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Objective: The purpose of this study was to explore the potential mechanism of Helicobacter pylori (Hp) eradication by probiotic therapy through 16S rRNA gene sequencing technology and untargeted metabolomics. Methods: Twenty four Hp-infected children were recruited from the Shanxi Bethune Hospital, and 24 healthy children were recruited as a blank control group. Group A: fecal samples from 24 healthy children. Group B: fecal samples of 24 children with Hp infection. Group B1 (n = 15): fecal samples of group B treated with probiotic therapy for 2 weeks. Group B2 (n = 19): fecal samples of group B treated with probiotic therapy for 4 weeks. The above fecal samples were analyzed by 16S rRNA gene sequencing technology and untargeted metabolomics. Results: There was no significant difference in alpha diversity and beta diversity among the four groups, but many bacteria with statistical difference were found in each group at the bacterial genus level and phylum level. LEfSe results showed that in group B, Porphyromonadaceae , Shigella and other microorganisms related to intestinal microecological dysbiosis were enriched. And in group B2, abundant characteristic microorganisms were found, namely Bacillales and Prevotella. KEGG metabolic pathway enrichment analysis showed that groups B1 and B2 were involved in 10 metabolic pathways potentially related to probiotic treatment: purine metabolism, nitrogen metabolism, arginine biosynthesis, alanine, aspartic acid and glutamate metabolism, glyoxylic acid and dicarboxylic acid metabolism, unsaturated fatty acid biosynthesis, fatty acid extension, fatty acid degradation, pyrimidine metabolism, fatty acid biosynthesis. Conclusion: Probiotic therapy can inhibit Hp to some extent and can relieve gastrointestinal symptoms, making it a preferred therapy for children with Hp infection and functional abdominal pain. Hp infection can reduce the diversity of intestinal microbes, resulting in the disturbance of intestinal microbiota and changes in the relative abundance of microbiota in children, while probiotic therapy can restore the diversity of intestinal microbes and intestinal microecological balance. [ABSTRACT FROM AUTHOR]

Amino acids are present in all known life, so identifying the environmental conditions under which they can be synthesized constrains where life on Earth might have formed and where life might be found on other planetary bodies. All known abiotic amino acid syntheses require ammonia, which is only produced in reducing and neutral atmospheres. Here, we demonstrate that the Fe-bearing hydroxide mineral ferroan brucite [Fe0.33,Mg0.67(OH)2] can mediate the reaction of nitrate and glyoxylate to form glycine, the simplest amino acid used in life. Up to 97% of this glycine was detected only after acid digestion of the mineral, demonstrating that it had been strongly partitioned to the mineral. The dicarboxylic amino acid 3-hydroxy aspartate was also detected, which suggests that reactants underwent a mechanism that simultaneously produced mono-and dicarboxylic amino acids. Nitrate can be produced in both neutral and oxidizing atmospheres, so reductive amination of nitrate and glyoxylate on a ferroan brucite surface expands origins of life scenarios. First, it expands the environmental conditions in which life's precursors could form to include oxidizing atmospheres. Second, it demonstrates the ability of ferroan brucite, an abundant, secondary mineral in serpentinizing systems where olivine is partly hydrated, to mediate reductive amination. Finally, the results demonstrate the need to consider mineral-bound products when analyzing samples for abiotic amino acid synthesis. [ABSTRACT FROM AUTHOR]

Summary: Malate and fumarate constitute a significant fraction of the carbon fixed by photosynthesis, and they are at the crossroad of central metabolic pathways. In Arabidopsis thaliana, they are transiently stored in the vacuole to keep cytosolic homeostasis.The malate and fumarate transport systems of the vacuolar membrane are key players in the control of cell metabolism. Notably, the molecular identity of these transport systems remains mostly unresolved. We used a combination of imaging, electrophysiology and molecular physiology to identify an important molecular actor of dicarboxylic acid transport across the tonoplast.Here, we report the function of the A. thaliana Aluminium‐Activated Malate Transporter 5 (AtALMT5). We characterised its ionic transport properties, expression pattern, localisation and function in vivo. We show that AtALMT5 is expressed in photosynthetically active tissues and localised in the tonoplast. Patch‐clamp and in planta analyses demonstrated that AtALMT5 is an ion channel‐mediating fumarate loading of the vacuole. We found in almt5 plants a reduced accumulation of fumarate in the leaves, in parallel with increased malate concentrations.These results identified AtALMT5 as an ion channel‐mediating fumarate transport in the vacuoles of mesophyll cells and regulating the malate/fumarate balance in Arabidopsis. [ABSTRACT FROM AUTHOR]

Photosynthetic eukaryotes have metabolic pathways that occur in distinct subcellular compartments. However, because metabolites synthesized in one compartment, including fixed carbon compounds and reductant generated by photosynthetic electron flows, may be integral to processes in other compartments, the cells must efficiently move metabolites among the different compartments. This review examines the various photosynthetic electron flows used to generate ATP and fixed carbon and the trafficking of metabolites in the green alga Chlamydomomas reinhardtii; information on other algae and plants is provided to add depth and nuance to the discussion. We emphasized the trafficking of metabolites across the envelope membranes of the two energy powerhouse organelles of the cell, the chloroplast and mitochondrion, the nature and roles of the major mobile metabolites that move among these compartments, and the specific or presumed transporters involved in that trafficking. These transporters include sugar-phosphate (sugar-P)/inorganic phosphate (Pi) transporters and dicarboxylate transporters, although, in many cases, we know little about the substrate specificities of these transporters, how their activities are regulated/coordinated, compensatory responses among transporters when specific transporters are compromised, associations between transporters and other cellular proteins, and the possibilities for forming specific 'megacomplexes' involving interactions between enzymes of central metabolism with specific transport proteins. Finally, we discuss metabolite trafficking associated with specific biological processes that occur under various environmental conditions to help to maintain the cell's fitness. These processes include C4 metabolism in plants and the carbon concentrating mechanism, photorespiration, and fermentation metabolism in algae. [ABSTRACT FROM AUTHOR]

Oxalate, the simplest dicarboxylic acid, is a prevalent antinutrient that chelates with various metals and can lead to the formation of kidney stones in humans. The accurate detection of the oxalate concentration in food and the cultivation of low-oxalate crops are important for enhancing public health. In this study, we established a high-throughput and highly sensitive technique for oxalate detection using ultra-high-performance liquid chromatographic–triple quadrupole tandem mass spectrometry (UPLC-QqQ-MS/MS). Additionally, we overexpressed the gene O7, which encodes oxalyl-CoA synthetase in the maize oxalate degradation pathway, resulting in O7-OE lines. By employing the UPLC-QqQ-MS/MS method to measure oxalate levels in these transgenic lines, we observed that the oxalate content in the kernels of O7-OE lines was reduced by approximately 43%, with a concurrent increase in some micronutrients such as zinc. Importantly, the transgenic maize showed normal seed storage compound accumulation or other agronomic characteristics. In summary, we developed a high-throughput detection method that advances oxalate measurement. Furthermore, by generating new maize germplasm with diminished oxalate, our work offers potential health advantages to consumers. [ABSTRACT FROM AUTHOR]

The singlet fission characteristics of aqueous nanoparticles, self‐assembled from ion pairs of tetracene dicarboxylic acid and various amines with or without chirality, are thoroughly investigated. The structure of the ammonium molecule, the counterion, is found to play a decisive role in determining the molecular orientation of the ion pairs and its regularity, spectroscopic properties, the strength of the intermolecular coupling between the tetracene chromophores, and the consequent singlet fission process. Using chiral amines has led to the formation of crystalline nanosheets and efficient singlet fission with a triplet quantum yield as high as 133% ±20% and a rate constant of 6.99 × 109 s−1. The chiral ion pairs also provide a separation channel to free triplets with yields as high as 33% ±10%. In contrast, nanoparticles with achiral counterions do not show singlet fission, which gave low or high fluorescence quantum yields depending on the size of the counterions. The racemic ion pair produces a correlated triplet pair intermediate by singlet fission, but no decorrelation into two free triplets is observed, as triplet‐triplet annihilation dominates. The introduction of chirality enables higher control over orientation and singlet fission in self‐assembled chromophores. It provides new design guidelines for singlet fission materials. [ABSTRACT FROM AUTHOR]

ABSTRACT Malate is an important dicarboxylic acid produced from fumarate in the tricarboxylic acid cycle. Deficiencies of fumarate hydrolase (FH) and malate dehydrogenase (MDH), responsible for malate formation and metabolism, respectively, are known to cause recessive forms of neurodevelopmental disorders (NDDs). The malic enzyme isoforms, malic enzyme 1 (ME1) and 2 (ME2), are required for the conversion of malate to pyruvate. To date, there have been no reports linking deficiency of either malic enzyme isoforms to any Mendelian disease in humans. We report a patient presenting with NDD, subtle dysmorphic features, resolved dilated cardiomyopathy, and mild blood lactate elevation. Whole exome sequencing (WES) revealed a homozygous frameshift variant (c.1379_1380delTT, p.Phe460fs*22) in the malic enzyme 2 (ME2) gene resulting in truncated and unstable ME2 protein in vitro. Subsequent deletion of the yeast ortholog of human ME2 (hME2) resulted in growth arrest, which was rescued by overexpression of hME2, strongly supporting an important role of ME2 in mitochondrial function. Our results also support the pathogenicity and candidacy of the ME2 gene and variant in association with NDD. To our knowledge, this is the first report of a Mendelian human disease resulting from a biallelic variant in the ME encoding gene. Future studies are warranted to confirm ME2‐associated recessive NDD. [ABSTRACT FROM AUTHOR]

Atmospheric secondary aerosols are often internally mixed with organic and inorganic components, particularly dicarboxylic acids, ammonium, sulfate, nitrate, and chloride. These complex compositions enable aqueous reaction between organic and inorganic species, significantly complicating aerosol phase behavior during aging and making phase predictions challenging. We investigated carboxylate–ammonium salt mixtures using attenuated total reflection Fourier-transformed infrared spectroscopy (ATR-FTIR). The mono-, di-, and tricarboxylates included sodium pyruvate (SP), sodium tartrate (ST), and sodium citrate (SC), while the ammonium salts included NH4NO3 , NH4Cl , and (NH4)2SO4. Our results demonstrated that aqueous replacement reactions between carboxylates and ammonium salts were promoted by the formation and depletion of NH3 as relative humidity (RH) changed. For SP/ammonium aerosols, NaNO3 and Na2SO4 crystallized from 35.7 % to 12.7 % and from 65.7 % to 60.1 % RH, respectively, which is lower than the values for pure inorganics (62.5 ± 9 %–32 % RH for NaNO3 and 82 ± 7 %–68 ± 5 % RH for Na2SO4). Upon hydration, the crystalline Na2SO4 and NaNO3 deliquesced at 88.8 %–95.2 % and 76.5 ± 2 %–81.9 %, which is higher than the values of pure Na2SO4 (74 ± 4 %–98 % RH) and NaNO3 (65 %–77.1 ± 3 % RH). In contrast, reaction between ST or SC and (NH4)2SO4 was incomplete due to the gel structure at low RH. Unexpectedly, aqueous Na2SO4 crystallized upon humidification in ST/ (NH4)2SO4 particles at 43.6 % RH and then deliquesced with increasing RH. This is attributed to increased ion mobility in viscous particles, leading to nucleation and growth of Na2SO4 crystals. Our findings highlight the intricate interplay between chemical components within organic/inorganic aerosol and the impact of replacement reactions on aerosol aging, phase state, and subsequently atmospheric processes. [ABSTRACT FROM AUTHOR]

The reactions of the angular ligand 4,4′-oxybis(N-(pyridin-3-yl)benzamide) (L1) and 1,4-naphthalenedicarboxylic acid (1,4-H2NDC) with divalent metal salts yielded three distinct coordination polymers (CPs): {[Zn2(L1)(1,4-NDC)2]·MeOH}n, 1, {[Cu(L1)(1,4-NDC)(H2O)]·3H2O}n, 2, and {[Cd(L1)(1,4-NDC)]·2H2O}n, 3. Complex 1 features a 2-fold interpenetrated 3D framework with the (412·63)-pcu topology, while complex 2 reveals a 1D triple-strained helical chain and complex 3 displays a 3-fold interpenetrated 3D framework with (66)-dia topology. Additionally, the reactions of the flexible ligand N,N′-bis(3-methylpyridyl) adipoamide (L2) afforded {[Co4(L2)0.5(1,4-NDC)3(H2O)3(µ3-OH)2]·EtOH·2H2O}n, 4, {[Zn2(L2)(1,4-NDC)2]·2CH3OH}n, 5, and [Cd(L2)(adipic)(H2O)]n (H2adipic = adipic acid), 6, exhibiting a self-catenated 3D framework with the (420·68)-8T32 topology, a 2D layer with the (413·62) − (4,4)IIb topology, and a 2D layer with the (44·62)-sql topology, respectively. The structural diversity observed in complexes 1–6 highlights the pivotal influence of the metal center on the degree of entanglement in CPs within mixed-ligand systems. The thermal stability and luminescent properties of complexes 1–3, 4, and 6 are also discussed. [ABSTRACT FROM AUTHOR]

Three nickel, copper, and zinc complexes with dicarboxylic acids (3,3′-dithiodipropionic acid (H2dtdp) and fumaric acid (H2fu)) and N-donor ligands (1,10-phenanthroline (phen), N′–methyldipropylenetriamine (mdpta), and N,N,N′,N″,N″-pentamethyldiethylenetriamine (pmdien)) were synthesized. These complexes were characterized using elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Interestingly, [Ni(dtdp)(phen)(H2O)3]∙0.5H2O (1) is a mononuclear complex, where the dtdp dianion employs only one carboxylate group for coordination to the central nickel atom. [(ClO4)(mdpta)Cu(μ-dtdp)Cu(mdpta)(H2O)](ClO4) (2) is a dinuclear copper complex with a dtdp bridge and different coordination on the copper center. [{Zn(pmdien)(H2O)}2(μ-fu)](ClO4)2 (3) is a symmetric dimer with a bridging fumarate ligand. These coordination compounds were tested for their antibacterial activities on Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Enterococcus faecalis bacteria strains. All the complexes show moderate activities on the mentioned strains. [ABSTRACT FROM AUTHOR]

Sixty-four phenols grouped as nitrated, bromo, amino, methyl, chloro-phenols, and cresols, and thirty-eight organic acids grouped as mono-carboxylic and dicarboxylic are analyzed in forty-two fog samples collected in the Alsace region between 2015 and 2021 to check their atmospheric behavior. Fogwater samples are collected using the Caltech Active Strand Cloudwater Collector (CASCC2), extracted using liquid–liquid extraction (LLE) on a solid cartridge (XTR Chromabond), and then analyzed using gas chromatography coupled with mass spectrometry (GC-MS). The results show the high capability of phenols and acids to be scavenged by fogwater due to their high solubility. Nitro-phenols and mono-carboxylic acids have the highest contributions to the total phenolic and acidic concentrations, respectively. 2,5-dinitrophenol, 3-methyl-4-nitrophenol, 4-nitrophenol, and 3,4-dinitrophenol have the highest concentration, originating mainly from vehicular emissions and some photochemical reactions. The top three mono-carboxylic acids are hexadecenoic acid (C16), eicosanoic acid (C18), and dodecanoic acid (C12), whereas succinic acid, suberic acid, sebacic acid, and oxalic acid are the most concentrated dicarboxylic acids, originated either from atmospheric oxidation (mainly secondary organic aerosols (SOAs)) or vehicular transport. Pearson's correlations show positive correlations between organic acids and previously analyzed metals (p < 0.05), between mono- and dicarboxylic acids (p < 0.001), and between the analyzed acidic compounds (p < 0.001), whereas no correlations are observed with previously analyzed inorganic ions. Total phenolic and acidic fractions are found to be much higher than those observed for pesticides, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) measured at the same region due to their higher scavenging by fogwater. [ABSTRACT FROM AUTHOR]

Garcinia gummi-gutta, commonly known as Garcinia cambogia (syn.), is a popular traditional herbal medicine known for its role in treating obesity, and has been incorporated into several nutraceuticals globally for this purpose. The fruit rind is also used as a food preservative and a condiment because of its high content of hydroxycitric acid, which imparts a sharp, sour flavour. This review highlights the major bioactive compounds present in the tree Garcinia gummi-gutta, with particular emphasis on (2S, 3S)-tetrahydro-3-hydroxy-5-oxo-2,3-furan dicarboxylic acid, commonly referred to as garcinia acid. This acid can be isolated in large amounts through a simple procedure. Additionally, it explores the synthetic transformations of garcinia acid into biologically potent and functionally useful enantiopure compounds, a relatively under-documented area in the literature. This acid, with its six-carbon skeleton, a γ-butyrolactone moiety, and two chiral centres bearing chemically amenable functional groups, offers a versatile framework as a chiron for the construction of diverse molecules of both natural and synthetic origin. The synthesis of chiral 3-substituted and 3,4-disubstituted pyrrolidine-2,5-diones, analogues of the Quararibea metabolite—a chiral enolic-γ-lactone; the concave bislactone skeletons of fungal metabolites (+)-avenaciolide and (−)-canadensolide; the structural skeletons of the furo[2,3-b]furanol part of the anti-HIV drug Darunavir; (−)-tetrahydropyrrolo[2,1-a]isoquinolinones, an analogue of (−)-crispine A; (−)-hexahydroindolizino[8,7-b]indolones, an analogue of the naturally occurring (−)-harmicine; and furo[2,3-b]pyrroles are presented here. [ABSTRACT FROM AUTHOR]

This investigation focuses on the prevalent continental oil shale within the Triassic Chang 7, a member of the Yanchang Formation in the Ordos Basin and the Permian Lucaogou Formation in the Junggar Basin of western China, and delves into the impacts of hydrocarbon generation and the derived organic acids on the physical attributes of oil shale reservoirs. Water-soluble organic acids (WSOAs) were extracted via Soxhlet extraction and analyzed by a 940 ion chromatograph (Metrohm AG), supplemented with core observations, thin-section analyses, pyrolysis, and trace element assays, as well as the qualitative observation of pore structures via FIB-SEM scanning electron microscopy. The study discloses substantial disparities in the types and abundances of organic acids within the oil shale strata of the two regions, with mono-acids being conspicuously more prevalent than dicarboxylic acids. The spatial distribution of organic acids within the oil shale strata in the two regions is non-uniform, and their generation is inextricably correlated with the type of organic matter, thermal maturity, and depth at which they are buried. During diverse stages of diagenesis, the hydrocarbons and organic acids produced from the pyrolysis of organic matter not only exert an impact on the properties of pore fluids but also interact with diagenetic processes such as compaction, dissolution, and metasomatism to enhance the reservoir quality of oil shale. The synergy between chemical interactions and physical alterations collectively governs the migration and distribution patterns of organic acids as well as the characteristics of oil shale reservoirs. Furthermore, the sources of organic acids within the oil shale series in the two regions demonstrate pronounced dissimilarities, which are intimately associated with the peculiarities of their sedimentary milieu. The oil shale of the Yanchang Formation was formed in a warm and humid freshwater lacustrine basin environment, while the oil shale of the Lucaogou Formation was deposited in a brackish to saline lacustrine setting under an arid to semi-arid climatic regime. These variances not only illuminate the intricacy and multiplicity of the sedimentary attributes of oil shale but also accentuate the impact of the sedimentary environment on the genesis and distribution of organic acids, especially the transformation and optimization of reservoir dissolution by organic acids generated during hydrocarbon generation—a factor of paramount significance for the precise identification and effective development of the "sweet spot" area of shale oil. These areas, characterized by an abundance of organic matter, their maturity, and superior reservoir properties, are the foci of the efficient exploration and development of continental shale oil. [ABSTRACT FROM AUTHOR]

Traditional polyamide elastomer synthesis via polycondensation of diamines and dicarboxylic acids involves high energy use and by‐product mass loss. Here, we present a novel method using thiol‐Michael addition click chemistry to produce these elastomers under mild conditions, marking the first use of this strategy. The polymerization involves coupling bis‐acrylamide (BAA) with 3,6‐dioxa‐1,8‐octanedithiol (DODT), catalyzed by 1,5‐diazabicyclo[4.3.0]non‐5‐ene (DBN). BAA is synthesized from polyetheramine and acryloyl chloride, creating a compound with amide groups and carbon double bonds at chain ends. These double bonds' electron‐withdrawing effect facilitates the click reaction efficiently, avoiding high energy and mass loss. The resulting polymers have a molecular weight of approximately 10,000 g/mol, verified by 1H NMR and FTIR spectroscopy, which show amide group presence. SAXS and AFM confirm nanophase separation of these groups. Tensile strength ranges from 0.235 to 0.542 MPa, decreasing with lower polyetheramine content but still showing notable elasticity. This method's low energy use, no mass loss, and good mechanical properties make it promising for developing high‐performance polyamide plastics and elastomers, appealing to researchers in both academia and industry. Highlights: High elasticity, softness, and high tensile polyamide elastomer.Thiol‐Michael addition click reaction conforms to atomic economy.Long molecular chain contains extraordinary evolution of hydrogen bonding. [ABSTRACT FROM AUTHOR]

The utilization of biomass resources in the production of bio‐based or bio‐recycled polyurethanes (PUs) enhances the sustainable development and eco‐friendliness of PU. Herein, a series of new bio‐based aliphatic poly(propylene dicarboxylate) diols were synthesized using bio‐based 1,3‐propanediol (bio‐PDO) and aliphatic dicarboxylic acids with different chain lengths. These bio‐based polyester diols and 1,4‐butanediol (BDO) reacted with 4,4′‐dicyclohexylmethane diisocyanate to produce aliphatic PU elastomers (PUEs). The study aimed to evaluate the impact of the structure of poly(propylene dicarboxylate) diols on the architecture, morphology, mechanical properties, and degradation of PUEs, thereby expanding the application of bio‐PDO. The results indicate a strong correlation between the degree of microphase separation, tensile properties, and degradation behavior of the synthesized PUEs and the number of methylene groups in the repeating unit of the poly(propylene dicarboxylate) diols. Notably, the PUE derived from poly(propylene pimelate) diol demonstrates the highest level of microphase separation and superior elasticity properties because of the high flexibility of the polyester. On the other hand, PUE prepared from poly(propylene succinate) diol exhibits the fastest degradation performance due to its high density of ester groups. Bio‐PDO based polyester diols show significant potential as raw materials for PUEs with biodegradable and adjustable mechanical properties. Highlights: Poly(propylene dicarboxylate) diols were prepared from bio‐based 1,3‐propanediol.The poly(propylene dicarboxylate) diols based polyurethane elastomers (PUEs) have high tensile strength (>22 MPa) and elongation at break (>920%).The morphology, mechanical properties and degradation of PUEs are highly related to the structure of the poly(propylene dicarboxylate) diols.The increasing repeating unit length of the poly(propylene dicarboxylate) diols increases elastic recovery of PUEs. [ABSTRACT FROM AUTHOR]

The composition of aerosols influenced by regional pollution sources during a post-monsoon haze event was studied including the isotopic, bulk, and molecular signatures. The air mass back trajectory and fire spot analysis revealed that the Delhi aerosols were influenced by the regional post-harvest crop (rice plant) residue-burning activities during the sampling period. To better understand the atmospheric processes during such an event, three samples of 4 h duration each (Period I: from 06:00–10:00, Period II: 10:00–14:00, and Period III: 14:00–18:00 h local time) were collected during the sampling period (8th -17th November, 2019) in the daytime. The average mass concentration of PM2.5, molecular compounds including the inorganic and carbonaceous components (dicarboxylic acid class compounds), along with the stable isotopes of C and N were observed to be elevated during Period I of the study. NH4+ and SO42− were found to be the most abundant inorganic ions during Period II and III with Cl− being the dominant ion during Period I. The OC/EC, WSOC/EC ratios indicated the influence of biomass burning on Delhi aerosols with little influence of local ageing processes evident from the minimal variation observed between the three periods of study during the day. High concentrations of dicarboxylic acids than previous studies are reported with oxalic and succinic acid being the most abundant diacids, a typical behaviour observed in biomass-burning influenced aerosols with an interesting observation of terephthalic acid to be found in an appreciable amount. The δ15 N of TN and δ13 C of TC signatures clearly indicated the influence of emissions from the burning of a C3 plant on the aerosols. The results strongly suggested that the aerosols were influenced by biomass-burning activities in the neighbouring regions and were aged during the atmospheric transport over to the city of Delhi with minimal effect of local ageing processes during the study period. [ABSTRACT FROM AUTHOR]

Zinc metal–organic frameworks have emerged as promising candidates, demonstrating excellent biological properties stemming from the unique characteristics of MOFs and zinc. In this study, we employed a facile method to synthesize a zinc metal–organic framework [Zn(IP)(H2O)] using ultrasound irradiation, with the linker being isophthalic acid (IPA) (1,3-benzene dicarboxylic acid). The parent Zn-MOF and two Ag/Zn-MOF samples prepared via loading and encapsulation methods were comprehensively characterized using various techniques, including FT-IR, XRD, SEM, TEM, N2 adsorption–desorption isotherm, UV–vis spectroscopy and TGA. The parent Zn-MOF and two Ag/Zn-MOF samples exhibited a broad spectrum of antibacterial effects. Remarkably, genomic DNA of P. aeruginosa was effectively degraded by Zn-MOF, further supporting its potent antibacterial results. The free radical inhibition assay demonstrated a 71.0% inhibition under the influence of Zn-MOF. In vitro cytotoxicity activity of Zn-MOF against HepG-2 and Caco-2 cell lines revealed differential cytotoxic effects, with higher cytotoxicity against Caco-2 as explored from the IC50 values. This cytotoxicity was supported by the high binding affinity of Zn-MOF to CT-DNA. Importantly, the non-toxic property of Zn-MOF was confirmed through its lack of cytotoxic effects against normal lung cell (Wi-38). The anti-inflammatory treatment of Zn-MOF achieved 75.0% efficiency relative to the standard Ibuprofen drug. DFT and docking provided insights into the geometric stability of Zn-MOF and its interaction with active amino acids within selected proteins associated with the investigated diseases. Finally, the synthesized Zn-MOF shows promise for applications in cancer treatment, chemoprevention, and particularly antibacterial purposes. [ABSTRACT FROM AUTHOR]

Background: Esophageal diseases (ED) are a kind of common diseases of upper digestive tract. Previous studies have proved that metabolic disorders are closely related to the occurrence and development of ED. However, there is a lack of evidence for causal relationships between metabolites and ED, as well as between metabolite ratios representing enzyme activities and ED. Herein, we explored the causality of genetically determined metabolites (GDMs) on ED through Mendelian Randomization (MR) study. Methods: Two-sample Mendelian randomization analysis was used to assess the causal effects of genetically determined metabolites and metabolite ratios on ED. A genome-wide association analysis (GWAS) encompassing 850 individual metabolites along with 309 metabolite ratios served as the exposures. Meanwhile, the outcomes were defined by 10 types of ED phenotypes, including Congenital Malformations of Esophagus (CME), Esophageal Varices (EV), Esophageal Obstructions (EO), Esophageal Ulcers (EU), Esophageal Perforations (EP), Gastroesophageal Reflux Disease (GERD), Esophagitis, Barrett's Esophagus (BE), Benign Esophageal Tumors (BETs), and Malignant Esophageal Neoplasms (MENs). The standard inverse variance weighted (IVW) method was applied to estimate the causal relationship between exposure and outcome. Sensitivity analyses were carried out using multiple methods, including MR-Egger, Weighted Median, MR-PRESSO, Cochran's Q test, and leave-one-out analysis. P < 0.05 was conventionally considered statistically significant. After applying the Bonferroni correction for multiple testing, a threshold of P < 4.3E-05 (0.05/1159) was regarded as indicative of a statistically significant causal relationship. Furthermore, metabolic pathway analysis was performed using the web-based MetaboAnalyst 6.0 software. Results: The findings revealed that initially, a total of 869 candidate causal association pairs ( P ivw < 0.05) were identified, involving 442 metabolites, 145 metabolite ratios and 10 types of ED. However, upon applying the Bonferroni correction for multiple testing, only 36 pairs remained significant, involving 28 metabolites (predominantly lipids and amino acids), 5 metabolite ratios and 6 types of ED. Sensitivity analyses and reverse MR were performed for these 36 causal association pairs, where the results showed that the pair of EV and 1-(1-enyl-palmitoyl)-2-linoleoyl-GPE (p-16:0/18:2) did not withstand the sensitivity tests, and Hexadecenedioate (C16:1-DC) was found to have a reverse causality with GERD. The final 34 robust causal pairs included 26 metabolites, 5 metabolite ratios and 5 types of ED. The involved 26 metabolites predominantly consisted of methylated nucleotides, glycine derivatives, sex hormones, phospholipids, bile acids, fatty acid dicarboxylic acid derivatives, and N-acetylated amino acids. Furthermore, through metabolic pathway analysis, we uncovered 8 significant pathways that played pivotal roles in five types of ED conditions. Conclusions: This study integrated genomics with metabolomics to assess causal relationships between ED and both metabolites and metabolite ratios, uncovering several key metabolic features in ED pathogenesis. These findings have potential as novel biomarkers for ED and provide insights into the disease's etiology and progression. However, further clinical and experimental validations are necessary [ABSTRACT FROM AUTHOR]

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Succinic acid (SA), a dicarboxylic acid of industrial importance, can be efficiently produced by metabolically engineered Mannheimia succiniciproducens. Although the importance of magnesium (Mg2+) ion on SA production has been evident from our previous studies, the role of Mg2+ ion remains largely unexplored. In this study, we investigated the impact of Mg2+ ion on SA production and developed a hyper-SA producing strain of M. succiniciproducens by reconstructing the Mg2+ ion transport system. To achieve this, optimal alkaline neutralizer comprising Mg2+ ion was developed and the physiological effect of Mg2+ ion was analyzed. Subsequently, the Mg2+ ion transport system was reconstructed by introducing an efficient Mg2+ ion transporter from Salmonella enterica. A high-inoculum fed-batch fermentation of the final engineered strain produced 152.23 ± 0.99 g/L of SA, with a maximum productivity of 39.64 ± 0.69 g/L/h. These findings highlight the importance of Mg2+ ions and transportation system optimization in succinic acid production by M. succiniciproducens. [ABSTRACT FROM AUTHOR]

Ferrous oxalate dihydrate is a versatile organic mineral with applications across fields. However, little is known about the feasibility of its synthesis directly from iron-bearing minerals using binary subcritical water (sCW) systems and its associated kinetics. In this study, the sCW+oxalic acid system at either 115 °C or 135 °C was investigated as a reaction medium for ferrous oxalate dihydrate (α-FeC2O4∙2H2O) synthesis, starting from ferrotitaniferous sands. The kinetics of the synthesis reaction were studied, and the physicochemical characterization of the as-synthetized ferrous oxalates was performed. Overall, the sCW synthesis was temperature-dependent, following second-order reaction kinetics according to the proposed precipitation pathway. A high reaction rate constant, significantly high yields (up to 89%), and reduced reaction times (2–8 h) were evident at 135 °C. The as-synthetized product corresponded to the monoclinic α-FeC2O4∙2H2O, showed relatively high specific surface areas (from 31.9 to 33.7 m2∙g−1), and exhibited band gap energies within the visible light range (~2.77 eV). These results suggest that α-FeC2O4∙2H2O can be synthesized using an organic dicarboxylic acid and iron-rich, widely available, low-cost mineral precursors. In addition, the as-prepared α-FeC2O4∙2H2O could be further optimized and tested for catalytic and visible light photocatalytic applications. [ABSTRACT FROM AUTHOR]

Two copper(II) mixed ligand complexes with dicarboxylate bridges were prepared and studied, namely [Cu2(μ-fu)(pmdien)2(H2O)2](ClO4)2 (complex No. 5) and [Cu2(μ-dtdp)(pmdien)2(H2O)2](ClO4)2 (complex No. 6), where H2fu = fumaric acid, pmdien = N,N,N′,N″,N″ pentamethyldiethylenetriamine, and H2dtdp = 3,3′-dithiodipropionic acid. The copper atoms are coordinated in the same mode by the tridentate pmdien ligand and oxygen of water molecules, and they only differ in the dicarboxylate bridge. This work is focused on the study of the inhibitory effect of these potential antimicrobial drugs on the activity of the most important human liver drug-metabolizing enzymes, cytochromes P450 (CYP), especially their forms CYP2C8, CYP2C19, and CYP3A4. The obtained results allow us to estimate the probability of potential drug interactions with simultaneously administrated drugs that are metabolized by these CYP enzymes. In conclusion, the presence of adverse effects due to drug–drug interactions with concomitantly used drugs cannot be excluded, and hence, topical application may be recommended as a relatively safe approach. [ABSTRACT FROM AUTHOR]

The 3-ketoacyl-CoA thiolase is the rate-limiting enzyme for linear dicarboxylic acids production. However, the promiscuous substrate specificity and suboptimal catalytic performance have restricted its application. Here we present both biochemical and structural analyses of a high-efficiency 3-ketoacyl-CoA thiolase Tfu_0875. Notably, Tfu_0875 displayed heightened activity and substrate specificity for succinyl-CoA, a key precursor in adipic acid production. To enhance its performance, a deep learning approach (DLKcat) was employed to identify effective mutants, and a computational strategy, known as the greedy accumulated strategy for protein engineering (GRAPE), was used to accumulate these effective mutants. Among the mutants, Tfu_0875N249W/L163H/E217L exhibited the highest specific activity (320% of wild-type Tfu_0875), the greatest catalytic efficiency (kcat/KM = 1.00 min-1 mM-1 ), the highest succinyl-CoA specificity (KM = 0.59 mM, 28.1% of Tfu_0875) and dramatically reduced substrate binding energy (− 30.25 kcal mol-1 v.s. -15.94 kcal mol−1 ). A structural comparison between Tfu_0875N249W/L163H/E217L and the wild type Tfu_0875 revealed that the increased interaction between the enzyme and succinyl-CoA was the primary reason for the enhanced enzyme activity. This interaction facilitated rapid substrate anchoring and stabilization. Furthermore, a reduced binding pocket volume improved substrate specificity by enhancing the complementarity between the binding pocket and the substrate in stereo conformation. Finally, our rationally designed mutant, Tfu_0875N249W/L163H/E217Lincreased the adipic acid titer by 1.35-fold compared to the wild type Tfu_0875 in shake flask. The demonstrated enzymatic methods provide a promising enzyme variant for the adipic acid production. The above effective substrate binding pocket engineering strategy can be beneficial for the production of other industrially competitive biobased chemicals when be applied to other thiolases. [ABSTRACT FROM AUTHOR]

[Display omitted] Photocatalytic nitrogen fixation is seen to be a potential technology for nitrogen reduction due to its eco-friendliness, low energy consumption, and environmental protection. In this study, photocatalysts with abundant oxygen vacancies (Zr-naphthalene dicarboxylic acid (Zr-NDC) and Zr-phthalic acid (Zr-BDC)) were designed using 1,4-naphthalene dicarboxylic acid (H 2 NDC) and 1,4-phthalic acid (H 2 BDC) as ligands. Since the structure of H 2 NDC includes one extra benzene ring than H 2 BDC, the charge density differential of the organic ligand is probably altered. The hypothesis is proved by density function theory (DFT) calculation. The abundant oxygen vacancies of the catalyst offer numerous active sites for nitrogen fixation. Concurrently, the process of ligand–metal charge transfer facilitates photo-electron transfer, creating an active center for nitrogen reduction. Additionally, the functionalization of ligand amplifies another pathway for charge transfer, broadening the light absorption range of Metal-organic framework (MOF) and increasing its capacity for nitrogen reduction. In contrast to H 2 BDC, the benzene ring added in H 2 NDC structure acts as an electron energy storage tank with a stronger electron density difference favorable for photogenerated electron-hole separation resulting in higher photocatalytic activity in Zr-NDC. The experimental results show that the nitrogen fixation efficiency of Zr-NDC is 163.7 µmol g−1h−1, which is significantly better than that of Zr-BDC (29.3 µmol g−1h−1). This work utilizes cost-effective and non-toxic ingredients to design highly efficient photocatalysts, thereby significantly contributing to the practical implementation of green chemistry principles. [ABSTRACT FROM AUTHOR]

We introduce a novel dual redox mediator synthesized by covalently linking ferrocene dicarboxylic acid (FcDA) and thionine (TH) onto a pre-treated glassy carbon electrode. This unique structure significantly enhances the electro-oxidation of dopamine (DA) and the reduction of hydrogen peroxide (H2O2), offering a sensitive detection method for both analytes. The electrode exhibits exceptional sensitivity, selectivity, and stability, demonstrating potential for practical applications in biosensing. It facilitates rapid electron transfer between the analyte and the electrode surface, detecting H2O2 concentrations ranging from 1.5 to 60 µM with a limit of detection (LoD) of 0.49 µM and DA concentrations from 0.3 to 230 µM with an LoD of 0.07 µM. The electrode's performance was validated through real-sample analyses, yielding satisfactory results. [ABSTRACT FROM AUTHOR]

Aldehyde dehydrogenases (ALDHs) represent a superfamily of enzymes, which oxidize aldehydes to the corresponding acids. Certain families, namely ALDH9 and ALDH10, are best active with ω-aminoaldehydes arising from the metabolism of polyamines such as 3-aminopropionaldehyde and 4-aminobutyraldehyde. Plant ALDH10s show broad specificity and accept many different aldehydes (aliphatic, aromatic and heterocyclic) as substrates. This work involved the above-mentioned aminoaldehydes acylated with dicarboxylic acids, phenylalanine, and tyrosine. The resulting products were then examined with native ALDH10 from pea and recombinant ALDH7s from pea and maize. This investigation aimed to find a common efficient substrate for the two plant ALDH families. One of the best natural substrates of ALDH7s is aminoadipic semialdehyde carrying a carboxylic group opposite the aldehyde group. The substrate properties of the new compounds were demonstrated by mass spectrometry of the reaction mixtures, spectrophotometric assays and molecular docking. The N-carboxyacyl derivatives were good substrates of pea ALDH10 but were only weakly oxidized by the two plant ALDH7s. The N-phenylalanyl and N-tyrosyl derivatives of 3-aminopropionaldehyde were good substrates of pea and maize ALDH7. Particularly the former compound was converted very efficiently (based on the kcat/Km ratio), but it was only weakly oxidized by pea ALDH10. Although no compound exhibited the same level of substrate properties for both ALDH families, we show that these enzymes may possess more common substrates than expected. [ABSTRACT FROM AUTHOR]

Background: Numerous research studies have indicated a possible association between type 2 diabetes (T2DM) and gut microbiota. To explore specific metabolic pathways connecting gut microbiota and T2DM, we employed Mendelian randomization (MR) and linkage disequilibrium score regression (LDSC) techniques. Methods: This research utilized data from genome-wide association studies (GWAS) that are publicly accessible. We evaluated the genetic correlation between gut microbiota and T2DM using LDSC. Causality was primarily determined through the inverse variance weighted (IVW) method. To verify the robustness of our results, we conducted sensitivity analyses using several approaches, including the weighted median, MR-Egger, and MR-PRESSO. We integrated summary effect estimates from LDSC, along with forward and reverse MR, into a meta-analysis for T2DM using various data sources. Additionally, mediation analysis was performed to explore the impact of plasma metabolites on the relationship between gut microbiota and T2DM. Results: Our study indicated a significant genetic correlation between genus RuminococcaceaeUCG005 (Rg = -0.26, Rg_;P = 2.07 x 10-4) and T2DM. Moreover, the forward MR analysis identified genus RuminococcaceaeUCG010 (OR = 0.857, 95% CI 0.795, 0.924; P = 6.33 x 10-5) and order Clostridiales (OR = 0.936, 95% CI 0.878, 0.997; P = 0.039) as being significantly associated with a decreased risk of T2DM. The analysis also highlighted several plasma metabolites as significant mediators in these relationships, with metabolites like octadecadienedioate (C18:2-DC) and branched chain 14:0 dicarboxylic acid being notably involved. Conclusion: The findings demonstrate a significant impact of gut microbiota on T2DM via plasma metabolites, suggesting potential metabolic pathways for therapeutic targeting. This study enhances our understanding of the microbiota's role in T2DM pathogenesis and supports the development of microbiota-based interventions. [ABSTRACT FROM AUTHOR]

Cinnamomum tamala leaf (CTL), also known as Indian bay leaf, is used all over the world for seasoning, flavoring, and medicinal purposes. These characteristics could be explained by the presence of several essential bioactive substances and lipid derivatives. In this work, rapid screening and identification of the chemical compounds in supercritical (SC)-CO2 extracts of CTL by use of UPLC-Q-TOF-MSE with a multivariate statistical analysis approach was established in both negative and positive mode. A total of 166 metabolites, including 66 monocarboxylic fatty acids, 52 dicarboxylic fatty acids, 27 fatty acid amides, and 21 cinnamic acid derivatives, were tentatively identified based on accurate mass and the mass spectrometric fragmentation pattern, out of which 142 compounds were common in all SC-CO2 extracts of CTL. Further, PCA and cluster hierarchical analysis clearly discriminated the chemical profile of analyzed extracts and allowed the selection of SC-CO2 extract rich in fatty acids, fatty acid amides, and other bioactive constituents. The result showed that the higher number of compounds was detected in CTL4 (300 bar/55 °C) extract than the other CTL extracts. The mono- and di-carboxylic fatty acids, fatty acid amides, and cinnamic acid derivatives were identified in CTL for the first time. UPLC-Q-TOF-MSE combined with chemometric analysis is a powerful method to rapidly screen the metabolite profiling to justify the quality of CTL as a flavoring agent and in functional foods. [ABSTRACT FROM AUTHOR]

Gelsemium sempervirens (L.) J.St.-Hil. is an evergreen shrub occurring naturally in North and Middle America. So far, more than 120 alkaloids have been identified in this plant in addition to steroids, coumarins and iridoids, and its use in traditional medicine has been traced back to these compound classes. However, a comprehensive phytochemical investigation of the plant with a special focus on further compound classes has not yet been performed. Therefore, the present study aimed at an extensive HPLC-MSn characterization of secondary metabolites and, for the first time, reports the occurrence of various depsides and phenolic glycerides in G. sempervirens roots and rhizomes, consisting of benzoic and cinnamic acid derivatives as well as dicarboxylic acids. Furthermore, mono- and disaccharides were assigned by GC-MS. Applying the Folin–Ciocalteu assay, the phenolic content of extracts obtained with different solvents was estimated to range from 30 to 50% calculated as chlorogenic acid equivalents per g dry weight and was related to the DPPH radical scavenging activity of the respective extracts. Upon lactic acid fermentation of aqueous G. sempervirens extracts, degradation of phenolic esters was observed going along with the formation of low-molecular volatile metabolites. [ABSTRACT FROM AUTHOR]

​​​​​​​Volatile organic compounds (VOCs) play a key role in tropospheric chemistry, giving rise to secondary products such as highly oxygenated organic molecules (HOMs) and secondary organic aerosols (SOAs). HOMs, a group of low-volatility gas-phase products, are formed through the autoxidation process of peroxy radicals (RO 2) originating from the oxidation of VOCs. The measurement of HOMs is made by a NO 3- ToFCIMS instrument, which also detects other species like small highly oxygenated VOCs (e.g., dicarboxylic acids) and sulfuric acid (H 2 SO 4). The instrument response to HOMs is typically estimated using H 2 SO 4 , as HOMs are neither commercially available nor easily synthesized in the laboratory. The resulting calibration factor is then applied to quantify all species detected using this technique. In this study, we explore the sensitivity of the instrument to commercially available small organic compounds, primarily dicarboxylic acids, given the limitations associated with producing known amounts of HOMs for calibration. We compare these single-compound calibration factors to the one obtained for H 2 SO 4 under identical operational conditions. The study found that the sensitivity of the NO 3- ToFCIMS varies depending on the specific type of organic compound, illustrating how a single calibration factor derived from sulfuric acid is clearly inadequate for quantifying all detected species using this technique. The results highlighted substantial variability in the calibration factors for the tested organic compounds, with 4-nitrocatechol exhibiting the highest sensitivity and pyruvic acid the lowest. The obtained sulfuric acid calibration factor agreed well with the previous values from the literature. In summary, this research emphasized the need to develop reliable and precise calibration methods for progressively oxygenated reaction products measured with a NO 3- chemical-ionization mass spectrometer (CIMS), for example, HOMs. [ABSTRACT FROM AUTHOR]

This study investigated the synthesis of α-hemihydrate gypsum (α-HH) through semiliquid autoclaving of phosphogypsum (PG) using various carboxylic acids as modifying agents. The impact of carboxyl group spatial location, auxiliary functional group type, and the number of carboxyl groups within the carboxylic acid modifiers on the mechanical strength and crystal morphology of α-HH was analyzed using scanning electron microscopy (SEM), strength testing, and molecular dynamics simulations. The results revealed a significant influence of the carboxylic acid molecular structure on the α-HH crystal morphology. Monocarboxylic acids and dicarboxylic acids with a long carbon chain length between carboxyl groups exhibited preferential adsorption on the (200), (110), and (-110) crystal planes, promoting crystal growth along the c-axis. In contrast, hydroxyl groups and cis double bonds in the modifier structure induced selective adsorption on the (001) plane, hindering growth along the c-axis. Conversely, trans double bonds favored adsorption on the (200), (110), and (-110) planes, enhancing growth along the c-axis. Based on these observations, screening principles for carboxylic acid modifiers were established, suggesting that: 1) the number of carboxyl groups should exceed 2; 2) the optimal carbon atom spacing between carboxyl groups is 3; and 3) auxiliary functional groups such as hydroxyl groups and cis double bonds should be introduced. Modifiers like citric acid, ethylene diamine tetraacetic acid (EDTA), and pyromellitic acid, within concentration ranges of 0.05%-0.1%, 0.1%-0.15%, and 0.05%-0.1%, respectively, yielded α-HH with flexural strengths exceeding 4 MPa and compressive strengths greater than 35 MPa, demonstrating the validity of these principles. [ABSTRACT FROM AUTHOR]

A series of novel salts based on aromatic polyamines and 2,3-pyrazinedicarboxylic acid, such as C10H12N6O5 (1), C10H9ClN6O4 (2), C11H10N8O4 (3), and C14H17N16O5.5 (4) or 3,4-thiophenedicarboxylic acid, such as C10H10N4O4S (5), C10H9ClN4O4S (6), and C10H10N4O4S2 (7), were synthesized and characterized by single-crystal X-ray diffraction. All compounds crystallize in a monoclinic space group. The structure was subjected to complex Hirshfeld surface analysis, molecular electrostatic potential, enrichment ratio, and energy framework calculations. The influence of different cations on the packing of 3-carboxypyrazine-2-carboxylate and 4-carboxythiophene-3-carboxylate anions in the crystal lattice was studied. O...H/H...O interactions are the main contributor in all crystals. In addition, in a series of pyrazine-containing structures, N(C)...H/H...N(C) interactions have relevance, while in a series of thiophene-based compounds, C...H/H...C and S...H(O)/H(O)...S. In addition, Cl-based interactions are observed in compound 2. According to the enrichment ratio calculations, O...H/H...O and C...C are the most preferable interactions in all structures. The energy frameworks are dominated by the dispersive contribution, only in compound 3 is the electrostatic term dominant. The analyzed structures reveal intra- and intermolecular recurrent supramolecular synthons. In both series of crystals, the robust H-bonded centrosymmetric dimer R22(8) as homo- or as heterosynthon (in compounds 2, 3, 6, and 7) and the intramolecular synthon S(7) generated by O-H...O interactions (in compounds 2, 6, and 7) are present. The supramolecular patterns formed by π...π (C...C) and C-O(Cl,S)...C are also noticeable. Notably, a dual synthon linking the supramolecular chain via π...π interactions and the homosynthon R22(8) via N-H...N interactions is visible in both series of new salts. A library of H-bonding motifs at diverse levels of supramolecular architecture is provided. We extended the analysis of intramolecular H-bonding motifs to similar structures deposited in the Cambridge Structural Database. Another important feature is the existence of an intramolecular O...H...O bridge between two neighboring carboxylic groups as substituents in anions in compounds 3 and 5. In this context, we performed quantum theory of atoms-in-molecule calculations to reveal more details. [ABSTRACT FROM AUTHOR]

In this study, crosslinked films of polyvinyl alcohol (PVA) were prepared using two dicarboxylic acids: saturated succinic acid (SA) and unsaturated maleic acid (MAL) as crosslinkers. The crosslinking capabilities of these acids were compared through physical, chemical, mechanical, morphological, thermal analysis, and swelling measurements to investigate their impact on the physicochemical properties of the resulting films. Attenuated total reflectance fourier transform infrared spectroscopy (FTIR) confirmed the occurrence of an esterification reaction between PVA and the dicarboxylic acids. Based on the degree of crosslinking and thermal properties, it was noted that the crosslinking achieved with maleic acid is more effective for PVA compared with succinic acid. The crosslinking degree of PVA‐MAL was determined to be 6.47 times higher than that of the PVA‐SA film. In terms of thermal stability, the decomposition temperature for crosslinked PVA‐MAL was measured at 365.57°C, whereas PVA‐SA exhibited a slightly lower decomposition temperature of 362.58°C. The findings indicate that the PVA‐MAL film displays lower crystallinity and a higher contact angle (80.60°) in contrast to PVA‐SA (76.0°) and PVA (30.4°). Atomic force microscopy analysis indicated that the PVA‐SA film exhibited more surface roughness compared with the smoother PVA‐MAL film. Also, crosslinked films displayed enhanced elasticity and resilience in comparison with neat PVA, which may be due to the difference in crosslinking density, disruption in intermolecular hydrogen bonding due to crosslinking, and incorporation of flexible crosslinkers. Highlights: PVA was crosslinked using SA and MAL.Unsaturated MAL exhibited superior crosslinking density over saturated SA.PVA‐SA film exhibited a porous surface compared to PVA‐MAL film.PVA crosslinked with unsaturated MAL showed higher thermal stability than SA.Both the films showed enhanced elasticity and resilience compared with neat PVA. [ABSTRACT FROM AUTHOR]

We report primordial aqueous alteration signatures in water-soluble organic molecules from the carbonaceous asteroid (162173) Ryugu by the Hayabusa2 spacecraft of JAXA. Newly identified low-molecular-weight hydroxy acids (HO-R-COOH) and dicarboxylic acids (HOOC-R-COOH), such as glycolic acid, lactic acid, glyceric acid, oxalic acid, and succinic acid, are predominant in samples from the two touchdown locations at Ryugu. The quantitative and qualitative profiles for the hydrophilic molecules between the two sampling locations shows similar trends within the order of ppb (parts per billion) to ppm (parts per million). A wide variety of structural isomers, including α- and β-hydroxy acids, are observed among the hydrophilic molecules. We also identify pyruvic acid and dihydroxy and tricarboxylic acids, which are biochemically important intermediates relevant to molecular evolution, such as the primordial TCA (tricarboxylic acid) cycle. Here, we find evidence that the asteroid Ryugu samples underwent substantial aqueous alteration, as revealed by the presence of malonic acid during keto–enol tautomerism in the dicarboxylic acid profile. The comprehensive data suggest the presence of a series for water-soluble organic molecules in the regolith of Ryugu and evidence of signatures in coevolutionary aqueous alteration between water and organics in this carbonaceous asteroid. In this study, the authors report primordial aqueous alteration signatures in water-soluble organic molecules from the carbonaceous asteroid Ryugu. This provides evidence o coevolutionary aqueous alteration between water and organics in this asteroid. [ABSTRACT FROM AUTHOR]

Background: An important step in replacing petrochemical products with sustainable, cost-effective alternatives is the use of feedstocks other than, e.g., pure glucose in the fermentative production of platform chemicals. Ustilaginaceae offer the advantages of a wide substrate spectrum and naturally produce a versatile range of value-added compounds under nitrogen limitation. A promising candidate is the dicarboxylic acid malic acid, which may be applied as an acidulant in the food industry, a chelating agent in pharmaceuticals, or in biobased polymer production. However, fermentable residue streams from the food and agricultural industry with high nitrogen content, e.g., sugar beet molasses, are unsuited for processes with Ustilaginaceae, as they result in low product yields due to high biomass and low product formation. Results: This study uncovers challenges in evaluating complex feedstock applicability for microbial production processes, highlighting the role of secondary substrate limitations, internal storage molecules, and incomplete assimilation of these substrates. A microliter-scale screening method with online monitoring of microbial respiration was developed using malic acid production with Ustilago trichophora on molasses as an application example. Investigation into nitrogen, phosphate, sulphate, and magnesium limitations on a defined minimal medium demonstrated successful malic acid production under nitrogen and phosphate limitation. Furthermore, a reduction of nitrogen and phosphate in the elemental composition of U. trichophora was revealed under the respective secondary substrate limitation. These adaptive changes in combination with the intricate metabolic response hinder mathematical prediction of product formation and make the presented screening methodology for complex feedstocks imperative. In the next step, the screening was transferred to a molasses-based complex medium. It was determined that the organism assimilated only 25% and 50% of the elemental nitrogen and phosphorus present in molasses, respectively. Due to the overall low content of bioavailable phosphorus in molasses, the replacement of the state-of-the-art nitrogen limitation was shown to increase malic acid production by 65%. Conclusion: The identification of phosphate as a superior secondary substrate limitation for enhanced malic acid production opens up new opportunities for the effective utilization of molasses as a more sustainable and cost-effective substrate than, e.g., pure glucose for biobased platform chemical production. [ABSTRACT FROM AUTHOR]

Background: Ideally, the barrier properties of a fruit's cuticle persist throughout its development. This presents a challenge for strawberry fruit, with their rapid development and thin cuticles. The objective was to establish the developmental time course of cuticle deposition in strawberry fruit. Results: Fruit mass and surface area increase rapidly, with peak growth rate coinciding with the onset of ripening. On a whole-fruit basis, the masses of cutin and wax increase but on a unit surface-area basis, they decrease. The decrease is associated with marked increases in elastic strain. The expressions of cuticle-associated genes involved in transcriptional regulation (FaSHN1, FaSHN2, FaSHN3), synthesis of cutin (FaLACS2, FaGPAT3) and wax (FaCER1, FaKCS10, FaKCR1), and those involved in transport of cutin monomers and wax constituents (FaABCG11, FaABCG32) decreased until maturity. The only exceptions were FaLACS6 and FaGPAT6 that are presumably involved in cutin synthesis, and FaCER1 involved in wax synthesis. This result was consistent across five strawberry cultivars. Strawberry cutin consists mainly of C16 and C18 monomers, plus minor amounts of C19, C20, C22 and C24 monomers, ω-hydroxy acids, dihydroxy acids, epoxy acids, primary alcohols, carboxylic acids and dicarboxylic acids. The most abundant monomer is 10,16-dihydroxyhexadecanoic acid. Waxes comprise mainly long-chain fatty acids C29 to C46, with smaller amounts of C16 to C28. Wax constituents are carboxylic acids, primary alcohols, alkanes, aldehydes, sterols and esters. Conclusion: The downregulation of cuticle deposition during development accounts for the marked cuticular strain, for the associated microcracking, and for their high susceptibility to the disorders of water soaking and cracking. [ABSTRACT FROM AUTHOR]

Dicarboxylic fatty acids are generated in the liver and kidney in a minor pathway called fatty acid ω-oxidation. The effects of consuming dicarboxylic fatty acids as an alternative source of dietary fat have not been explored. Here, we fed dodecanedioic acid, a 12-carbon dicarboxylic (DC12), to mice at 20% of daily caloric intake for 9 weeks. DC12 increased metabolic rate, reduced body fat, reduced liver fat, and improved glucose tolerance. We observed DC12-specific breakdown products in liver, kidney, muscle, heart, and brain, indicating that oral DC12 escaped first-pass liver metabolism and was utilized by many tissues. In tissues expressing the “a” isoform of acyl-CoA oxidase-1 (ACOX1), a key peroxisomal fatty acid oxidation enzyme, DC12 was chain shortened to the TCA cycle intermediate succinyl-CoA. In tissues with low peroxisomal fatty acid oxidation capacity, DC12 was oxidized by mitochondria. In vitro, DC12 was catabolized even by adipose tissue and was not stored intracellularly. We conclude that DC12 and other dicarboxylic acids may be useful for combatting obesity and for treating metabolic disorders. [ABSTRACT FROM AUTHOR]

2,6-pyridine dicarboxylic acid (DPA) is an exceptional biomarker of notorious anthrax spores. Therefore, the rapid, sensitive, and selective quantitative detection of DPA is extremely significant and urgent. This paper reports a Zn(II) metal–organic framework with the formula of {[Zn6(NDA)6(DPBT)3] 2H2O·3DMF}n (MOF-1), which consists of 2,6-naphthalenedicarboxylic acid (2,6-NDA), 4,7-di(4-pyridyl)-2,1,3-benzothiadiazole (DPBT), and Zn(II) ions. Structural analysis indicated that MOF-1 is a three-dimensional (3D) network which crystallized in the monoclinic system with the C2/c space group, revealing high pH, solvent, and thermal stability. Luminescence sensing studies demonstrated that MOF-1 had the potential to be a highly selective, sensitive, and recyclable fluorescence sensor for the identification of DPA. Furthermore, fluorescent test paper was made to detect DPA promptly with color changes. The enhancement mechanism was established by the hydrogen-bonding interaction and photoinduced electron transfer transition between MOF-1 and DPA molecules. [ABSTRACT FROM AUTHOR]

Two new triarylamine-based diamine monomers, namely, N,N′-bis(4-methoxyphenyl)-N,N′-bis(4-(4-aminophenyl-4′-methoxyphenylamino)phenyl)-p-phenylenediamine (3) and N,N′-bis(4-methoxyphenyl)-N,N′-bis(4-((4-aminophenyl-1-naphthyl)amino)phenyl)-p-phenylenediamine (7), were successfully synthesized and led to two series of electroactive polyamides by polycondensation reactions with common aromatic dicarboxylic acids. The polymers demonstrated multicolored electrochromism, high optical contrast, and remarkable enhancements in redox and electrochromic stability. Compared to other triarylamine-based polymers, the studied polyamides exhibited enhanced electrochromic stability (only 3~6% decay of its coloration efficiency at 445 nm after 14,000 switching cycles) at the first oxidation stage. The polyamides also showed strong absorption in the near-infrared region upon oxidation. Polymers with multicolored electrochromism and high redox stability can be developed by incorporation of four triarylamine cores in each repeat unit and electron-donating methoxy groups on the active sites of the triphenylamine units. [ABSTRACT FROM AUTHOR]

Saline-sodic stress induces iron deficiency in rice, reduces leaf photosynthetic performance, and inhibits yield enhancement. In this study, we investigated the effects of exogenous Fe on the photosynthetic performance and transcriptomics of two different tolerant rice cultivars CB9 (Changbai9: saline tolerant cultivar) and TH899 (Tonghe899: saline sensitive cultivar) with 4-week-old Fe-deficient rice seedlings under saline stress, Fe deficiency stress, and both co-stresses. The results showed that under saline and alkaline stress, spraying exogenous iron favored the growth of the two cultivars of rice, with a 32.68% and 39.82 increase in fresh weight, a 2.20-fold and 2.16-fold increase in pigment, respectively, and an 80.28% and 100.00% increase in net photosynthetic rate, respectively, as compared with the iron-deficiency treatment. Transcriptome analysis showed that we found a higher number of differentially expressed genes (7785 differentially expressed genes) in response to exogenous Fe spraying in the soda-salt sensitive variety TH899. The differentially expressed genes that are common to the two cultivars are primarily enriched in metabolic pathways, including plant hormone signal transduction (map04075) and phenylpropanoid biosynthesis (map00940). Specifically, among these genes, 14 are differentially expressed in the carotenoid biosynthetic metabolic pathway. The differentially expressed genes specific to the salinity-tolerant variety CB9 were mainly enriched in the metabolic pathways of glyoxylate and dicarboxylic acid methyl metabolism (map00630), and carbon fixation in photosynthetic organisms (map00710), among which 20 genes were significantly expressed in the pathway for carbon fixation in photosynthetic organisms (map00710). The research results offer specific theoretical support for enhancing the salt tolerance of rice. [ABSTRACT FROM AUTHOR]

Dendrimers are potent nanocarriers in drug delivery systems because their structure can be precisely controlled. We previously reported that polyamidoamine (PAMAM) dendrimers that were modified with 1,2-cyclohexanedicarboxylic acid (CHex) and phenylalanine (Phe), PAMAM-CHex-Phe, exhibited an effective association with various immune cells, including T-cells. In this study, we synthesized various carboxy-terminal Phe-modified dendrimers with different linkers using phthalic acid and linear dicarboxylic acids to determine the association of these dendrimers with Jurkat cells, a T-cell model. PAMAM-n-hexyl-Phe demonstrated the highest association with Jurkat T-cells. In addition, dendri-graft polylysine (DGL) with CHex and Phe, DGL-CHex-Phe, was synthesized, and its association with Jurkat cells was investigated. The association of DGL-CHex-Phe with T-cells was higher than that of PAMAM-CHex-Phe. However, it was insoluble in water and thus it is unsuitable as a drug carrier. Model drugs, such as protoporphyrin IX and paclitaxel, were loaded onto these dendrimers, and the most model drug molecules could be loaded into PAMAM-CHex-Phe. PTX-loaded PAMAM-CHex-Phe exhibited cytotoxicity against Jurkat cells at a similar level to free PTX. These results suggest that PAMAM-CHex-Phe exhibited both efficient T-cell association and drug loading properties. [ABSTRACT FROM AUTHOR]

Solid electrolyte materials with high structural stability and excellent proton conductivity (σ) have long been a popular and challenging research topic in the fuel cell field. This problem can be addressed because of the crystalline metal–organic frameworks' (MOFs') high structural stability, adjustable framework composition, and dense H-bonded networks. Herein, one highly stable Sr(II) MOF, {[Sr(H2tmidc)2(H2O)3]·4H2O}n (1) (H3tmidc = 2-(1H-tetrazolium-1-methylene)-1H-imidazole-4,5-dicarboxylic acid) was successfully fabricated, which was structurally characterized by single-crystal X-ray diffraction and electrochemically examined by the AC impedance determination. The results demonstrated that the σ of the compound manifested a positive dependence on temperature and humidity, and the optimal proton conductivity is as high as 1.22 × 10−2 S/cm under 100 °C and 98% relative humidity, which is at the forefront of reported MOFs with ultrahigh σ. The analysis of the proton conduction mechanism reveals that numerous tetrazolium groups, carboxyl groups, coordination, and crystallization water molecules in the framework are responsible for the high efficiency of proton transport. This work offers a fresh perspective on how to create novel crystalline proton conductive materials. [ABSTRACT FROM AUTHOR]

Octacalcium phosphate (OCP) is an attractive base material to combine into components developed for medical purposes, especially those used in bone replacement procedures, not only because of its excellent biocompatibility but also because of its ability to intercalate with multiple types of molecular layers such as silica, dicarboxylic acid, and various cations. On the other hand, there are no examples of simultaneous substituting for several different compounds on OCPs. Therefore, in this study, the physical and mechanical strength (DTS: diametral tensile strength) of OCPs substituted with both silica and dicarboxylic acids (thiomalate: SH-malate) were evaluated. By optimizing the amount of SH-malate, we were able to prepare a block consisting of OCPs with both silica and SH-malate supported in the interlayer. The composition of the OCP-based compound comprising this block was Ca8Na1.07H6.33(PO4)4.44(SiO4)1.32(SH-malate)2.40·nH2O. Interestingly, the low mechanical strength, a drawback of silica-substituted OCP blocks, could be improved by dicarboxylic acid substituting. The dicarboxylic acid addition increased the mechanical strength of silica-substituted OCP blocks, and the acid successfully incorporated into the interlayer, even with the presence of silica. These results are expected to advance the creation of better silica-substituted OCPs and improved bone replacement materials. [ABSTRACT FROM AUTHOR]

Background: Dodecanedioic acid (DDA), a typical medium-chain dicarboxylic fatty acid with widespread applications, has a great synthetic value and a huge industrial market demand. Currently, a sustainable, eco-friendly and efficient process is desired for dodecanedioic acid production. Results: Herein, a multi-enzymatic cascade was designed and constructed for the production of DDA from linoleic acid based on the lipoxygenase pathway in plants. The cascade is composed of lipoxygenase, hydroperoxide lyase, aldehyde dehydrogenase, and unidentified double-bond reductase in E. coli for the main cascade reactions, as well as NADH oxidase for cofactor recycling. The four component enzymes involved in the cascade were co-expressed in E. coli, together with the endogenous double-bond reductase of E. coli. After optimizing the reaction conditions of the rate-limiting step, 43.8 g L− 1 d− 1 of DDA was obtained by a whole-cell one-pot process starting from renewable linoleic acid. Conclusions: Through engineering of the reaction system and co-expressing the component enzymes, a sustainable and eco-friendly DDA biosynthesis route was set up in E. coli, which afforded the highest space time yield for DDA production among the current artificial multi-enzymatic routes derived from the LOX-pathway, and the productivity achieved here ranks the second highest among the current research progress in DDA biosynthesis. [ABSTRACT FROM AUTHOR]

A family of silver(I) and copper(I) complexes containing carboxylate ligands were prepared from the corresponding carboxylic acids and Ag2O. The compounds were characterized by various spectroscopic methods and X-ray diffraction. In the solid state, the silver(I) salts are coordination polymers based on dinuclear silver species with bridging carboxylate ligands. The reaction of these silver salts with Ph3P gives four-coordinate, tetrahedral bis(phosphine) complexes. Analogous copper(I) bis(phosphine) compounds were prepared by the reduction of copper(II) carboxylates with Ph3P. Decomposition temperatures and thermal decomposition products were studied by TGA/DSC measurements. The metal compounds decomposed cleanly to their respective metals (silver or copper) at temperatures ranging from 206 to 338 °C. [ABSTRACT FROM AUTHOR]

The rapid development of 3D printing technology and the emerging applications of shape memory elastomer have greatly stimulated the research of photocurable polymers. In this work, glycerol (Gly) was polycondensed with sebacic, dodecanedioic, or tetradecanedioic acids to provide precursor polyesters with hydroxyl or carboxyl terminal groups, which were further chemically functionalized by acryloyl chloride to introduce sufficient, photocurable, and unsaturated double bonds. The chemical structures of the acrylated polyesters were characterized by FT IR and NMR spectroscopies. The photoinitiated crosslinking behavior of the acrylated polyesters under ultraviolet irradiation without the addition of any photoinitiator was investigated. The results showed that the precursor polyesters that had a greater number of terminated hydroxyls and a less branched structure obtained a relatively high acetylation degree. A longer chain of aliphatic dicarboxylic acids (ADCAs) and higher ADCA proportion lead to a relatively lower photopolymerization rate of acrylated polyesters. However, the photocured elastomers with a higher ADCA proportion or longer-chain ADCAs resulted in better mechanical properties and a lower degradation rate. The glass transition temperature (Tg) of the elastomer increased with the alkyl chain length of the ADCAs, and a higher Gly proportion resulted in a lower Tg of the elastomer due to its higher crosslinking density. Thermal gravimetric analysis (TGA) showed that the chain length of the ADCAs and the molar ratio of Gly to ADCAs had less of an effect on the thermal stability of the elastomer. As the physicochemical properties can be adjusted by choosing the alkyl chain length of the ADCAs, as well as changing the ratio of Gly:ADCA, the photocurable polyesters are expected to be applied in multiple fields. [ABSTRACT FROM AUTHOR]

[Display omitted] • A new 3-D bi-metal organic framework was synthesized by hydrothermal method. • After pyrolysis, binary metal oxides were prepared and applied to the anode materials of LIBs. • CeCo-700 has the highest specific capacity of 952 mAh g−1 at 100 mA g−1 after 150 cycles. Precursor method is a well-known technology for preparing certain functional materials. In this work, a novel 3d-4f bimetallic organic framework, denoted as 45MCeCo (45 M representing 4,5-imidazole dicarboxylic acid), was successfully synthesized via a hydrothermal technique. The compound thus obtained has the molecular formula of C 10 H 11 CeCoN 4 O 12. By meticulously controlling the amounts of the experimental materials, it was feasible to prepare flower-like crystals possessing identical single crystal structures and significantly larger specific surface areas. As a precursor for electrode materials, this structure underwent calcination at different temperatures to prepare Co 3 O 4 /CeO 2 composites with in situ composite heterostructures. Post-electrochemical tests revealed that CeO 2 remains unreactive across all potentials, thereby contributing to the stabilization of the electrode material structure. In contrast, Co 3 O 4 participated in redox reactions to provide a specific capacity to the sample. In addition, when comparing the performance of the electrode material under different calcination conditions, it became evident that the material exhibited optimal electrochemical performance when subjected to a temperature of 700 °C for 2 h. [ABSTRACT FROM AUTHOR]

Furan dicarboxylic acid (FDCA) has gained significant attention due to its use as a precursor in the production of polyethylene furanoate (PEF). PEF is a bio-based plastic that can be used as a sustainable alternative in the production of plastics to replace PET derived from petroleum. In the FDCA production from biomass, there are three main steps: conversion of biomass to glucose, conversion of glucose to 5-hydroxy-methylfurfural (HMF), and oxidation of HMF to FDCA. The HMF production processes use high amounts of solvents such as dimethyl sulfoxide (DMSO), dichloromethane (DCM), and acetic acid, etc., to enhance the solubility, assist in the separation, and increase the production yield. The HMF and FDCA productions require the purification process and solvent recovery process. To assess the performance and improve the system efficiency of FDCA production from biomass, this work aims to design the integrated processes of HMF synthesis from biomass, FDCA production from HMF, HMF purification, and solvent recovery. The result indicates that the pressure and temperature of the evaporator for HMF separation affect the purity of HMF. The solvent recovery process of DMSO and DCM can enhance HMF yield by 21.6% and FDCA yield by 36.71%. [ABSTRACT FROM AUTHOR]

A series of 5-alkoxy-1,3-benzenedicarbaldehydes and related dimers were prepared in three steps from dimethyl 5-hydroxyisophthalate. Acid catalyzed condensation of the dialdehydes with a tripyrrane dicarboxylic acid, followed by oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, afforded good yields of 3-alkoxybenziporphyrins, although dimeric tetraaldehydes failed to give isolatable porphyrinoid products. Proton NMR spectroscopy gave no indication of an aromatic ring current, but addition of trifluoroacetic acid resulted in the formation of dications that exhibited weakly diatropic characteristics. Spectroscopic titration with TFA demonstrated that stepwise protonation took place, generating monocationic and dicationic species. 3-Alkoxybenziporphyrins reacted with nickel(II) or palladium(II) acetate to give the related nickel(II) or palladium(II) complexes. These stable organometallic derivatives showed increased diatropic properties that were most pronounced for the palladium(II) complexes. These unique porphyrinoids provide further insights into the properties of benziporphyrins. [ABSTRACT FROM AUTHOR]

Background: Glycine is an integral component of the human detoxification system as it reacts with potentially toxic exogenous and endogenously produced compounds and metabolites via the glycine conjugation pathway for urinary excretion. Because individuals with obesity have reduced glycine availability, this detoxification pathway may be compromised. However, it should be restored after bariatric surgery because of increased glycine production. Objective: To examine the impact of obesity-associated glycine deficiency on the glycine conjugation pathway. We hypothesize that the synthesis rates of acylglycines from endogenous and exogenous sources are significantly reduced in individuals with obesity but increase after bariatric surgery. Methods: We recruited 21 participants with class III obesity and 21 with healthy weight as controls. At baseline, [1,2-13C2] glycine was infused to study the glycine conjugation pathway by quantifying the synthesis rates of several acylglycines. The same measurements were repeated in participants with obesity six months after bariatric surgery. Data are presented as mean ± standard deviation, and p-value < 0.05 is considered statistically significant. Results: Baseline data of 20 participants with obesity were first compared to controls. Participants with obesity were significantly heavier than controls (mean BMI 40.5 ± 7.1 vs. 20.8 ± 2.1 kg/m²). They had significantly lower plasma glycine concentration (168 ± 30 vs. 209 ± 50 µmol/L) and slower absolute synthesis rates of acetylglycine, isobutyrylglycine, tigylglycine, isovalerylglycine, and hexanoylglycine. Pre- and post-surgery data were available for 16 participants with obesity. Post-surgery BMI decreased from 40.9 ± 7.3 to 31.6 ± 6.0 kg/m². Plasma glycine concentration increased from 164 ± 26 to 212 ± 38 µmol/L) and was associated with significantly higher rates of excretion of acetylglycine, isobutyrylglycine, tigylglycine, isovalerylglycine, and hexanoylglycine. Benzoic acid (a xenobiotic dicarboxylic acid) is excreted as benzoylglycine; its synthesis rate was significantly slower in participants with obesity but increased after bariatric surgery. Conclusion: Obesity-associated glycine deficiency impairs the human body's ability to eliminate endogenous and exogenous metabolites/compounds via the glycine conjugation pathway. This impairment is ameliorated when glycine supply is restored after bariatric surgery. These findings imply that dietary glycine supplementation could treat obesity-associated metabolic complications due to the accumulation of intramitochondrial toxic metabolites. Clinical trial registration: https://clinicaltrials.gov/study/NCT04660513, identifier NCT04660513. [ABSTRACT FROM AUTHOR]