involves a base‐mediated Michael addition, cleavage of C−C bonds, intramolecular cyclization, [1,5]‐H shift, and aromatization. The benefits of this process include high efficiency, mild reaction conditions, simplicity, and a wide range of products. To the best of our knowledge, there are no previous reports for the synthesis of these classes of quinoline and quinazoline‐substituted carboxylate derivatives. [ABSTRACT FROM AUTHOR]

A semi-flexible imidazole-based urea ligand, 1-(3-(1H-imidazol-1-yl)propyl)-3-phenylurea, and three zincdicarboxylate coordination polymers possessing the ligand were synthesized and characterized. The stoichiometry and coordination number of the zinc(II) ions in the coordination polymers were found to be dependent on the positional isomers of the benzene dicarboxylate. The 1,3-benzenedicarboxylate-based coordination polymer has a one-dimensional structure, whereas, the one possessing 1,4-benzenedicarboxylate has a two-dimensional architecture. The solvent used in the synthesis of the zinc-1,3-benzenedicarboxylate coordination polymer with the ligand played a decisive role on the solvation and conformation of the ligand. The anhydrous form was obtained from a reaction in methanol in which one of the urea moieties has a puckered geometry and the assembly has layers from one-dimensional bunches of coordination chains. However, the same reaction in ethanol provided a solvate having water and ethanol as the solvents of crystallization and it has the two ligands with a stretched geometry forming a cleft-like geometry to include the ethanol molecules. The two forms were not inter-convertible. The coordination polymer with 1,4-benzenedicarboxylate has a 2-dimensional structure with 2 × 2 grids having self-included urea that held DMF molecules by hydrogen bonds. [ABSTRACT FROM AUTHOR]

In the title compound, C20H17BrO5S, molecules are connected by intermolecular C--H...S hydrogen bonds with R22(10) ring motifs, forming ribbons along the baxis direction. C--H...π interactions consolidate the ribbon structure while van der Waals forces between the ribbons ensure the cohesion of the crystal structure. According to a Hirshfeld surface analysis, H...H (40.5%), O...H/H...O (27.0%), C...H/H...C (13.9%) and Br...H/H...Br (11.7%) interactions are the most significant contributors to the crystal packing. The thiophene ring and its adjacent dicarboxylate group and the three adjacent carbon atoms of the central hexene ring to which they are attached were refined as disordered over two sets of sites having occupancies of 0.8378 (15) and 0.1622 (15). The thiophene group is disordered by a rotation of 180° around one bond. [ABSTRACT FROM AUTHOR]

Hybrid systems with antioxidant properties have been developed by integrating bioactive compounds derived from plant resources with layered double hydroxides (LDHs). Anion exchange has been used to substitute intercalated nitrate anions in Mg-Al LDH with carboxylate anions derived from trans-ferulic acid, rosmarinic acid, and 18β-glycyrrhetinic acid. These organic compounds are known for their powerful antioxidant, anti-inflammatory and antimicrobial properties and are highly suitable for cosmetics, biomedicine, and food packaging. To enhance sustainability, a multistage procedure has been developed with the aim of recovering unexchanged carboxylate anions from residual reaction water, ensuring an environmentally friendly and easily scalable preparation process. The process, adapted for each of the three molecules, allows the production of a consistently high-quality hybrid product containing an organic fraction ranging from 10 to 48% by weight, depending on the specific molecule used. The immobilization of organic compounds has occurred either within the layers of LDH through intercalation or on the external surface through adsorption. Good antioxidant capacity has been exhibited by these powdered hybrid systems, as assessed through both the DPPH and linoleic acid/β-carotene tests. Sustainable production practices are enabled by this innovative approach, which also opens avenues for the development of advanced materials for diverse applications across various industries. [ABSTRACT FROM AUTHOR]

A hafnium‐based coordination vitrimer (Hf−CooAN‐10) has been prepared by carboxylate ligand exchange from [Hf6O4(OH)4(O2CMe)12]2 and poly‐((ethylhexyl methacylate)‐co‐(carboxyethyl acrylate)) (Mn = 14.4 kg mol−1, Đ = 2.2, 90 : 10 comonomer molar ratio), using a 10 % molar Hf loading with respect to the polymer maximum crosslinking capacity. The material shows high insoluble fraction and expected properties for a 3D network and has been reshaped three times at 50 °C under a 3‐ton pressure without significant property alteration. The Hf−CooAN‐10 thermomechanical and rheological properties are very similar to those previously reported for the analogous Zr−CooAN‐10. The associative nature of carboxylate exchange between the [Hf6O4(OH)4(O2CR)12] crosslinks and the polymer matrix free −COOH functions is suggested by parallel 1H NMR line‐broadening kinetic investigations of acetate exchange in the [Hf6O4(OH)4(O2CMe)12]2 precursor with free MeCOOH, the rate of which has a zero‐order dependence on [MeCOOH], and by DFT calculations on a [Hf(μ‐O2CMe)(O2CMe)2(OH)(H2O)]2 model. The results of these investigations, including the activation parameters for the exchange of both chelating and bridging ligands, are very similar to those of the previously investigated zirconium system and suggest partial acetate dissociation assisted by H‐bond formation with a (μ3‐OH) ligand as the rate‐determining step, followed by acid coordination and intramolecular proton transfer. [ABSTRACT FROM AUTHOR]

The catalytic oxidation of glycerol, a surplus byproduct of biodiesel, has received increasing attention due to the popular applications of its oxidation products, such as aldehydes, ketones, and carboxylates. Photoelectrochemical (PEC) methods provide a clean and sustainable pathway for glycerol oxidation and upgrading. However, selective oxidation of glycerol is a challenge due to its complex oxidation path, where the cleavage of C−O or C−C bonds at different positions can lead to a variety of products. This concept aims to describe the recent advances in PEC selective glycerol oxidation for the preparation of multiple high value‐added products, and discuss the reaction mechanism and selective production strategies in detail. Finally, the remaining challenges and future prospects for the PEC glycerol oxidation system are presented. [ABSTRACT FROM AUTHOR]

Background and aims: Belowground interspecific plant facilitation is supposed to play a key role in enabling species co-existence in hyperdiverse ecosystems in extremely nutrient-poor, semi-arid habitats, such as Banksia woodlands in southwestern-Australia. Manganese (Mn) is readily mobilised by Banksia cluster root activity in most soils and accumulates in mature leaves of native Australian plant species without significant remobilisation during leaf senescence. We hypothesised that neighbouring shrubs are facilitated in terms of Mn uptake depending on distance to surrounding cluster root-forming Banksia trees. Methods: We mapped all Banksia trees and selected neighbouring shrubs within a study site in Western Australia. Soil samples were collected and analysed for physical properties and nutrient concentrations. To assesses the effect of Banksia tree proximity on leaf Mn concentrations [Mn] of non-cluster-rooted woody shrubs, samples of similarly aged leaves were taken. We used multiple linear models to test for factors affecting shrub leaf [Mn]. Results: None of the assessed soil parameters showed a significant correlation with shrub leaf Mn concentrations. However, we observed a significant positive effect of very close Banksia trees (2 m) on leaf [Mn] in one of the understorey shrubs. We found additional effects of elevation and shrub size. Conclusions: Leaf micronutrient concentrations of understorey shrubs were enhanced when growing within 2 m of tall Banksia trees. Our model predictions also indicate that belowground facilitation of Mn uptake was shrub size-dependent. We discuss this result in the light of plant water relations and shrub root system architecture. [ABSTRACT FROM AUTHOR]

Background and aims: In extremely low-phosphorus (P) environments, most Proteaceae exude carboxylates from cluster roots. These carboxylates mobilise inorganic P which leads to a relatively high leaf manganese concentration ([Mn]). However, we found that Adenanthos cygnorum (Proteaceae) in a low-P habitat did not invariably have a high leaf [Mn] in south-western Australia. We aimed to explore how A. cygnorum acquires P in severely P-impoverished habitats. Methods: We determined soil P concentrations and leaf [Mn] of A. cygnorum growing within 1 m and more than 10 m away from other large Proteaceae. We also grew plants in a glasshouse to determine its root carboxylate exudation and rhizosheath phosphatase activity. Results: Adenanthos cygnorum did not produce functional cluster roots. It depended on carboxylates released by a P-mobilising neighbour, Banksia attenuata (Proteaceae), to acquire P when growing in severely P-impoverished soil (< 8 mg P kg− 1 dry soil). In slightly less P-impoverished soil (> 11 mg P kg− 1 dry soil), phosphatases released by A. cygnorum hydrolysed sufficient organic P that was relatively mobile. Conclusion: The reliance on facilitation of P acquisition in A cygnorum depended strongly on location. We demonstrated the exudation of phosphatases, which mobilise inorganic P; this P was adequate for growth when there was sufficient organic P in soil. Facilitation of P acquisition by B. attenuata allowed A. cygnorum to extend its range into severely P-impoverished habitats where it cannot exist without facilitation. This knowledge provides a better understanding of the diversity of P-acquisition strategies in severely P-impoverished environments. [ABSTRACT FROM AUTHOR]

Sulfur (S) plays a crucial role in plant growth and development and serves numerous biological functions in plants. To investigate the role of sulfur in drought stress protection, two experiments were conducted under greenhouse and growth chamber conditions in 2021 Also, to evaluate the influence of foliar application of sulfur on the expression of Pyrroline-5-carboxylate synthase, (P5CS), proline concentration, and antioxidant enzyme activities, the plants of wheat Sardari and Ivan cultivars were exposed to two levels of water regimes. Plants under well-watered irrigation and drought stress conditions showed different P5CS expression levels and accumulated proline. The P5CS expression level in the Ivan cultivar was significantly increased by foliar application of S, while the same application had no significant effect on P5CS expression in the Sardari cultivar. Plants exposed to drought stress and foliarsprayed with S showed a higher proline accumulation The activities of antioxidant enzymes, including peroxidase (POD), catalase, glutathione peroxidase (GP), and glutathione reductase, were increased by 134 %, 40.4 %, 45.4 %, and 77.4 %, respectively, in plants exposed to drought stress. POD and GR were significantly increased by 19.6 % and 51.8 %, respectively, due to S application. Drought-induced plants that were foliar-sprayed with S exhibited a significantly lower rate of ion leakage and higher leaf-relative water content than those of control plants. Based on the results of the present research, it was revealed that S substantially enhances the expression rate of the P5CS gene, leading to proline accumulation, and activates defense reactions in waterstressed wheat. [ABSTRACT FROM AUTHOR]

Poor light absorption ability severely limit the photocatalytic efficiency of metal–organic frameworks (MOFs) for chemical transformations. Herein, we have integrated the zinc(terpyridine) complex as "molecular antennas" into backbone of MOFs, to harvest visible light for aerobic oxidative coupling of amines. Two photoactive MOFs of Zn-CTP [CTP = (4′-(4-carboxyl)-terpyridine] and Zn-TPBA {TPBA = 4-([2,2′:6′,2′′-terpyridin]-4'-yl)benzoic acid} were thus prepared by employing the terpyridine-containing aromatic carboxylate ligands of CTP and TPBA as the organic linkers, respectively, to coordinate with zinc nitrate under solvothermal condition. Characterization results suggested the successful chelation of terpyridine with zinc(II) ions, giving zinc(terpyridine)-containing MOFs with high crystallinity. The incorporated zinc(terpyridine) complexes indeed acted as the "molecular antennas" in MOF to harvest visible light. Furthermore, π-conjugated terpyridine in organic linkers favored the charge transfer, leading to efficient charge separation in MOFs. Both zinc(terpyridine)-containing MOFs thus demonstrated high activities in the visible light-driven oxidation of amines to imines in air at room temperature. Particularly, extended π-conjugated linker of TPBA could further enhance the delocalization of conjugated electrons and optimize the electronic band structure that in favour of photocatalytic activity. As a result, Zn-TPBA enables almost quantitative oxidative coupling of benzylamine under visible light irradiation in atmospheric air, which was even more efficient than other reported photocatalysts in pure oxygen atmosphere. The salient advantages, such as operational simplicity, environmentally friendly, energy efficient, and high efficiency, made such photocatalytic system highly promising and practical in industrial application. Zinc(terpyridine) complex acted as "light antennas" in MOFs, making oxidative coupling of amines highly efficient under visible light in air. [ABSTRACT FROM AUTHOR]

Background and Aims Soils in south-western Australia are severely phosphorus (P) impoverished, and plants in this region have evolved a variety of P-acquisition strategies. Phosphorus acquisition by Adenanthos cygnorum (Proteaceae) is facilitated by P-mobilizing neighbours which allows it to extend its range of habitats. However, we do not know if other Adenanthos species also exhibit a strategy based on facilitation for P acquisition in P-impoverished environments. Methods We collected leaf and soil samples of Adenanthos barbiger , A. cuneatus , A. meisneri, A. obovatus , A. sericeus and Adenanthos sp. Whicher Range (G.J. Keighery 9736) growing in their natural habitats at different locations within the severely P-limited megadiverse environment of south-western Australia. Hydroponic experiments were conducted to collect the carboxylates exuded by cluster roots. Pot experiments in soil were carried out to measure rhizosheath phosphatase activity. Key Results We found no evidence for facilitation of P uptake in any of the studied Adenanthos species. Like most Proteaceae, A. cuneatus , A. meisneri , A. obovatus , A. sericeus and Adenanthos sp. Whicher Range (G.J. Keighery 9736) expressed P-mining strategies, including the formation of cluster roots. Cluster roots of A. obovatus were less effective than those of the other four Adenanthos species. In contrast to what is known for most Proteaceae, we found no cluster roots for A. barbiger. This species probably expressed a post-fire P-acquisition strategy. All Adenanthos species used P highly efficiently for photosynthesis, like other Proteaceae in similar natural habitats. Conclusions Adenanthos is the first genus of Proteaceae found to express multiple P-acquisition strategies. The diversity of P-acquisition strategies in these Proteaceae, coupled with similarly diverse strategies in Fabaceae and Myrtaceae, demonstrates that caution is needed in making family- or genus-wide extrapolations about the strategies exhibited in severely P-impoverished megadiverse ecosystems. [ABSTRACT FROM AUTHOR]

Two kinds of indium-based MOF materials (In-MOF 1 and In-MOF 2) were synthesized using a solvothermal method using two different pyridine carboxylic acid ligands. Single crystal X-ray diffraction shows that In-MOF 1 is a three-dimensional frame containing four connected [In(CO2)4] units and nine connected [In3(μ3-O)(CO2)6N3] units, while In-MOF 2 is a three-dimensional structure with eight connected [In(CO2)3(CO)N] units. Moreover, the adsorption and separation properties of the MOFs for C2H2, CO2 and CH4 were investigated systematically in order to study the regulation of porosity by the subtle changes in the structure of organic linkers. The results show that both kinds of MOFs have certain gas adsorption and separation capacity, which is mainly determined by the structure, function and adjustable porosity. This work not only reports two MOFs with the potential to separate C2H2/CH4, CO2/CH4 and C2H2/CO2, but also provides valuable guidance for the design and synthesis of porous MOFs with better performance in the future. [ABSTRACT FROM AUTHOR]