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1.
J Hazard Mater ; 421: 126790, 2022 01 05.
Artigo em Inglês | MEDLINE | ID: mdl-34358973

RESUMO

Acid mine drainage (AMD) system represents one of the most unfavorable habitats for microorganisms due to its low pH and high concentrations of metals. Compared to bacteria and fungi, our understanding regarding the response of soil protozoa to such extremely acidic environments remains limited. This study characterized the structures of protozoan communities inhabiting a terrace heavily contaminated by AMD. The sharp environmental gradient of this terrace was generated by annual flooding from an AMD lake located below, which provided a natural setting to unravel the environment-protozoa interactions. Previously unrecognized protozoa, such as Apicomplexa and Euglenozoa, dominated the extremely acidic soils, rather than the commonly recognized members (e.g., Ciliophora and Cercozoa). pH was the most important factor regulating the abundance of protozoan taxa. Metagenomic analysis of protozoan metabolic potential showed that many functional genes encoding for the alleviation of acid stress and various metabolic pathways were enriched, which may facilitate the survival and adaptation of protozoa to acidic environments. In addition, numerous co-occurrences between protozoa and bacterial or fungal taxa were observed, suggesting shared environmental preferences or potential bio-interactions among them. Future studies are required to confirm the ecological roles of these previously unrecognized protozoa as being important soil microorganisms.


Assuntos
Mineração , Solo , Ácidos , Bactérias , Microbiologia do Solo
2.
Artigo em Inglês | MEDLINE | ID: mdl-34639299

RESUMO

The composition of diet strongly affects acid-base homeostasis. Western diets abundant in acidogenic foods (meat and cheese) and deficient in alkalizing foods (fruits and vegetables) increase dietary acid load (DAL). A high DAL has been associated with numerous health repercussions, including cardiovascular disease and type-2-diabetes. Plant-based diets have been associated with a lower DAL; however, the number of trials exploring this association is limited. This randomized-controlled trial sought to examine whether an isocaloric vegan diet lowers DAL as compared to a meat-rich diet. Forty-five omnivorous individuals were randomly assigned to a vegan diet (n = 23) or a meat-rich diet (n = 22) for 4 weeks. DAL was determined using potential renal acid load (PRAL) and net endogenous acid production (NEAP) scores at baseline and after 3 and 4 weeks, respectively. After 3 weeks, median PRAL (-23.57 (23.87)) and mean NEAPR (12.85 ± 19.71) scores were significantly lower in the vegan group than in the meat-rich group (PRAL: 18.78 (21.04) and NEAPR: 60.93 ± 15.51, respectively). Effects were mediated by a lower phosphorus and protein intake in the vegan group. Our study suggests that a vegan diet is a potential means to reduce DAL, whereas a meat-rich diet substantially increases the DAL burden.


Assuntos
Diabetes Mellitus Tipo 2 , Dieta Vegana , Ácidos , Dieta , Alimentos , Humanos
3.
Int J Mol Sci ; 22(19)2021 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-34638844

RESUMO

Identification of a natural human leukocyte antigen (HLA) ligandome is a key element to understand the cellular immune response. Advanced high throughput mass spectrometry analyses identify a relevant, but not complete, fraction of the many tens of thousands of self-peptides generated by antigen processing in live cells. In infected cells, in addition to this complex HLA ligandome, a minority of peptides from degradation of the few proteins encoded by the viral genome are also bound to HLA class I molecules. In this study, the standard immunopeptidomics strategy was modified to include the classical acid stripping treatment after virus infection to enrich the HLA ligandome in virus ligands. Complexes of HLA-B*27:05-bound peptide pools were isolated from vaccinia virus (VACV)-infected cells treated with acid stripping after virus infection. The HLA class I ligandome was identified using high throughput mass spectrometry analyses, yielding 37 and 51 natural peptides processed and presented untreated and after acid stripping treatment VACV-infected human cells, respectively. Most of these virus ligands were identified in both conditions, but exclusive VACV ligands detected by mass spectrometry detected on acid stripping treatment doubled the number of those identified in the untreated VACV-infected condition. Theoretical binding affinity prediction of the VACV HLA-B*27:05 ligands and acute antiviral T cell response characterization in the HLA transgenic mice model showed no differences between HLA ligands identified under the two conditions: untreated and under acid stripping condition. These findings indicated that acid stripping treatment could be useful to identify HLA class I ligands from virus-infected cells.


Assuntos
Antígenos HLA/imunologia , Antígenos de Histocompatibilidade Classe I/imunologia , Linfócitos/imunologia , Espectrometria de Massas em Tandem/métodos , Vírus Vaccinia/imunologia , Ácidos/química , Animais , Linfócitos T CD8-Positivos/imunologia , Linfócitos T CD8-Positivos/metabolismo , Linfócitos T CD8-Positivos/virologia , Linhagem Celular , Antígenos HLA/genética , Antígenos HLA/metabolismo , Antígenos de Histocompatibilidade Classe I/genética , Antígenos de Histocompatibilidade Classe I/metabolismo , Humanos , Interferon gama/imunologia , Interferon gama/metabolismo , Ligantes , Linfócitos/metabolismo , Linfócitos/virologia , Camundongos Transgênicos , Peptídeos/imunologia , Peptídeos/metabolismo , Ligação Proteica , Vírus Vaccinia/fisiologia
4.
Water Sci Technol ; 84(8): 1981-1996, 2021 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-34695025

RESUMO

Discharge of acid mine drainage (AMD) from abandoned coal mines of the YuDong catchment in Kaili City, Guizhou Province, China, has severely damaged local ecological environments. In this study, a laboratory-scale dispersed alkaline substrate (DAS) was studied for the treatment of simulated AMD. The experimental conditions and reaction mechanisms were preliminarily explored. The treatment effect and variation law of vertical effluent water quality of the experimental conditions were thoroughly analysed. The results indicated that small-sized limestone (diameter 5-7 mm) having a 20:1 mixture ratio with shavings and minimum HRT of 20 hours result in increasing effluent pH from 3.5 to 6.6, achieving 66.2% and 99.1% removal of Fe and Al, respectively. There were obvious differences in each reaction layer for the removal of various pollutants from AMD along the depth by DAS, the main reaction zone was first 20-30 cm of the reaction column. The removal process of metal ions and sulfate was accompanied by bio-mineralization reaction. This test provided a valuable support for the local practical engineering applications, enriched the AMD processing technology experimental cases, and provided reference for the treatment technology of similar polluted areas.


Assuntos
Mineração , Poluentes Químicos da Água , Ácidos , Carvão Mineral , Concentração de Íons de Hidrogênio , Metais , Sulfatos , Poluentes Químicos da Água/análise
5.
Environ Sci Technol ; 55(21): 14595-14606, 2021 11 02.
Artigo em Inglês | MEDLINE | ID: mdl-34668375

RESUMO

The partition of gas-phase organic nitrates (ONs) to aerosols and subsequent hydrolysis are regarded as important loss mechanisms for ON species. However, the hydrolysis mechanisms and the major factors controlling the hydrolysis lifetime are not fully understood. In this work, we synthesized seven monoterpene-derived ONs and systematically investigated their hydrolysis in bulk solutions at different pH values. The hydrolysis lifetimes ranged from 12.9 min to 8.5 h for allylic primary ON and tertiary ONs, but secondary ONs were stable at neutral pH. The alkyl substitution numbers, functional groups, and carbon skeletons were three important factors controlling hydrolysis rates. Tertiary and secondary ONs were found to hydrolyze via the acid-catalyzed unimolecular (SN1) mechanism, while a competition of SN1 and bimolecular (SN2) mechanisms accounted for the hydrolysis of primary ONs. The consistency of experimental and theoretical hydrolysis rates calculated by density functional theory further supported the proposed mechanisms. Reversible reactions including hydrolysis and nitration were first reported to explain the hydrolysis of ONs, highlighting the possibility that particulate nitric acid can participate in nitration to generate new nitrogen-containing compounds. These findings demonstrate that ON hydrolysis is a complex reaction that proceeds via different mechanisms and is controlled by various parameters.


Assuntos
Monoterpenos , Nitratos , Ácidos , Aerossóis , Hidrólise
6.
Nutrients ; 13(10)2021 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-34684342

RESUMO

Plant-based low protein diets (LPDs) have gained popularity for managing chronic kidney disease (CKD) patients. The nutritional adequacy of these and other LPDs prescribed for CKD patients have not been carefully examined. This study assessed the nutrient composition of such LPDs and moderately high protein diets (MHPDs) that might be prescribed for patients in the Asia Pacific region with CKD who are not dialyzed or undergoing maintenance dialysis. Conventional diets containing at least 50% animal-based proteins and plant-based diets were also planned with protein prescriptions of 0.5 to 0.8 g/kg/day and MHPDs with protein prescriptions of 1.0 to 1.2 g/kg/day. Plant-based, lacto-, ovo-, and lacto-ovo-vegetarian and vegan LPDs and MHPDs were planned by replacing some or all of the animal proteins from the conventional diet. With 0.5 g protein/kg/day, all diets were below the Recommended Dietary Allowances (RDA) for at least one essential amino acid (EAA). At a protein prescription of 0.6 g/kg/day, only the conventional LPD met the RDA for all EAAs. This deficiency with the plant-based LPDs persisted even with several plant food substitutions. With a protein prescription ≥0.7 g/kg/day, all the plant-based and vegetarian LPDs provided the RDA for all EAA. The plant-based and vegetarian diets also contained relatively greater potassium, phosphorus, and calcium content but lower long-chain n-3 polyunsaturated fatty acids and vitamin B-12 than the conventional diet. Other essential micronutrients were commonly below the RDA even at higher protein intakes. The low contents of some essential micronutrients were found in both animal-based and plant-based diets. Prescription of all LPDs for CKD patients, especially plant-based and vegetarian LPDs, requires careful planning to ensure the adequacy of all nutrients, particularly essential amino acids. Consideration should be given to supplementing all animal-based and plant-based LPDs and MHPDs with multivitamins and certain trace elements.


Assuntos
Dieta , Modelos Teóricos , Estado Nutricional , Plantas , Insuficiência Renal Crônica/dietoterapia , Ácidos/análise , Animais , Dieta Rica em Proteínas , Dieta Vegetariana , Rim/patologia , Nutrientes/análise , Recomendações Nutricionais
7.
Vet Res ; 52(1): 117, 2021 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-34521475

RESUMO

Edwardsiella tarda is a facultative intracellular pathogen in humans and animals. The Gram-negative bacterium is widely considered a potentially important bacterial pathogen. Adaptation to acid stress is important for the transmission of intestinal microbes, so the acid-resistance (AR) system is essential. However, the AR systems of E. tarda are totally unknown. In this study, a lysine-dependent acid resistance (LDAR) system in E. tarda, CadBA, was characterized and identified. CadB is a membrane protein and shares high homology with the lysine/cadaverine antiporter. CadA contains a PLP-binding core domain and a pyridoxal phosphate-binding motif. It shares high homology with lysine decarboxylase. cadB and cadA are co-transcribed under one operon. To study the function of the cadBA operon, isogenic cadA, cadB and cadBA deletion mutant strains TX01ΔcadA, TX01ΔcadB and TX01ΔcadBA were constructed. When cultured under normal conditions, the wild type strain and three mutants exhibited the same growth performance. However, when cultured under acid conditions, the growth of three mutants, especially TX01ΔcadA, were obviously retarded, compared to the wild strain TX01, which indicates the important involvement of the cadBA operon in acid resistance. The deletion of cadB or cadA, especially cadBA, significantly attenuated bacterial activity of lysine decarboxylase, suggesting the vital participation of cadBA operon in lysine metabolism, which is closely related to acid resistance. The mutations of cadBA operon enhanced bacterial biofilm formation, especially under acid conditions. The deletions of the cadBA operon reduced bacterial adhesion and invasion to Hela cells. Consistently, the deficiency of cadBA operon abated bacterial survival and replication in macrophages, and decreased bacterial dissemination in fish tissues. Our results also show that the expression of cadBA operon and regulator cadC were up-regulated upon acid stress, and CadC rigorously regulated the expression of cadBA operon, especially under acid conditions. These findings demonstrate that the AR CadBA system was a requisite for the resistance of E. tarda against acid stress, and played a critical role in bacterial infection of host cells and in host tissues. This is the first study about the acid resistance system of E. tarda and provides new insights into the acid-resistance mechanism and pathogenesis of E. tarda.


Assuntos
Biofilmes , Edwardsiella tarda/fisiologia , Edwardsiella tarda/patogenicidade , Fatores de Virulência/genética , Ácidos/metabolismo , Edwardsiella tarda/genética
8.
Environ Pollut ; 290: 118064, 2021 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-34481302

RESUMO

Acid mine drainage (AMD) is a serious environmental problem worldwide that requires efficient and sustainable remediation technologies including the use of biological mechanisms. A key challenge for AMD bioremediation is to provide optimal conditions for microbial-mediated immobilisation of trace metals. Although organic carbon and oxygen can enhance treatment efficiency, the effect on microbial communities is unclear. In this study, surface sediments from a natural wetland with proven efficiency for AMD bioremediation were artificially exposed to oxygen (by aeration) and/or organic carbon (in the form of mixed organic acids) and incubated under laboratory conditions. In addition to measuring changes in water chemistry, a metagenomics approach was used to determine changes in sediment bacterial, archaeal and fungal community structure, and functional gene abundance. The addition of organic carbon produced major changes in the abundance of microorganisms related to iron and sulfur metabolism (including Geobacter and Pelobacter) and increased levels of particulate metals via sulfate reduction. Aeration resulted in an increase in Sideroxydans abundance but no significant changes in metal chemistry were observed. The study concludes that the utilisation of organic carbon by microorganisms is more important for achieving efficient AMD treatment than the availability of oxygen, yet the combination of oxygen with organic carbon addition did not inhibit the improvements to water quality.


Assuntos
Microbiota , Áreas Alagadas , Ácidos , Mineração , Qualidade da Água
9.
Proc Natl Acad Sci U S A ; 118(39)2021 09 28.
Artigo em Inglês | MEDLINE | ID: mdl-34544862

RESUMO

Ocean-warming and acidification are predicted to reduce coral reef biodiversity, but the combined effects of these stressors on overall biodiversity are largely unmeasured. Here, we examined the individual and combined effects of elevated temperature (+2 °C) and reduced pH (-0.2 units) on the biodiversity of coral reef communities that developed on standardized sampling units over a 2-y mesocosm experiment. Biodiversity and species composition were measured using amplicon sequencing libraries targeting the cytochrome oxidase I (COI) barcoding gene. Ocean-warming significantly increased species richness relative to present-day control conditions, whereas acidification significantly reduced richness. Contrary to expectations, species richness in the combined future ocean treatment with both warming and acidification was not significantly different from the present-day control treatment. Rather than the predicted collapse of biodiversity under the dual stressors, we find significant changes in the relative abundance but not in the occurrence of species, resulting in a shuffling of coral reef community structure among the highly species-rich cryptobenthic community. The ultimate outcome of altered community structure for coral reef ecosystems will depend on species-specific ecological functions and community interactions. Given that most species on coral reefs are members of the understudied cryptobenthos, holistic research on reef communities is needed to accurately predict diversity-function relationships and ecosystem responses to future climate conditions.


Assuntos
Ácidos/efeitos adversos , Antozoários/fisiologia , Biodiversidade , Mudança Climática , Recifes de Corais , Ecossistema , Estresse Fisiológico , Animais , Concentração de Íons de Hidrogênio , Oceanos e Mares
10.
PLoS One ; 16(9): e0256964, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34492053

RESUMO

Cross-pollination affects the fruit characteristics of many crops but the effects of cross-pollination on fruit quality of strawberry (Fragaria × ananassa Duch.) are poorly known. This study determined how cross-pollination affects fruit quality of the strawberry cultivar, Redlands Joy, under controlled environment conditions. Plants were allocated to one of four treatments, with all flowers on each plant receiving either: (1) unassisted self-pollination (Autogamy); (2) hand-pollination with Redlands Joy pollen (Self); (3) hand-pollination with cross-pollen from a small-fruited cultivar (Sugarbaby); or (4) hand-pollination with cross-pollen from a large-fruited cultivar (Rubygem). Cross-pollination did not significantly affect plant yield or fruit mass, size, shape, firmness or shelf life. However, cross-pollination affected fruit colour and taste attributes. Cross-pollinated fruit were 3%-5% darker than self-pollinated fruit. They also had 26%-34% lower acidity and 43%-58% higher Brix:acid ratio. Cross-pollination by Sugarbaby increased fruit P, K, Ca, Fe and Mn, but decreased B, Cu and Zn, concentrations. Cross-pollination by Rubygem increased fruit Mn, but decreased K and Na, concentrations and reduced shelf life. Fruit mass, length, diameter and firmness within all treatments increased with increasing numbers of fertilized seeds per fruit. Hand self-pollinated fruit had a higher percentage of fertilized seeds than fruit arising from autogamy and they were also darker, redder, firmer, and had a longer shelf life, higher protein concentration, and lower Al and Na concentrations. The results indicate that strawberry fruit quality can be affected by both the source of pollen and the number of stigmas pollinated.


Assuntos
Fertilização/genética , Fragaria/crescimento & desenvolvimento , Frutas/genética , Reprodução/genética , Ácidos/química , Cor , Produtos Agrícolas , Fertilização/fisiologia , Flores/genética , Flores/crescimento & desenvolvimento , Armazenamento de Alimentos , Fragaria/genética , Frutas/crescimento & desenvolvimento , Pólen/genética , Polinização/genética , Reprodução/fisiologia , Sementes/genética , Sementes/crescimento & desenvolvimento
11.
Molecules ; 26(18)2021 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-34577093

RESUMO

Dietary fiber can be obtained by dextrinization, which occurs while heating starch in the presence of acids. During dextrinization, depolymerization, transglycosylation, and repolymerization occur, leading to structural changes responsible for increasing resistance to starch enzymatic digestion. The conventional dextrinization time can be decreased by using microwave-assisted heating. The main objective of this study was to obtain dietary fiber from acidified potato starch using continuous and discontinuous microwave-assisted heating and to investigate the structure and physicochemical properties of the resulting dextrins. Dextrins were characterized by water solubility, dextrose equivalent, and color parameters (L* a* b*). Total dietary fiber content was measured according to the AOAC 2009.01 method. Structural and morphological changes were determined by means of SEM, XRD, DSC, and GC-MS analyses. Microwave-assisted dextrinization of potato starch led to light yellow to brownish products with increased solubility in water and diminished crystallinity and gelatinization enthalpy. Dextrinization products contained glycosidic linkages and branched residues not present in native starch, indicative of its conversion into dietary fiber. Thus, microwave-assisted heating can induce structural changes in potato starch, originating products with a high level of dietary fiber content.


Assuntos
Fibras na Dieta/análise , Temperatura Alta , Micro-Ondas , Amido/química , Ácidos/química , Configuração de Carboidratos , Cor , Dextrinas/análise , Dextrinas/química , Glucose/análise , Glucose/química , Microscopia Eletrônica de Varredura , Fenômenos Físicos , Solanum tuberosum/química , Solubilidade , Difração de Raios X
12.
J Hazard Mater ; 420: 126665, 2021 10 15.
Artigo em Inglês | MEDLINE | ID: mdl-34351284

RESUMO

Microbial communities are crucial to the effectiveness and stability of bioremediation systems treating acid mine drainage (AMD); however, little research has addressed how they correlate to system performance under changing environmental conditions. In this study, 16S rRNA gene sequencing and quantitative PCR (qPCR) were used to characterize microbial communities within different substrate combinations of crab shell (CS) and spent mushroom compost (SMC) and their association with chemical performance in pilot-scale vertical flow ponds (VFPs) treating high risk AMD in central Pennsylvania over 643 days of operation. As compared to a control containing SMC, VFPs containing CS sustained higher alkalinity, higher sulfate-reducing rates, and more thorough metals removal (>90% for Fe and Al, >50% for Mn and Zn). Correspondingly, CS VFPs supported the growth of microorganisms in key functional groups at increasing abundance and diversity over time, especially more diverse sulfate-reducing bacteria. Through changing seasonal and operational conditions over almost two years, the relative abundance of the core phyla shifted in all reactors, but the smallest changes in functional gene copies were observed in VFPs containing CS. These results suggest that the high diversity and stability of microbial communities associated with CS are consistent with effective AMD treatment.


Assuntos
Braquiúros , Microbiota , Ácidos , Animais , Braquiúros/genética , Mineração , RNA Ribossômico 16S/genética
13.
J Insect Physiol ; 133: 104288, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34343520

RESUMO

Larvae of chironomid Chironomus sulfurosus mainly live in acidic rivers near hot springs, suggesting that they naturally select acidic environments as preferred habitats. Here we showed that C. sulfurosus larvae moved toward acidic areas and stayed alive on agar gels with a pH gradient of H2SO4, and the body fluid pH of the homogenized larvae was near neutral even acclimated under the acidic conditions, indicating mechanisms for acid tolerance. In order to gain insights into this mechanism at the molecular level, de novo RNA-seq analysis was performed on C. sulfurosus larvae. As a result, 1,208 genes were found to be significantly up-regulated in larvae acclimated at pH 2.0 compared to controls at pH 7.0. Among the up-regulated genes, ones encoding cuticle proteins, peritrophic matrix proteins, mucus-forming proteins, F-type ATPase subunits, glutathione S transferases, ß-1,3-D-glucan synthetase, hemoglobin, and cytochrome P450 were identified. This transcriptome analysis in conjunction with behavioral and biochemical assays expands our knowledge of gene expression in C. sulfurosus larvae living in acidic environments, which will provide a basis for further studies to elucidate the molecular mechanisms for acid tolerance employed by organisms in nature.


Assuntos
Chironomidae/fisiologia , Água Doce/química , Genes de Insetos , Proteínas de Insetos/metabolismo , Transcriptoma , Ácidos/metabolismo , Animais , Chironomidae/genética , Chironomidae/crescimento & desenvolvimento , Perfilação da Expressão Gênica , Concentração de Íons de Hidrogênio , Larva/genética , Larva/crescimento & desenvolvimento , Larva/fisiologia
14.
Biomolecules ; 11(8)2021 07 23.
Artigo em Inglês | MEDLINE | ID: mdl-34439752

RESUMO

Global agricultural intensification has prompted investigations into biostimulants to enhance plant nutrition and soil ecosystem processes. Metal lactates are an understudied class of organic micronutrient supplement that provide both a labile carbon source and mineral nutrition for plant and microbial growth. To gain a fundamental understanding of plant responses to metal lactates, we employed a series of sterile culture-vessel experiments to compare the uptake and toxicity of five metals (Zn, Mn, Cu, Ni, and Co) supplied in lactate and chloride salt form. Additionally, primary root growth in plate-grown Arabidopsis thaliana seedlings was used to determine optimal concentrations of each metal lactate. Our results suggest that uptake and utilization of metals in wheat (Triticum aestivum L.) when supplied in lactate form is comparable to that of metal chlorides. Metal lactates also have promotional growth effects on A. thaliana seedlings with optimal concentrations identified for Zn (0.5-1.0 µM), Mn (0.5-1.0 µM), Cu (0.5 µM), Ni (1.0 µM), and Co (0.5 µM) lactate. These findings present foundational evidence to support the use of metal lactates as potential crop biostimulants due to their ability to both supply nutrients and stimulate plant growth.


Assuntos
Arabidopsis/metabolismo , Cloretos/química , Lactatos/química , Metais/química , Ácidos/química , Agricultura/métodos , Quelantes , Ecossistema , Hidroponia , Ácido Láctico , Metais Pesados , Micronutrientes/química , Compostos Orgânicos , Plântula , Sementes/metabolismo , Solo , Poluentes do Solo/análise , Triticum , Zinco/química
15.
Molecules ; 26(16)2021 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-34443543

RESUMO

The thermodynamic, kinetic, and structural properties of Ln3+ complexes with the bifunctional DO3A-ACE4- ligand and its amide derivative DO3A-BACE4- (modelling the case where DO3A-ACE4- ligand binds to vector molecules) have been studied in order to confirm the usefulness of the corresponding Gd3+ complexes as relaxation labels of targeted MRI contrast agents. The stability constants of the Mg2+ and Ca2+ complexes of DO3A-ACE4- and DO3A-BACE4- complexes are lower than for DOTA4- and DO3A3-, while the Zn2+ and Cu2+ complexes have similar and higher stability than for DOTA4- and DO3A3- complexes. The stability constants of the Ln(DO3A-BACE)- complexes increase from Ce3+ to Gd3+ but remain practically constant for the late Ln3+ ions (represented by Yb3+). The stability constants of the Ln(DO3A-ACE)4- and Ln(DO3A-BACE)4- complexes are several orders of magnitude lower than those of the corresponding DOTA4- and DO3A3- complexes. The formation rate of Eu(DO3A-ACE)- is one order of magnitude slower than for Eu(DOTA)-, due to the presence of the protonated amine group, which destabilizes the protonated intermediate complex. This protonated group causes the Ln(DO3A-ACE)- complexes to dissociate several orders of magnitude faster than Ln(DOTA)- and its absence in the Ln(DO3A-BACE)- complexes results in inertness similar to Ln(DOTA)- (as judged by the rate constants of acid assisted dissociation). The 1H NMR spectra of the diamagnetic Y(DO3A-ACE)- and Y(DO3A-BACE)- reflect the slow dynamics at low temperatures of the intramolecular isomerization process between the SA pair of enantiomers, R-Λ(λλλλ) and S-Δ(δδδδ). The conformation of the Cα-substituted pendant arm is different in the two complexes, where the bulky substituent is further away from the macrocyclic ring in Y(DO3A-BACE)- than the amino group in Y(DO3A-ACE)- to minimize steric hindrance. The temperature dependence of the spectra reflects slower ring motions than pendant arms rearrangements in both complexes. Although losing some thermodynamic stability relative to Gd(DOTA)-, Gd(DO3A-BACE)- is still quite inert, indicating the usefulness of the bifunctional DO3A-ACE4- in the design of GBCAs and Ln3+-based tags for protein structural NMR analysis.


Assuntos
Complexos de Coordenação/química , Espectroscopia de Ressonância Magnética , Propionatos/química , Ácidos/química , Catálise , Íons , Cinética , Ligantes , Prótons , Soluções , Termodinâmica
16.
Bioresour Technol ; 341: 125773, 2021 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-34419879

RESUMO

The movement of solid material into and between unit operations within a biorefinery is a bottleneck in reaching design capacity, with formation of biomass slurries needed to introduce feedstock. Corn stover slurries have been achieved from dilute acid, pretreated materials resulting in slurry concentrations of up to about 150 g/L, above which flowability is compromised. We report a new strategy to liquefy corn stover at higher solids concentration (300 g/L) by initially cooking it with the enzyme mimetic maleic acid at 40 mM and 150 °C. This is followed by 6 h of enzymatic modification at 1 FPU (2.2 mg protein)/g solids, resulting in a yield stress of 171 Pa after 6 h and 58 Pa in 48 h compared to 6806 Pa for untreated stover. Mimetic treatment of corn stover pellets minimizes the inhibitory effect of xylo-oligomers on hydrolytic enzymes. This strategy allows for the delivery of solid lignocellulosic slurry into a pretreatment reactor by pumping, improving operability of a biorefinery.


Assuntos
Ácidos , Zea mays , Biomassa , Hidrólise
17.
J Agric Food Chem ; 69(33): 9642-9653, 2021 Aug 25.
Artigo em Inglês | MEDLINE | ID: mdl-34382782

RESUMO

Radical formation in isohumulones was investigated under different types of stress, including temperature, transition metal ions, and hydrogen peroxide. Including dihydroisohumulones and tetrahydroisohumulones, as relevant analogues, allowed us to evaluate critical functionalities in radical formation. Using spin-trapping methodology with 5,5-dimethyl-1-pyrroline N-oxide and N-tert-butyl-α-phenylnitrone as relevant traps, followed by simulation of corresponding spin adducts, identification of incipient radicals was attempted. The isohexenoyl side chain in isohumulones, but not present in dihydro- and tetrahydroisohumulones, was most sensitive to radical formation. Kinetic profiles further demonstrated that radical formation in this moiety was accelerated in the presence of ferrous ions. Reactivity of parent six-membered-ring humulones in radical formation was different, as scavenging of free radical species was more important. Lupulones, despite similarity with humulones, showed a different behavior with an obvious radical decay pathway during ageing, mainly ascribed to radical formation on the ring structure. Quantification of final spin adducts allowed us to determine absolute importance of the different degradation pathways. Eventually, mechanisms are presented explaining why isohumulones are more prone to radical processes in (aut)oxidation and thermal decay than close relatives such as dihydroisohumulones.


Assuntos
Ácidos , Óxidos N-Cíclicos , Espectroscopia de Ressonância de Spin Eletrônica , Radicais Livres , Oxirredução , Marcadores de Spin , Detecção de Spin
18.
Nutrients ; 13(7)2021 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-34371931

RESUMO

The purpose of this study was to examine the independent and joint associations of acid-producing diets and depressive symptoms with physical health among breast cancer survivors. We studied a cohort of 2944 early stage breast cancer survivors who provided dietary, physical health, demographic, and lifestyle information at baseline, year 1, and year 4. We assessed the intakes of acid-producing diets via two commonly used dietary acid load scores: potential renal acid load (PRAL) and net endogenous acid production (NEAP). Physical health was measured using the Rand 36-Item Short Form Health Survey (SF-36), consisting of physical functioning, role limitation due to physical function, bodily pain, general health, and overall physical health subscales. Increased dietary acid load and depression were each independently and significantly associated with reduced physical health subscales and overall physical health. Further, dietary acid load and depression were jointly associated with worse physical health. For instance, depressed women with dietary acid load higher than median reported 2.75 times the risk (odds ratio = 2.75; 95% confidence interval: 2.18-3.47) of reduced physical function and 3.10 times the risk of poor physical health (odds ratio = 3.10; 95% confidence interval: 2.53-3.80) compared to non-depressed women with dietary acid load lower than median. Our results highlight the need of controlling acid-producing diets and the access of mental care for breast cancer survivors.


Assuntos
Ácidos/efeitos adversos , Afeto , Neoplasias da Mama/terapia , Sobreviventes de Câncer/psicologia , Depressão/complicações , Dieta/efeitos adversos , Saúde Mental , Ácidos/metabolismo , Adulto , Depressão/diagnóstico , Depressão/psicologia , Feminino , Nível de Saúde , Humanos , Concentração de Íons de Hidrogênio , Pessoa de Meia-Idade , Prognóstico , Ensaios Clínicos Controlados Aleatórios como Assunto , Medição de Risco , Fatores de Risco , Fatores de Tempo
19.
Food Res Int ; 147: 110494, 2021 09.
Artigo em Inglês | MEDLINE | ID: mdl-34399490

RESUMO

Slightly acidic electrolysed water (SAEW) and high-pressure processing (HPP) are well-established non-thermal preservation technologies. This study investigated the deactivation mechanisms of Listeria monocytogenes by label-free quantitative proteomics analysis. Samples were treated through HPP (300 MPa for 3 min), SAEW (20 ppm available chlorine concentration), and their combinations. The KEGG pathway analysis found SAEW + HPP induced differentially expressed proteins (DEPs) associated to biofunctions of ribosomes, secondary metabolite biosynthesis, microbial metabolism in diverse environments, carbon metabolism, and biosynthesis of amino acid and aminoacyl-transfer RNA. The results showed these non-thermal treatments were able to induce the shifting of ribosome biogenesis to initiate translation in L. monocytogenes. During protein translation, the initiation stage was upregulated. However, subsequent elongation, termination, and recycling of used ribosomes were retarded. Comparing various treatments, the combination of hurdles showed greater deactivation of L. monocytogenes than any single one. The approaches developed in this study provided crucial information for minimally processing in the food industries on the application of foodborne listeriosis prevention.


Assuntos
Listeria monocytogenes , Ácidos , Eletrólise , Proteoma , Água
20.
Biomed Res Int ; 2021: 9731280, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34368356

RESUMO

A fluoride-releasing adhesive system is expected to promote mineralization of demineralized dentin/enamel around a composite restoration, thereby contributing to the longevity of the restoration. Scanning electron microscopic (SEM) and transmission electron microscopic (TEM) observations revealed the formation of an "acid-base resistant zone" (ABRZ) beneath the hybrid layer when dentin was treated with a self-etch adhesive system. A thicker ABRZ was formed from the upper slope to the end of the outer lesion, indicating greater resistance against an acid-base challenge, when a fluoride-releasing self-etch adhesive system was used. The slope formation of a fluoride-releasing adhesive is believed to be due to fluoride-release from the adhesive. Quantitative assessment of the acid resistance was performed at the interface using the region of interest (ROI) mode of a digital image analysis software package. The area of the ABRZ is influenced by the concentration of fluoride release from the adhesive resin. The threshold of fluoride concentration in the adhesive may exist to influence the morphology of the ABRZ. X-ray absorption fine structure (XAFS) analysis of the dentin treated with different concentrations of NaF-mouth rinses suggested that different fluoride concentrations result in the formation of different chemical compounds, such as fluorapatite and CaF2-like structures, on the dentin surface. This may explain the differences in µTBS values and morphological appearance of the ABRZ. NaF is effective in enhancing the enamel/dentin bond durability and also helps create a high quality of ARBZ to improve the clinical success of restorations.


Assuntos
Condicionamento Ácido do Dente , Ácidos/química , Adesivos/química , Álcalis/química , Fluoretos/análise , Dentina/ultraestrutura
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