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1.
AAPS PharmSciTech ; 25(6): 159, 2024 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-38987438

RESUMO

Vitamin C is extensively used in cosmetic formulation, howbeit stability is the supreme demerit that limits its use in beautifying products. Numerous techniques are being employed to inhibit the degradation of vitamin C caused by formulation components to facilitate the use in skin rejuvenating products. Diverse materials are being exercised in formulation to stabilize the ascorbic acid and ingredients selected in this formulation composition help for stabilization. The initial stable prototype is developed and further optimization is accomplished by applying the design of experiment tools. The stable pharmaceutical formulations were evaluated for the evaluation parameters and designated as two optimized formulations. The analytical method for the assay of ascorbic acid from the United States pharmacopeia and the related substance method from European pharmacopeia has been modified to be used for cream formulation. The DoE design exhibited that the stability of formulation is impacted by citric acid and tartaric acid but not by propylene glycol and glycerin. The analysis results of topical formulations for the evaluation parameter exhibited satisfactory results. The in-vitro release study method has been developed, optimized, and validated to fit the analysis. The in-vitro studies have been performed for selected compositions and both the formulation has similar kinds of release patterns. The stability study as per ICH guidelines exhibited that the product is stable for accelerated, intermediate, and room-temperature storage conditions. The optimized formulation shows constant release and permeation of ascorbic acid through the skin. The formulation with the combinations of citric acid, tartaric acid, and tocopherol is more stable and the degradation of vitamin C has been reduced significantly. The beaucoup strategies in the unique composition help to protect the degradation by inhibiting the multitudinous degradation pathways.


Assuntos
Ácido Ascórbico , Química Farmacêutica , Estabilidade de Medicamentos , Ácido Ascórbico/química , Química Farmacêutica/métodos , Tartaratos/química , Ácido Cítrico/química , Composição de Medicamentos/métodos , Excipientes/química
2.
Environ Geochem Health ; 46(8): 289, 2024 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-38970698

RESUMO

Low molecular weight organic acids (LMWOAs) are important soil components and play a key role in regulating the geochemical behavior of heavy metal(loid)s. Biochar (BC) is a commonly used amendment that could change LMWOAs in soil. Here, four LMWOAs of oxalic acid (OA), tartaric acid (TA), malic acid (MA), and citric acid (CA) were evaluated for their roles in changing Cd and SB desorption behavior in contaminated soil with (S1-BC) or without BC (S1) produced from Paulownia biowaste. The results showed that OA, TA, MA, and CA reduced soil pH with rising concentrations, and biochar partially offset the pH reduction by LMWOAs. The LMWOAs reduced Cd desorption from the soil at low concentrations but increased Cd desorption at high concentrations, and CA was the most powerful in this regard. The LMWOAs had a similar effect on Sb desorption, and CA was the most effective species of LMWOAs. Adding BC to the soil affects Cd and Sb dynamics by reducing the Cd desorption but increasing Sb desorption from the soil and increasing the distribution coefficient (Kd) values of Cd but lowering the Kd values of Sb. This study helped understand the effects of LMWOAs on the geochemical behavior of Cd and Sb in the presence of biochar, as well as the potential risks of biochar amendment in enhancing Sb desorption from contaminated soil.


Assuntos
Carvão Vegetal , Metais Pesados , Poluentes do Solo , Solo , Carvão Vegetal/química , Poluentes do Solo/química , Metais Pesados/química , Solo/química , Peso Molecular , Concentração de Íons de Hidrogênio , Cádmio/química , Tartaratos/química , Malatos/química , Ácido Cítrico/química , Recuperação e Remediação Ambiental/métodos , Ácido Oxálico/química , Adsorção , Oryza/química
3.
J Pharm Biomed Anal ; 247: 116256, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-38850847

RESUMO

A long-term stability study using high performance liquid chromatography (HPLC) revealed an unidentified impurity in the bromhexine hydrochloride injection, which was employed as a mucolytic agent. Investigations into stress degradation and elemental impurities revealed one of the elemental impurities Fe3+ in this injection as the primary generator of these impurities. This impurity, named N-carboxymethyl bromhexine, was a product formed during drug-excipient interaction between bromhexine and tartaric acid with Fe3+. The structure of the impurity was identified through ultra-high-performance liquid chromatography with diode array detector (UHPLC-DAD), liquid chromatograph mass spectrometer (LC-MS). Further, the formation mechanism of the impurity was discussed. Overall, this study elucidates the cause, origin, and mechanism of an unknown impurity in bromhexine hydrochloride injection, providing a basis for quality control for bromhexine hydrochloride injections and drug products containing both amine and tartaric acid.


Assuntos
Bromoexina , Contaminação de Medicamentos , Excipientes , Bromoexina/química , Bromoexina/análise , Cromatografia Líquida de Alta Pressão/métodos , Excipientes/química , Excipientes/análise , Tartaratos/química , Tartaratos/análise , Espectrometria de Massas/métodos , Estabilidade de Medicamentos , Controle de Qualidade
4.
Molecules ; 29(11)2024 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-38893387

RESUMO

The extraction of cannabinoids from the inflorescence and leaves of Cannabis sativa L. is gaining interest from researchers, in addition to addressing the under-utilization of the by-products in the stems and roots of the trees. The present study investigated the recovery of pectin from the left-over parts of hemp tress using an eco-friendly method with the aid of organic acids. Different cannabis cultivars-Chalotte's Angels (CHA) and Hang-Krarog (HKR)-were used as plant materials. The stems of both cannabis cultivars contained more pectin than the roots, and tartaric acid-aided extraction provided higher yields than from citric acid. Extracting the acid solution affected some characteristics, thereby differentiating the functional properties of the derived pectin. Extraction using tartaric acid provided pectin with a higher galacturonic acid content, whereas pectin with a higher methylation degree could be prepared using citric acid. The pectin samples extracted from the stems of CHA (P-CHA) and HKR (P-HKR) had low methoxyl pectin. P-CHA had better free radical scavenging capability, whereas P-HKR showed more potent reducibility. Considering the functional properties, P-CHA showed greater emulsion formability and foaming activity, whereas P-HKR possessed a better thickening effect. The present work suggests the feasible utilization of P-CHA and P-HKR as food additives with bioactivity.


Assuntos
Cannabis , Pectinas , Extratos Vegetais , Pectinas/química , Pectinas/isolamento & purificação , Cannabis/química , Extratos Vegetais/química , Ácido Cítrico/química , Folhas de Planta/química , Caules de Planta/química , Tartaratos/química , Raízes de Plantas/química , Ácidos Hexurônicos/química , Ácidos Hexurônicos/análise
5.
Eur J Pharmacol ; 975: 176668, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-38788791

RESUMO

Tartaric acid (TA) has been shown beneficial effects on blood pressure and lipid levels. However, its effect on non-alcoholic fatty liver disease (NAFLD) remains unknown. This study aimed to investigate the role of TA in experimental NAFLD. Mice were fed a Western diet for 8 weeks, followed by administration of TA or a vehicle for an additional 12 weeks while continuing on the Western diet. Blood biochemistry including transaminases and glucose tolerance test and liver tissue RNA sequencing (RNA-seq), lipid content, and histology were investigated. The HepG2 cell line was used to explore the mechanism by which TA regulates lipid metabolism. We found that TA significantly improved weight gain, insulin resistance, hepatic steatosis, inflammation and fibrosis in Western diet-fed mice. By comparing gene expression differences, we found that TA affects pathways related to lipid metabolism, inflammatory response, and fibrosis. Furthermore, TA effectively reduced oleic acid-induced lipid accumulation in HepG2 cells and downregulated the genes associated with fatty acid synthesis, which were enriched in the AMP-activated protein kinase (AMPK) signaling pathway. TA also enhanced the phosphorylation of AMPK which could be reverted by the AMPK inhibitor Compound C in HepG2 cells. Our study suggests that TA improves experimental NAFLD by activating the AMPK signaling pathway. These findings indicate that TA may serve as a potential therapy for the human NAFLD.


Assuntos
Proteínas Quinases Ativadas por AMP , Metabolismo dos Lipídeos , Camundongos Endogâmicos C57BL , Hepatopatia Gordurosa não Alcoólica , Transdução de Sinais , Tartaratos , Hepatopatia Gordurosa não Alcoólica/tratamento farmacológico , Hepatopatia Gordurosa não Alcoólica/patologia , Hepatopatia Gordurosa não Alcoólica/metabolismo , Animais , Humanos , Células Hep G2 , Proteínas Quinases Ativadas por AMP/metabolismo , Transdução de Sinais/efeitos dos fármacos , Masculino , Camundongos , Tartaratos/farmacologia , Metabolismo dos Lipídeos/efeitos dos fármacos , Fígado/efeitos dos fármacos , Fígado/metabolismo , Fígado/patologia , Modelos Animais de Doenças
6.
Biochemistry ; 63(12): 1578-1587, 2024 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-38803051

RESUMO

l-(+)-Tartaric acid plays important roles in various industries, including pharmaceuticals, foods, and chemicals. cis-Epoxysuccinate hydrolases (CESHs) are crucial for converting cis-epoxysuccinate to l-(+)-tartrate in the industrial production process. There is, however, a lack of detailed structural and mechanistic information on CESHs, limiting the discovery and engineering of these industrially relevant enzymes. In this study, we report the crystal structures of RoCESH and KoCESH-l-(+)-tartrate complex. These structures reveal the key amino acids of the active pocket and the catalytic triad residues and elucidate a dynamic catalytic process involving conformational changes of the active site. Leveraging the structural insights, we identified a robust BmCESH (550 ± 20 U·mg-1) with sustained catalytic activity even at a 3 M substrate concentration. After six batches of transformation, immobilized cells with overexpressed BmCESH maintained 69% of their initial activity, affording an overall productivity of 200 g/L/h. These results provide valuable insights into the development of high-efficiency CESHs and the optimization of biotransformation processes for industrial uses.


Assuntos
Biocatálise , Tartaratos , Tartaratos/metabolismo , Tartaratos/química , Domínio Catalítico , Cristalografia por Raios X , Hidrolases/química , Hidrolases/metabolismo , Hidrolases/genética , Modelos Moleculares , Conformação Proteica
7.
mBio ; 15(6): e0035024, 2024 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-38682906

RESUMO

Enteric pathogens such as Salmonella enterica serovar Typhimurium experience spatial and temporal changes to the metabolic landscape throughout infection. Host reactive oxygen and nitrogen species non-enzymatically convert monosaccharides to alpha hydroxy acids, including L-tartrate. Salmonella utilizes L-tartrate early during infection to support fumarate respiration, while L-tartrate utilization ceases at later time points due to the increased availability of exogenous electron acceptors such as tetrathionate, nitrate, and oxygen. It remains unknown how Salmonella regulates its gene expression to metabolically adapt to changing nutritional environments. Here, we investigated how the transcriptional regulation for L-tartrate metabolism in Salmonella is influenced by infection-relevant cues. L-tartrate induces the transcription of ttdBAU, genes involved in L-tartrate utilization. L-tartrate metabolism is negatively regulated by two previously uncharacterized transcriptional regulators TtdV (STM3357) and TtdW (STM3358), and both TtdV and TtdW are required for the sensing of L-tartrate. The electron acceptors nitrate, tetrathionate, and oxygen repress ttdBAU transcription via the two-component system ArcAB. Furthermore, the regulation of L-tartrate metabolism is required for optimal fitness in a mouse model of Salmonella-induced colitis. TtdV, TtdW, and ArcAB allow for the integration of two cues, i.e., substrate availability and availability of exogenous electron acceptors, to control L-tartrate metabolism. Our findings provide novel insights into how Salmonella prioritizes the utilization of different electron acceptors for respiration as it experiences transitional nutrient availability throughout infection. IMPORTANCE: Bacterial pathogens must adapt their gene expression profiles to cope with diverse environments encountered during infection. This coordinated process is carried out by the integration of cues that the pathogen senses to fine-tune gene expression in a spatiotemporal manner. Many studies have elucidated the regulatory mechanisms of how Salmonella sense metabolites in the gut to activate or repress its virulence program; however, our understanding of how Salmonella coordinates its gene expression to maximize the utilization of carbon and energy sources found in transitional nutrient niches is not well understood. In this study, we discovered how Salmonella integrates two infection-relevant cues, substrate availability and exogenous electron acceptors, to control L-tartrate metabolism. From our experiments, we propose a model for how L-tartrate metabolism is regulated in response to different metabolic cues in addition to characterizing two previously unknown transcriptional regulators. This study expands our understanding of how microbes combine metabolic cues to enhance fitness during infection.


Assuntos
Proteínas de Bactérias , Regulação Bacteriana da Expressão Gênica , Salmonella typhimurium , Tartaratos , Salmonella typhimurium/genética , Salmonella typhimurium/metabolismo , Camundongos , Animais , Tartaratos/metabolismo , Proteínas de Bactérias/metabolismo , Proteínas de Bactérias/genética , Infecções por Salmonella/microbiologia , Feminino
8.
PLoS One ; 19(4): e0299218, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38662654

RESUMO

To enhance the yield of the one-step synthesis of terpinyl acetate from α-pinene and acetic acid, this study evaluated α-hydroxycarboxylic acid (HCA)-boric acid composite catalysts based on orthogonal experimental design. The most important factor affecting the terpinyl acetate content in the product was the HCA content. The catalytic performance of the composite catalyst was related to the pKa1 of HCA. The tartaric acid-boric acid composite catalyst showed the highest catalytic activity. The α-pinene conversion reached 91.8%, and the terpinyl acetate selectivity reached 45.6%. When boric acid was replaced with B2O3, the HCA composite catalyst activity was enhanced, which reduced the use of HCA. When the lactic acid and B2O3 content accounted for 10% and 4% of the α-pinene mass content, respectively, the α-pinene conversion reached 93.2%, and the terpinyl acetate selectivity reached up to 47.1%. In addition, the presence of water was unfavorable to HCA-boric acid composite catalyst. However, a water content less than 1% of the α-pinene mass content improved the catalytic activity of HCA-B2O3. When the tartaric acid-B2O3 was used as catalyst, and the water content was 1% of the α-pinene mass content, the α-pinene conversion was 89.6%, and the terpinyl acetate selectivity was 47.5%.


Assuntos
Monoterpenos Bicíclicos , Ácidos Bóricos , Monoterpenos , Catálise , Monoterpenos Bicíclicos/química , Ácidos Bóricos/química , Monoterpenos/química , Tartaratos/química , Acetatos/química , Ácidos Carboxílicos/química , Terpenos/química , Terpenos/síntese química
9.
J Hazard Mater ; 471: 134350, 2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38643580

RESUMO

Biotransformation is a major dissipation process of tetrabromobisphenol A and its derivatives (TBBPAs) in soil. The biotransformation and ultimate environmental fate of TBBPAs have been widely studied, yet the effect of root exudates (especially low-molecular weight organic acids (LMWOAs)) on the fate of TBBPAs is poorly documented. Herein, the biotransformation behavior and mechanism of TBBPAs in bacteriome driven by LMWOAs were comprehensively investigated. Tartaric acid (TTA) was found to be the main component of LMWOAs in root exudates of Helianthus annus in the presence of TBBPAs, and was identified to play a key role in driving shaping bacteriome. TTA promoted shift of the dominant genus in soil bacteriome from Saccharibacteria_genera_incertae_sedis to Gemmatimonas, with a noteworthy increase of 24.90-34.65% in relative abundance of Gemmatimonas. A total of 28 conversion products were successfully identified, and ß-scission was the principal biotransformation pathway for TBBPAs. TTA facilitated the emergence of novel conversion products, including 2,4-dibromophenol, 3,5-dibromo-4-hydroxyacetophenone, para-hydroxyacetophenone, and tribromobisphenol A. These products were formed via oxidative skeletal cleavage and debromination pathways. Additionally, bisphenol A was observed during the conversion of derivatives. This study provides a comprehensive understanding about biotransformation of TBBPAs driven by TTA in soil bacteriome, offering new insights into LMWOAs-driven biotransformation mechanisms.


Assuntos
Biotransformação , Bifenil Polibromatos , Microbiologia do Solo , Poluentes do Solo , Tartaratos , Poluentes do Solo/metabolismo , Poluentes do Solo/química , Bifenil Polibromatos/metabolismo , Bifenil Polibromatos/química , Tartaratos/metabolismo , Tartaratos/química , Biodegradação Ambiental , Raízes de Plantas/metabolismo
10.
Appl Environ Microbiol ; 90(4): e0235123, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38517167

RESUMO

In rice paddies, soil and plant-derived organic matter are degraded anaerobically to methane (CH4), a powerful greenhouse gas. The highest rate of methane emission occurs during the reproductive stage of the plant when mostly dicarboxylic acids are exudated by the roots. The emission of methane at this stage depends largely on the cooperative interaction between dicarboxylic acid-fermenting bacteria and methanogenic archaea in the rhizosphere. The fermentation of tartrate, one of the major acids exudated, has been scarcely explored in rice paddy soils. In this work, we characterized an anaerobic consortium from rice paddy soil composed of four bacterial strains, whose principal member (LT8) can ferment tartrate, producing H2 and acetate. Tartrate fermentation was accelerated by co-inoculation with a hydrogenotrophic methanogen. The assembled genome of LT8 possesses a Na+-dependent oxaloacetate decarboxylase and shows that this bacterium likely invests part of the H2 produced to reduce NAD(P)+ to assimilate C from tartrate. The phylogenetic analysis of the 16S rRNA gene, the genome-based classification as well as the average amino acid identity (AAI) indicated that LT8 belongs to a new genus within the Sporomusaceae family. LT8 shares a few common features with its closest relatives, for which tartrate degradation has not been described. LT8 is limited to a few environments but is more common in rice paddy soils, where it might contribute to methane emissions from root exudates.IMPORTANCEThis is the first report of the metabolic characterization of a new anaerobic bacterium able to degrade tartrate, a compound frequently associated with plants, but rare as a microbial metabolite. Tartrate fermentation by this bacterium can be coupled to methanogenesis in the rice rhizosphere where tartrate is mainly produced at the reproductive stage of the plant, when the maximum methane rate emission occurs. The interaction between secondary fermentative bacteria, such as LT8, and methanogens could represent a fundamental step in exploring mitigation strategies for methane emissions from rice fields. Possible strategies could include controlling the activity of these secondary fermentative bacteria or selecting plants whose exudates are more difficult to ferment.


Assuntos
Euryarchaeota , Oryza , Solo/química , Oryza/microbiologia , Fermentação , Tartaratos/metabolismo , RNA Ribossômico 16S/genética , RNA Ribossômico 16S/metabolismo , Filogenia , Composição de Bases , Análise de Sequência de DNA , Bactérias , Bactérias Anaeróbias/metabolismo , Euryarchaeota/metabolismo , Firmicutes/metabolismo , Bactérias Gram-Negativas/genética , Metano/metabolismo
11.
Environ Sci Pollut Res Int ; 31(12): 18540-18548, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38347356

RESUMO

Although Mn(III) complexes with organic ligands have been previously identified, the information about their stability and reactivity is scarce. In the present study, we analyzed the formation and stability of three different complexes: Mn(III)-citrate, Mn(III)-tartrate, and Mn(III)-humic acid (HA), as well as their reactivity toward an element of high environmental concern, lead (Pb).Our results indicate that the stability of studied complexes is highly dependent on pH. The Mn(III) complexes with citrate and tartrate degrade below pH 8, due to the electron transfer reaction between Mn(III) and the ligand, while the Mn(III)-HA complex's degradation is slower and less sensitive to pH. At pH 4, less than 40% of the initial Mn(III)-HA was found to be stable.The reactivity of the complexes was different depending on the ligand and its concentration. The Mn(III)-citrate and Mn(III)-tartrate complexes effectively reduced PbO2 and releases aqueous Pb2+, although significant differences were found with increasing ligand concentration. There was no evidence of the reduction of PbO2 by Mn(III) when it forms a complex with HA. This is likely due to the large size of HA moieties that prevent the Mn(III) component of the complex from getting close enough to the PbO2 surface to initiate electron transfer and lead to the reduction of Pb(IV) by HA itself.


Assuntos
Substâncias Húmicas , Tartaratos , Oxirredução , Ligantes , Chumbo , Peso Molecular , Citratos
12.
Int J Biol Macromol ; 263(Pt 2): 130273, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38368990

RESUMO

Blueberries are highly perishable after harvest, so a simple preservation method is needed to extend the shelf life of blueberries. In this study, sodium chlorite-loaded sepiolite was added to polylactide solution with tartaric acid to create a ClO2 gas slow-release fresh-keeping card. The fresh-keeping card absorbs moisture in the air, which causes tartaric acid to enter the sepiolite and react with sodium chlorite to release ClO2 gas slowly. The study investigated the impact of fresh-keeping cards on the quality attributes of blueberries, including appearance, decay rate, ethylene release rate, respiration rate, hardness, ascorbic acid content, and anthocyanin concentration. Low-field nuclear magnetic technology was used to analyze the water state and distribution of blueberries during storage. The results showed that the ClO2 gas released by the fresh-keeping card can destroy ethylene in the air and kill microorganisms in blueberries, thereby delaying fruit decay.


Assuntos
Cloretos , Compostos Clorados , Cloro , Conservação de Alimentos , Silicatos de Magnésio , Poliésteres , Tartaratos , Conservação de Alimentos/métodos , Óxidos , Etilenos
13.
J Nutr Health Aging ; 28(2): 100003, 2024 02.
Artigo em Inglês | MEDLINE | ID: mdl-38388107

RESUMO

OBJECTIVES: Several studies suggest that moderate wine consumption, particularly red wine, may have benefits for cardiovascular health. Red wine contains a variety of bioactive compounds, including polyphenols like phenolic acids, which have demonstrated anti-inflammatory effects in experimental models. The aim of this study was to assess the anti-inflammatory properties of wine, measured as urinary tartaric acid, a new biomarker of wine consumption. DESIGN, SETTINGS, AND PARTICIPANTS: One-year longitudinal study that included 217 participants from the PREDIMED trial. MEASUREMENTS: Plasma inflammatory biomarkers and urinary tartaric acid were analyzed using xMAP technology and high-performance liquid chromatography, respectively. Multivariable regression analyses were performed to assess the relationship between variations over 1-year in urinary tartaric acid concentrations and 1-year changes in serum inflammatory molecules, including adhesion cell molecules, interleukine-6, tumour necrosis factor alpha, and monocyte chemotactic protein 1. Three categories were built according to tertiles of 1-y changes in urinary tartaric acid. RESULTS: Using a ROC curve, urinary tartaric acid was corroborated as a reliable biomarker of wine consumption (AUC = 0.818 (95% CI: 0.76; 0.87). In the continuous analysis, participants with higher increases in tartaric acid significantly reduced their concentrations in soluble vascular adhesion molecule (sVCAM-1) after 1-year of follow-up (-0.20 (-0.38; -9,93) ng/mL per 1-SD increment, p-value = 0.031). Moreover, tertiles 2 and 3 of 1-year changes in tartaric acid presented a significant reduction in soluble intercellular cell adhesion molecule (sICAM-1) as compared to tertile 1 (-0.31 (-0.52; -0.10) ng/mL, p-value = 0.014 and -0.29 (-0.52; -0.07) ng/mL, p-value = 0.023, respectively). Participants in the third tertile also exhibited a reduced concentration of sVCAM-1 compared to those in the first tertile (-0.31 (-0.55; -0.06) ng/mL, p-value = 0.035). CONCLUSIONS: Our findings suggest that wine consumption is associated with lower levels of inflammation due to the anti-inflammatory properties of wine compounds.


Assuntos
Aterosclerose , Tartaratos , Vinho , Humanos , Vinho/análise , Estudos Longitudinais , Inflamação , Anti-Inflamatórios/análise , Biomarcadores
14.
J Biol Chem ; 300(2): 105635, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38199576

RESUMO

Microbial epoxide hydrolases, cis-epoxysuccinate hydrolases (CESHs), have been utilized for commercial production of enantiomerically pure L(+)- and D(-)-tartaric acids for decades. However, the stereo-catalytic mechanism of CESH producing L(+)-tartaric acid (CESH[L]) remains unclear. Herein, the crystal structures of two CESH[L]s in ligand-free, product-complexed, and catalytic intermediate forms were determined. These structures revealed the unique specific binding mode for the mirror-symmetric substrate, an active catalytic triad consisting of Asp-His-Glu, and an arginine providing a proton to the oxirane oxygen to facilitate the epoxide ring-opening reaction, which has been pursued for decades. These results provide the structural basis for the rational engineering of these industrial biocatalysts.


Assuntos
Biocatálise , Epóxido Hidrolases , Hidrolases , Epóxido Hidrolases/metabolismo , Hidrolases/química , Hidrolases/genética , Hidrolases/metabolismo , Tartaratos/metabolismo , Modelos Moleculares , Estrutura Terciária de Proteína , Estrutura Quaternária de Proteína
15.
BJOG ; 131(5): 665-674, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-37705143

RESUMO

OBJECTIVE: Xenobiotic metabolites are exogenous biochemicals that can adversely impact reproductive health. We previously identified xenobiotics in cervicovaginal fluid during pregnancy in association with short cervix. In other organ systems, xenobiotics can modify epithelial barrier function. We hypothesise that xenobiotics dysregulate epithelial cell and macrophage immune responses as a mechanism to disrupt the cervicovaginal barrier. DESIGN: In vitro cell culture system. SETTING: Laboratory within academic institution. SAMPLE: Vaginal, ectocervical and endocervical epithelial cell lines and primary macrophages. METHODS: Cells were treated with diethanolamine (2.5 mM), ethyl glucoside (5 mM) or tartrate (2.5 mM) for 24 h. MAIN OUTCOME MEASURES: Cytokines and matrix metalloproteinases were measured in cell supernatants (n = 3 per condition). One-way analysis of variance (ANOVA) with Dunnett's test for multiple comparisons was performed. RESULTS: Diethanolamine induces inflammatory cytokines, whereas ethyl glucoside and tartrate generally exert anti-inflammatory effects across all cells. Diethanolamine increases interleukin 6 (IL-6), IL-8, interferon γ-induced protein 10 kDa (IP-10), growth-regulated oncogene (GRO), fractalkine, matrix metalloproteinase 1 (MMP-1), MMP-9 and MMP-10 (p < 0.05 for all), factors involved in acute inflammation and recruitment of monocytes, neutrophils and lymphocytes. Ethyl glucoside and tartrate decrease multiple cytokines, including RANTES and MCP-1 (p < 0.05 for all), which serve as chemotactic factors. Vaginal cells exhibit heightened inflammatory tone compared with cervical cells and macrophages, with a greater number of differentially expressed analytes after xenobiotic exposure. CONCLUSIONS: Xenobiotic metabolites present in the cervicovaginal space during pregnancy modify immune responses, unveiling potential pathways through which environmental exposures may contribute to the pathogenesis of cervical remodelling preceding preterm birth. Future work identifying xenobiotic sources and routes of exposure offers the potential to modify environmental risks to improve pregnancy outcomes.


Assuntos
Etanolaminas , Nascimento Prematuro , Tartaratos , Recém-Nascido , Gravidez , Feminino , Humanos , Xenobióticos , Citocinas/metabolismo , Epitélio , Imunidade
16.
Environ Sci Pollut Res Int ; 31(2): 3222-3238, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38085482

RESUMO

Although assisted phytoremediation using chemical treatments is a suitable technique for the removal of heavy metals (HMs), the estimation of this process using simple models is also crucial. For this purpose, a greenhouse trial was designed to evaluate the effectiveness of citric, oxalic, and tartaric acid on Cd, Pb, Ni, and Zn phytoremediation by maize and sorghum and to estimate this process using sigmoid HMs uptake model. Results showed that mean values of root and shoot dry weight and metals uptake, translocation factor (TF) of Pb and Zn, and uptake efficiency (UE) of Cd in maize were higher than sorghum but the TF of Cd and the phytoextraction efficiency (PEE) and UE of Pb in sorghum were higher than maize. Citric, oxalic, and tartaric acid significantly increased the UE of Pb by 17.7%, 22.5%, and 32.5%, respectively. Tartaric acid significantly increased the mean values of shoot dry weight, shoot Cd, Pb, and Ni uptake, and PEE of Pb and Ni, but decreased TF of Zn. The R2, NRMSE, and KM values indicated the ability of sigmoid HM uptake model in estimating HMs uptake in maize and sorghum treated with organic acids. Thus, tartaric acid was more effective than citric and oxalic acids to enhance phytoremediation potential. Sigmoid HM uptake model is suitable to estimate the HMs uptake in plants treated with organic acids at different growth stages.


Assuntos
Metais Pesados , Poluentes do Solo , Sorghum , Tartaratos , Zea mays , Cádmio/análise , Chumbo , Poluentes do Solo/análise , Metais Pesados/análise , Biodegradação Ambiental , Ácido Cítrico , Solo
17.
Int J Biol Macromol ; 257(Pt 2): 128734, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38086429

RESUMO

Tartaric acid (TA) is a major non-fermentable plant soluble acid that abundantly occur in grapes and wines, imparting low pH and tart flavour to berries thereby regulating numerous quality attributes of wine, such as flavour, microbial stability, and aging potential. Evaluation of acidity in mature fruits of 21 wine grape (Vitis vinifera) varieties revealed significant variation between 'Beichun' and 'Gewürztraminer', which was correlated with TA content. RNA-seq analysis of fruits from the two cultivars at different developmental stages revealed that a transketolase gene, VvTK2, was significantly dominantly expressed in the high TA phenotype 'Beichun' variety. Subcellular localization assay showed that VvTK2 protein was located in the chloroplast. Virus-induced VvTK2 gene silencing significantly decreased the expression of 2-keto-L-gulonic acid reductase (Vv2-KGR) as well as L-idonate dehydrogenase (VvL-IdnDH3) and inhibited TA accumulation, while its transient over-expression in grape showed the opposite results. Heterologous VvTK2 over-expression in tomato demonstrated its obvious capacity to induce TA synthesis. Overall, these results highlights a novel role of VvTK2 in modulating TA biosynthesis, which could be an excellent strategy for future genetic improvement of grape flavour.


Assuntos
Solanum lycopersicum , Tartaratos , Vitis , Vinho , Vitis/genética , Vitis/metabolismo , Frutas/química , Transcetolase/análise , Transcetolase/metabolismo , Vinho/análise , Oxirredutases/metabolismo
18.
Plant Physiol Biochem ; 206: 108107, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38029613

RESUMO

Selenium (Se) can reduce uptake and translocation of cadmium (Cd) in plants via plenty of ways, including regulation of root morphology. However, the underlying mechanisms on how Se will regulate root morphology under metal(loid) stresses are not fully illustrated. To fill up this knowledge gap, we investigated the effects of 0.5 mg L-1 selenite (Se(IV)) on root exudates, root morphology, root endogenous hormones, and Cd uptake efficiency of rice under the 1 mg L-1 Cd stress condition. The results showed that Se(IV) significantly reduced shoot and root Cd concentrations, and decreased Cd uptake efficiency via root hairs determined by a non-invasive micro-test (NMT) technology. When compared to the 1 mg L-1 Cd (Cd1) treatment, addition of 0.5 mg L-1 Se(IV) (1) significantly reduced root surface area and tip numbers, and non-significantly reduced root length, but significantly enhanced root diameter and root volume; (2) significantly enhanced concentrations of tartaric acid in the root exudate solution, root auxin (IAA) and root jasmonic acid (JA) via a UHPLC or a HPLC analysis; (3) significantly up-regulated metabolites correlated with synthesis of IAA, JA, gibberellin (GA), and salicylic acid, such as GA53, M-SA, (+/-)7-epi-JA, and derivatives of tryptophan and indole in the metabolome analysis. However, results of transcriptome analysis showed that (1) no upregulated differentially expressed genes (DEGs) were enriched in IAA synthesis; (2) some upregulated DEGs were found to be enriched in JA and GA53 synthesis pathways. In summary, although Se(IV) stimulated the synthesis of IAA, JA, and GA53, it significantly inhibited root growth mainly by 1) affecting signal transduction of IAA and GA; 2) altering IAA polar transport and homeostasis; and 3) regulating DEGs including SAUR32, SAUR36, SAUR76, OsSub33, OsEXPA8, OsEXPA18, and Os6bglu24.


Assuntos
Cádmio , Reguladores de Crescimento de Plantas , Tartaratos , Reguladores de Crescimento de Plantas/farmacologia , Reguladores de Crescimento de Plantas/metabolismo , Cádmio/metabolismo , Ácido Selenioso/farmacologia , Ácido Selenioso/metabolismo , Transcriptoma , Raízes de Plantas/metabolismo , Transdução de Sinais , Metaboloma
19.
Environ Sci Pollut Res Int ; 31(4): 6411-6424, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38148461

RESUMO

The interactions between organic pollutants and iron minerals play an important role in their environmental fate. In this study, the effects of low-molecular-weight organic acids (LMWOAs) on the adsorption and degradation of tetracycline (TC) on goethite were investigated. Tartaric acid (TA) was taken as the representative of LMWOAs to study the influencing mechanism through batch experiments and microscale characterization. In addition, the properties of TC-TA clusters under different pHs were determined by density functional theory (DFT) calculations. The results showed that all five LMWOAs inhibited TC adsorption and degradation. The preferential adsorption of TA on goethite changed TC adsorption from inner spherical to outer spherical complexation and mainly inhibited TC adsorption and degradation of the singly coordinated hydroxyl group. TC degradation rate decreased from 0.0287 to 0 h-1 in the first stage. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy results showed that TA could influence the interactions of amide groups, C = O on the A-ring, and dimethylamino group of TC with goethite, and the formation of ≡Fe(II) was inhibited. In addition to competing for the effective sites, the effects of complexation between TA and TC in solution should be considered. According to DFT calculations, hydrogen bonds could be formed between the carboxyl group of TA and the H atom of TC at different pH. These findings can provide evidence for estimating the contribution of adsorption and degradation to TC removal by iron oxides with the coexistence of LMWOAs in a soil-water environment.


Assuntos
Antibacterianos , Compostos de Ferro , Tartaratos , Adsorção , Antibacterianos/química , Tetraciclina/química , Minerais/química , Compostos de Ferro/química , Ferro , Concentração de Íons de Hidrogênio , Espectroscopia de Infravermelho com Transformada de Fourier
20.
Protein J ; 43(1): 96-114, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38127181

RESUMO

Divergently evolved Tartrate dehydrogenase (TDH) exhibits multiple catalytic activities at a single active site; the enzyme from P. putida (pTDH) being structurally and biochemically well-characterized. Occurrence of TDH-associated ability to aerobically metabolize L-tartrate in Bacillus isolates and limited resemblance of ycsA-encoded protein sequences with pTDH rendered Bacillus TDH as an intriguing enzyme with possible catalytic diversity as well as evolutionary significance. The present study explores substrate interactions of TDHs from B. subtilis 168 (168bTDH) and B. licheniformis DSM-13 (429bTDH) through kinetic, structural and molecular docking-based analysis. Heterologously expressed bTDHs, purified from insoluble fractions of E. coli BL21(DE3) cells, could significantly catalyze L-tartrate and meso-tartrate as substrates in forward reaction. Unlike pTDH, bTDHs distinctly and more efficiently catalyzed the reverse reaction using dihydroxyfumarate substrate following sigmoidal kinetics; the ability being ~ 4 fold higher in 168bTDH. Their binding energies predicted from molecular docking, further substantiated the relative substrate specificities, while revealing major residues involved in protein-ligand interactions at active site. The kinetic analysis and homology modelling validated using Ramachandran Plot analysis predicted a dimeric nature for bTDH. Collectively, the results highlight unique catalytic potential of phylogenetically recent bTDHs, offering an important protein engineering target to mediate efficient enantioselective enzymatic biotransformations.


Assuntos
Oxirredutases do Álcool , Bacillus , Bacillus/enzimologia , Bacillus/genética , Catálise , Escherichia coli/genética , Cinética , Simulação de Acoplamento Molecular , Especificidade por Substrato , Tartaratos
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