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A multicomponent synthesis of 1,8-naphthyridine with high yields utilizing benzaldehydes, malononitrile, phenol, and acetylenic esters in aqueous solution at room temperature in the presence of SiO2/Fe3O4 as a reusable catalyst is reported. Using the MTT test, the cytotoxic properties of all the produced compounds were assessed in vitro against cancer cell lines (MCF-7 and A549) and normal cell lines (BEAS-2B). It was discovered that the most effective cytotoxic agent, doxorubicin-like in its lack of selectivity, was the derivative 5h. On the other hand, the compound 5c might be regarded as an equipotent molecule with greater selectivity in relation to doxorubicin. Also, this study investigates the antioxidant effects of 1,8-naphthyridine carboxylates, along with other studies conducted in this study.

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Twelve novel longifolene-derived primary amine carboxylates were synthesized and evaluated for herbicidal activity. The structures of title compounds were confirmed by Fourier-transform infrared spectroscopy, 1H nuclear magnetic resonance (NMR), 13C NMR, and high-resolution mass spectrometry. The results showed that all the synthesized compounds exhibited higher herbicidal activity than the corresponding carboxylic acids involved in the reaction and the commercial herbicide glyphosate; some of them even possessed inhibition rates of 100% against Lolium multiflorum Lam. and Brassica campestris at low concentrations (0.039-0.313 mmol/L). Moreover, structural factors, including types of carboxylates and carbon chain length, had a great influence on the herbicidal performance. The herbicidal activity of dicarboxylates was similar to or much higher than that of corresponding monocarboxylates and glyphosate. Furthermore, compound 5l was found to be the most active candidate against the root and shoot growth of L. multiflorum Lam. and B. campestris with half maximal inhibitory concentrations (IC50) of around 0.010 and 0.023 mmol/L. The present work indicated that those prepared compounds have great potential to serve as high-performance botanical herbicides used at low doses.

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Within the new circular economy paradigm, this work evaluates the performance of tailored mixed metal oxides (MMO) anodes, based on ruthenium and antimony, for their application into an electrochemically-assisted organic refinery process. This process is designed to transform pollutants into value-added products with minimal mineralization. Oxidation of synthetic wastes consisting of phenol solutions was used to validate the electrochemical conversion of phenolic wastes into carboxylates, which are then considered as bricks to be used for electrosynthesis or to produce fuels. The MMO anodes were manufactured using two synthesis routes (Pechini method and ionic liquid method), each followed by one of three different heating treatments: furnace, microwave, and CO2 laser. The selection of the optimal electrode for the organic electrorefinery was based on a combination of physical and electrochemical properties, degradation performance of phenol to carboxylates, and long-term stability, looking for a truly sustainable solution. Results indicate that anodes synthesized by the ionic liquid (IL) method, regardless of the heating treatment, demonstrated superior performance, with larger active areas (with furnace 82 mC cm-2, microwave 97 mC cm-2, and laser 127 mC cm-2) and higher phenol degradation rates, resulting in a greater generation of carboxylates during electrolysis, yielding primarily oxalate and achieving up to 40% conversion with furnace heating. However, laser-treated anodes exhibited greater stability than furnace-made ones, attributed to the formation of an insulating TiO2 layer. Although the electrode with the longest service life did not show the best catalytic properties for minimizing mineralization, the observed variations in coatings with identical chemical compositions highlight the importance of this research. This study positions itself at the forefront of developing more efficient and sustainable electrochemical technologies for organic waste treatment.

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Alumoxanes are typically produced via controlled hydrolysis of short-chain alkyl aluminium compounds which leads to oligomeric species that are usually difficult to obtain in crystalline form. Simultaneously, various alternative non-hydrolytic approaches to alumoxanes have also been used. In this work, we report on a new methylalumoxane scaffold derived from the alkylation of a series of dicarboxylic acids: itaconic acid (HO2CCH2C(=CH2)CO2H), succinic acid (HO2CCH2CH2CO2H) and homophthalic acid (HO2CCH2C6H4CO2H). The reactions of AlMe3 with a selected dicarboxylic acid in the molar ratio 4:1 conducted at elevated temperature occur with double methylation of each carboxylic group and provide to the formation of a new methylalumoxane aggregate, Me10Al6O4, flanked by methylaluminium diolate units. We also aimed to obtain dialkylaluminium derivatives of dicarboxylic acids by the controlled reaction of the appropriate acid with AlMe3 in the 1:2 stoichiometry. While the synthesis of organoaluminium derivatives of flexible aliphatic dicarboxylic acids (itaconic and succinic acids) is challenging due to their insolubility, the related homophtalate compound readily forms a molecular tetranuclear cluster, [(homophtalate)(AlMe2)2]2. The molecular and crystal structures of the resulting compounds were determined via NMR spectroscopic analysis and single crystal X-ray diffraction crystallography.

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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.

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Three distinctive end group-containing organotin (IV) carboxylates complexes (YDCOOSn, CLCOOSn and BZCOOSn) were designed and synthesized. Together with theoretical calculations, a thorough examination was carried out to investigate the photophysical properties of these compounds. The cytotoxicity of the synthesized compounds was tested using normal cell line GES-1 and was assessed against four cancer cell lines (A549, Hela, H1299 and HepG2). The outcomes of the experiments demonstrated that these complexes had superior selectivity than cisplatin towards cancerous cells, particularly in the A549 cell line. BZCOOSn was selected as a candidate compound for additional research because it exhibited the lowest IC50 value and the most impressive inducing effect on cell death and G2/M phase arrest. Increased caspase-3 and -9 enzyme activity, a decline in mitochondrial membrane potential (MMP), characteristic nuclear apoptotic morphology, and an accumulation of intracellular reactive oxygen species (ROS) were seen in A549 exposed to BZCOOSn. These findings demonstrated that BZCOOSn exhibited strong cytotoxicity by triggering cell death in A549 via the mitochondrial route. Furthermore, using the scratch wound healing assay, it was discovered that BZCOOSn reduced the migration of A549 cancerous cells. These data all pointed to BZCOOSn as a possible candidate for more research and development as a chemotherapeutic drug.

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Anaerobic fermentation technology enables the production of medium chain carboxylates and alcohols through microbial chain elongation. This involves steering reactor microbiomes to yield desired products, with CO2 supply playing a crucial role in controlling ethanol-based chain elongation and facilitating various bioprocesses simultaneously. In the absence of CO2 supply (Phase I), chain elongation predominantly led to n-caproate with a high selectivity of 96 Cmol%, albeit leaving approximately 80% of ethanol unconverted. During this phase, C. kluyveri and Proteiniphilum-related species dominated the reactors. In Phase II, with low CO2 input (2.0 NmL L-1 min-1), formation of n-butyrate, butanol, and hexanol was stimulated. Increasing CO2 doses in Phase III (6 NmL L-1 min-1) led to CO2 utilization via homoacetogenesis, coinciding with the enrichment of Clostridium luticellarii, a bacterium that can use CO2 as an electron acceptor. Lowering CO2 dose to 0.5 NmL L-1 min-1 led to a shift in microbiome composition, diminishing the dominance of C. luticellarii while increasing C. kluyveri abundance. Additionally, other Clostridia, Proteiniphilum, and Lactobacillus sakei-related species became prevalent. This decrease in CO2 load from 6 to 0.5 NmL L-1 min-1 minimized excessive ethanol oxidation from 30%-50% to 0%-3%, restoring a microbiome favoring net n-butyrate consumption and n-caproate production. The decreased ethanol oxidation coincided with the resurgence of hydrogen formation at partial pressures above 1%. High concentrations of butyrate, caproate, and ethanol in the reactor, along with low acetate concentration, promoted the formation of butanol and hexanol. It is evident that CO2 supply is indispensable for controlling chain elongation in an open culture and it can be harnessed to stimulate higher alcohol formation or induce CO2 utilization as an electron acceptor.

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Sub-high temperature Daqu, a traditional solid fermenting agent used in Chinese strong-aroma Baijiu production, is abundant in diverse microorganisms, including bacteria, yeasts, molds, and actinomycetes. Among these, yeasts are pivotal for ethanol production and flavor formation. However, counting yeasts in Daqu is challenging due to interference from molds and bacteria. Antibiotics are employed to inhibit bacterial growth, but there is no practical way to suppress molds without affecting the growth of yeasts. In this study, short-chain carboxylates (C1-C6) were added to the culture medium at various pH conditions to investigate their effects on the growth of molds and yeasts. The results demonstrated distinct inhibitory effects of the short-chain carboxylates, depending on both pH and concentration. Several tested short-chain carboxylates effectively suppressed mold growth on agar plates while leaving yeast growth unaffected. This suggests a simple and feasible method for enhancing the efficiency of yeast isolation and counting in Daqu. Such an approach is valuable for studying yeasts in diverse and complex habitats.

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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.

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Several new per- and polyfluoroalkyl substances (PFASs) have been synthesized to replace traditional (legacy) PFASs frequently without clear information on their structure, use and potential toxicity. Among them, chloroperfluoropolyether carboxylates (ClPFPECAs) are an emerging group used as processing aids in the production of fluoropolymers to replace the ammonium salt of perfluorononanoic acid (PFNA). The Solvay Company has produced ClPFPECAs as a mixture of six congeners (oligomers) since the mid-1990s, but other possible manufacturers and annual quantities synthesized and used worldwide are unknown. Initial studies to monitor their presence were conducted because of public authority concerns about suspect environmental contamination near fluoropolymer plants. As of 2015, these chemicals have been found in soil, water, vegetative tissues and wildlife, as well as in biological fluids of exposed workers and people, in research carried out mainly in the United States (New Jersey) and Italy. Analysis of wildlife collected even in non-industrialized areas demonstrated widespread occurrence of ClPFPECAs. From the analytical point of view, the (presumptive) evidence of their presence was obtained through the application of non-targeted approaches performed by liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS). Available toxicological data show that ClPFPECAs have similar adverse effects than the compounds which they have replaced, whereas their carcinogenic potential and reproductive damage are currently unknown. All these observations once again cast doubt on whether many alternatives to traditional PFAS are actually safer for the environment and health.

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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.

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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. Supplementary Information: The online version contains supplementary material available at 10.1007/s11104-023-06092-6.

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An unprecedented meglumine-based three-component deep eutectic solvent (3c-DES) (MegPAc) was synthesized using meglumine, p-toluenesulfonic acid (PTSA), and acetic acid as a renewable, and non-toxic solvent. The exploitation of the MegPAc as an eco-friendly reaction media to construct a selective and sensitive small organic molecular sensing probe, namely, pyrazolo[5,1-b]quinazoline-3-carboxylates (PQCs) was executed. Captivatingly, the MegPAc served the dual role of solvent and catalyst, and it delivered the title components with 69-94 % yields within 67-150 minutes. Furthermore, a UV-visible study unfolds the selective detection of Cu2+ ions with our synthetic probe 4 ba and resulted in hypsochromic shift due to electrostatic interactions. Additionally, 1H NMR titration study and density functional theory (DFT) calculations were performed to attest the binding mechanism of sensing probe 4 ba and Cu2+ ions. Worthy of mention, this protocol unveils the efficacy of meglumine-based 3c-DES for the first time as a bio-renewable system to synthesize the PQCs.

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Aim: To synthesize novel more potent trypanocidal and leishmanicidal agents. Methods: Hantzsch's synthetic strategy was used to synthesize 1,3-thiazole-4-carboxylates and their N-benzylated derivatives. Results: 28 new thiazole-carboxylates and their N-benzylated derivatives were established to test their trypanocidal and leishmanicidal activities. From both series, compounds 3b, 4f, 4g, 4j and 4n exhibited a better or comparable trypanocidal profile to benznidazole. Among all tested compounds, 4n was found to be the most potent and was better than benznidazole. Conclusion: Further variation of substituents around 1,3-thiazole-4-carboxylates and or hydrazinyl moiety may assist in establishing better and more potent trypanocidal and leishmanicidal agents.

Chagas disease and leishmaniasis are neglected tropical diseases. Herein, 28 1,3-thiazoles have been synthesized from thiosemicarbazones in a rapid, efficient and cost-effective manner. In vitro assays were performed against intracellular amastigotes of Trypanosoma cruzi (T. cruzi) and promastigotes and intracellular amastigote forms of Leishmania infantum (L. infantum) and Leishmania amazonensis (L. amazonensis). Some of the 1,3-thiazole-4-carboxylates inhibited the amastigote form of T. cruzi without affecting macrophage viability, compound 4n being the most potent and better than benznidazole. Our synthesized compounds exhibited promising activity against T. cruzi, thus broadening options for scaffold and lead compound optimization. Concerning the leishmanicidal activity, compound 4g was the best prototype in terms of potency and selectivity. Compounds 4g and 3m showed moderate selectivity and potency against intracellular amastigotes of L. amazonensis and L. infantum, respectively.

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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 Adenanthosbarbiger, 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.

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Understanding the dissolution of boehmite in highly alkaline solutions is important to processing complex nuclear waste stored at the Hanford (WA) and Savannah River (SC) sites in the United States. Here, we report the adsorption of model carboxylates on boehmite nanoplates in alkaline solutions and their effects on boehmite dissolution in 3 M NaOH at 80 °C. Although expectedly lower than at circumneutral pH, adsorption of oxalate occurred at pH 13, with adsorption decreasing linearly to 3 M NaOH. Classical molecular dynamics simulations suggest that the adsorption of oxalate dianions onto the boehmite surface under high pH can occur through either inner- or outer-sphere complexation mechanisms depending on adsorption sites. However, both adsorption models indicate relatively weak binding, with an energy preference of 1.26 to 2.10 kcal/mol. By preloading boehmite nanoplates with oxalate or acetate, we observed suppression of dissolution rates by 23 or 10%, respectively, compared to pure solids. Scanning electron microscopy and transmission electron microscopy characterizations revealed no detectable difference in the morphologic evolution of the dissolving boehmite materials. We conclude that preadsorbed carboxylates can persist on boehmite surfaces, decreasing the density of dissolution-active sites and thereby adding extrinsic controls on dissolution rates.

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Laying hens were exposed to feeds spiked with a series of perfluoroalkyl carboxylates (PFCAs) ranging from perfluorobutanoic acid (C4) to perfluorooctadecanoic acid (C18) to investigate their bioaccumulation, tissue distribution, and maternal transfer. We found that PFCAs with longer carbon chains (>8) were more efficiently absorbed in the gastrointestinal tract than those with shorter chains (≤8), and that the rate of depuration varied inversely with the carbon chain length in a U-shaped pattern. Moreover, bioaccumulation potential increased with increasing carbon-chain length, except for C4. Distinct affinities were observed for specific carbon-chain PFCAs across various tissues, evident from their differential accumulation during both uptake and depuration phases. Specifically, C9 showed a higher affinity for serum and liver, C12 was more prevalent in yolk, C14 was notably abundant in the brain, and C18 was predominant in other tissues. Furthermore, the egg-maternal ratio (EMR) increased with increasing carbon-chain length from C7 to C11 and reached a plateau phase for C12 to C18. Our study also confirmed the key role of phospholipids in the tissue distribution and maternal transfer of long-chain PFCAs. This study sheds light on the interaction between PFCAs and biological tissues and reveals the toxicokinetic factors that influence the bioaccumulation of PFCAs. Further research is needed to identify the specific proteins or components that mediate the tissue-specific affinity for different carbon-chain lengths of PFCAs.

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To establish a circular economy, waste streams should be used as a resource to produce valuable products. Biodegradable plastic waste represents a potential feedstock to be microbially recycled via a carboxylate platform. Bioplastics such as polylactic acid food packaging waste (PLA-FPW) are theoretically suitable feedstocks for producing carboxylates. Once feasible, carboxylates such as acetate, n-butyrate, or n-caproate can be used for various applications like lubricants or building blocks for making new bioplastics. In this study, pieces of industrial compostable PLA-FPW material (at 30 or 60 g/L) were added to a watery medium with microbial growth nutrients. This broth was exposed to 70 °C for a pretreatment process to support the hydrolysis of PLA into lactic acid at a maximum rate of 3.0 g/L×d. After 21 days, the broths of the hydrolysis experiments were centrifugated and a part of the supernatant was extracted and prepared for anaerobic fermentation. The mixed microbial culture, originating from a food waste fermentation bioprocess, successfully fermented the hydrolyzed PLA into a spectrum of new C2-C6 multi-carbon carboxylates. n-butyrate was the major product for all fermentations and, on average, 6.5 g/L n-butyrate was obtained from 60 g/L PLA-FPW materials. The wide array of products were likely due to various microbial processes, including lactate conversion into acetate and propionate, as well as lactate-based chain elongation to produce medium-chain carboxylates. The fermentation process did not require pH control. Overall, we showed a proof-of-concept in using real bioplastic waste as feedstock to produce valuable C2-C6 carboxylates via microbial recycling.

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CO2:H2-based gas fermentation with acetogenic Clostridium species are at an early stage of development. This work exploited the Adaptive Laboratory Evolution technique to improve the growth of C. carboxidivorans P7 on CO2 and H2. An adapted strain with decreased growth lag phase and improved biomass production was obtained. Genomic analysis revealed a conserved frameshift mutation in the catalytic subunit of the hexameric hydrogenase gene. The resulted truncated protein variant, most likely lacking its functionality, suggests that other hydrogenases might be more efficient for H2-based growth of this strain. Furthermore, the adapted strain generated hexanol as primary fermentation product. For the first time, hexanol was produced directly from CO2:H2 blend, achieving the highest maximum productivity reported so far via gas fermentation. Traces of valerate, pentanol, eptanol and octanol were observed in the fermentation broth. The adapted strain shows promising to enrich the product spectrum targetable by future gas fermentation processes.

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Low-valent main group compounds that fluoresce in the solid-state were previously unknown. To address this, we investigated room-temperature photoluminescence from a series of crystals of germylenes 3-8 in this article; they exhibited emissions nearly reaching the NIR. Germylene carboxylates (3-8) were synthesized by reacting dipyrromethene stabilized germylene pyrrolide (2) with carboxylic acids such as acetic acid, trifluoroacetic acid, benzoic acid, p-cyanobenzoic acid, p-nitrobenzoic acid, and acetylsalicylic acid.