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1.
Nature ; 586(7828): 287-291, 2020 10.
Artigo em Inglês | MEDLINE | ID: mdl-32728214

RESUMO

All metazoans depend on the consumption of O2 by the mitochondrial oxidative phosphorylation system (OXPHOS) to produce energy. In addition, the OXPHOS uses O2 to produce reactive oxygen species that can drive cell adaptations1-4, a phenomenon that occurs in hypoxia4-8 and whose precise mechanism remains unknown. Ca2+ is the best known ion that acts as a second messenger9, yet the role ascribed to Na+ is to serve as a mere mediator of membrane potential10. Here we show that Na+ acts as a second messenger that regulates OXPHOS function and the production of reactive oxygen species by modulating the fluidity of the inner mitochondrial membrane. A conformational shift in mitochondrial complex I during acute hypoxia11 drives acidification of the matrix and the release of free Ca2+ from calcium phosphate (CaP) precipitates. The concomitant activation of the mitochondrial Na+/Ca2+ exchanger promotes the import of Na+ into the matrix. Na+ interacts with phospholipids, reducing inner mitochondrial membrane fluidity and the mobility of free ubiquinone between complex II and complex III, but not inside supercomplexes. As a consequence, superoxide is produced at complex III. The inhibition of Na+ import through the Na+/Ca2+ exchanger is sufficient to block this pathway, preventing adaptation to hypoxia. These results reveal that Na+ controls OXPHOS function and redox signalling through an unexpected interaction with phospholipids, with profound consequences for cellular metabolism.


Assuntos
Transporte de Elétrons , Hipóxia/metabolismo , Mitocôndrias/metabolismo , Sistemas do Segundo Mensageiro , Sódio/metabolismo , Animais , Neoplasias da Mama/metabolismo , Neoplasias da Mama/patologia , Fosfatos de Cálcio/metabolismo , Linhagem Celular Tumoral , Precipitação Química , Humanos , Masculino , Fluidez de Membrana , Camundongos Endogâmicos C57BL , Membranas Mitocondriais/química , Membranas Mitocondriais/metabolismo , Proteínas Mitocondriais/metabolismo , Fosforilação Oxidativa , Ratos , Ratos Wistar , Espécies Reativas de Oxigênio/metabolismo , Trocador de Sódio e Cálcio/metabolismo
2.
Mol Cell Proteomics ; 23(10): 100837, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39243857

RESUMO

Universal sample preparation for proteomic analysis that enables unbiased protein manipulation, flexible reagent use, and low protein loss is required to ensure the highest sensitivity of downstream liquid chromatography-mass spectrometry (LC-MS) analysis. To address these needs, we developed a ZnCl2 precipitation-assisted sample preparation method (ZASP) that depletes harsh detergents and impurities in protein solutions prior to trypsin digestion via 10 min of ZnCl2 and methanol-induced protein precipitation at room temperature (RT). ZASP can remove trypsin digestion and LC-MS incompatible detergents such as SDS, Triton X-100, and urea at high concentrations in solution and unbiasedly recover proteins independent of the amount of protein input. We demonstrated the sensitivity and reproducibility of ZASP in an analysis of samples with 1 µg to 1000 µg of proteins. Compared to commonly used sample preparation methods such as SDC-based in-solution digestion, acetone precipitation, FASP, and SP3, ZASP has proven to be an efficient approach. Here, we present ZASP, a practical, robust, and cost-effective proteomic sample preparation method that can be applied to profile different types of samples.


Assuntos
Cloretos , Proteômica , Compostos de Zinco , Proteômica/métodos , Compostos de Zinco/química , Cloretos/análise , Cloretos/química , Humanos , Precipitação Química , Cromatografia Líquida/métodos , Tripsina/química , Tripsina/metabolismo , Reprodutibilidade dos Testes , Detergentes/química
3.
Proc Natl Acad Sci U S A ; 120(1): e2211442120, 2023 01 03.
Artigo em Inglês | MEDLINE | ID: mdl-36574693

RESUMO

In this study, an aqueous nonlinear synaptic element showing plasticity behavior is developed, which is based on the chemical processes in an ionic diode. The device is simple, fully ionic, and easily configurable, requiring only two terminals-for input and output-similar to biological synapses. The key processes realizing the plasticity features are chemical precipitation and dissolution, which occur at forward- or reverse-biased ionic diode junctions in appropriate reservoir electrolytes. Given that the precipitate acts as a physical barrier in the circuit, the above processes change the diode conductivity, which can be interpreted as adjusting "synaptic weight" of the system. By varying the operating conditions, we first demonstrate the four types of plasticity that can be found in biological system: long-term potentiation/depression and short-term potentiation/depression. The plasticity of the proposed iontronic device has characteristics similar to those of neural synapses. To demonstrate its potential use in comparatively complex information processing, we develop a precipitation-based iontronic synapse (PIS) capable of both potentiation and depression. Finally, we show that the postsynaptic signals from the multiple excitatory or inhibitory PISs can be integrated into the total "dendritic" current, which is a function of time and input history, as in actual hippocampal neural circuits.


Assuntos
Hidrogéis , Plasticidade Neuronal , Solubilidade , Potenciação de Longa Duração , Sinapses , Íons , Precipitação Química
4.
Proteomics ; 24(15): e2400071, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38700387

RESUMO

Plasma is an abundant source of proteins and potential biomarkers to aid in the detection, diagnosis, and prognosis of human diseases. These proteins are often present at low levels in the blood and difficult to identify and measure due to the large dynamic range of proteins. The goal of this work was to characterize and compare various protein precipitation methods related to how they affect the depth and breadth of plasma proteomic studies. Abundant protein precipitation with perchloric acid (PerCA) can increase protein identifications and depth of plasma proteomic studies. Three acid- and four solvent-based precipitation methods were evaluated. All methods tested provided excellent plasma proteomic coverage (>600 identified protein groups) and detected protein in the low pg/mL range. Functional enrichment analysis revealed subtle differences within and larger changes between the precipitant groups. Methanol-based precipitation outperformed the other methods based on identifications and reproducibility. The methods' performance was verified using eight lung cancer patient samples, where >700 protein groups were measured and proteins with an estimated plasma concentration of ∼10 pg/mL were detected. Various protein precipitation agents are amenable to extending the depth and breadth of plasma proteomes. These data can guide investigators to implement inexpensive, high-throughput methods for their plasma proteomic workflows.


Assuntos
Proteínas Sanguíneas , Precipitação Química , Proteômica , Humanos , Proteômica/métodos , Proteínas Sanguíneas/análise , Proteínas Sanguíneas/isolamento & purificação , Proteínas Sanguíneas/química , Proteoma/análise , Neoplasias Pulmonares/sangue , Espectrometria de Massas em Tandem/métodos
5.
Proteomics ; 24(10): e2300339, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38299459

RESUMO

Detergent-based workflows incorporating sodium dodecyl sulfate (SDS) necessitate additional steps for detergent removal ahead of mass spectrometry (MS). These steps may lead to variable protein recovery, inconsistent enzyme digestion efficiency, and unreliable MS signals. To validate a detergent-based workflow for quantitative proteomics, we herein evaluate the precision of a bottom-up sample preparation strategy incorporating cartridge-based protein precipitation with organic solvent to deplete SDS. The variance of data-independent acquisition (SWATH-MS) data was isolated from sample preparation error by modelling the variance as a function of peptide signal intensity. Our SDS-assisted cartridge workflow yield a coefficient of variance (CV) of 13%-14%. By comparison, conventional (detergent-free) in-solution digestion increased the CV to 50%; in-gel digestion provided lower CVs between 14% and 20%. By filtering peptides predicting to display lower precision, we further enhance the validity of data in global comparative proteomics. These results demonstrate the detergent-based precipitation workflow is a reliable approach for in depth, label-free quantitative proteome analysis.


Assuntos
Precipitação Química , Detergentes , Proteômica , Dodecilsulfato de Sódio , Fluxo de Trabalho , Proteômica/métodos , Dodecilsulfato de Sódio/química , Detergentes/química , Proteoma/análise , Proteoma/química , Humanos , Peptídeos/química , Peptídeos/análise
6.
J Proteome Res ; 23(9): 3933-3943, 2024 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-39140748

RESUMO

Immunoglobulin G (IgG) purification is a critical process for evaluating its role in autoimmune diseases, which are defined by the occurrence of autoantibodies. Affinity chromatography with protein G is widely considered to be the optimal technique for laboratory-scale purification. However, this technique has some limitations, including the exposure of IgG to low pH, which can compromise the quality of the purified IgG. Here, we show that alternative methods for IgG purification are possible while maintaining the quality of IgG. Different techniques for IgG purification from serum were evaluated and compared with protein G-based approaches: Melon Gel, caprylic acid-ammonium sulfate (CAAS) precipitation, anion-exchange chromatography with diethylamino ethyl (DEAE) following ammonium sulfate (AS) precipitation, and AS precipitation alone. The results demonstrated that the purification yield of these techniques surpassed that of protein G. However, differences in the purity of IgG were observed using GeLC-MS/MS. The avidity of purified IgG against selected targets (SARS-CoV-2 and topoisomerase-I) was similar between purified IgG obtained using all techniques and unpurified sera. Our work provides valuable insights for future studies of IgG function by recommending alternative purification methods that offer advantages in terms of yield, time efficiency, cost-effectiveness, and milder pH conditions than protein G.


Assuntos
Sulfato de Amônio , Cromatografia de Afinidade , Imunoglobulina G , Humanos , Imunoglobulina G/isolamento & purificação , Imunoglobulina G/sangue , Imunoglobulina G/química , Cromatografia de Afinidade/métodos , Sulfato de Amônio/química , Cromatografia por Troca Iônica/métodos , Espectrometria de Massas em Tandem/métodos , SARS-CoV-2/imunologia , Caprilatos/química , Precipitação Química , COVID-19/sangue , COVID-19/imunologia , COVID-19/virologia , Afinidade de Anticorpos
7.
Small ; 20(30): e2306877, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38415820

RESUMO

Complexation between oppositely charged polyelectrolytes offers a facile single-step strategy for assembling functional micro-nano carriers for efficient drug and vaccine delivery. However, the stability of the delivery system within the physiological environment is compromised due to the swelling of the polyelectrolyte complex, driven by the charge shielding effect, and consequently leads to uncontrollable burst release, thereby limiting its potential applications. In a pioneering approach, cellular pathway-inspired calcium carbonate precipitation pathways are developed that are integrated into polyelectrolyte capsules (MICPC). These innovative capsules are fabricated at the interface of all-aqueous microfluidic droplets, resulting in a precisely controllable and sustained release profile in physiological conditions. Unlike single-step polyelectrolyte assembly capsules which always perform rapid burst release, the MICPC exhibits a sustainable and tunable release pattern, releasing biomolecules at an average rate of 3-10% per day. Remarkably, the degree of control over MICPC's release kinetics can be finely tuned by adjusting the quantity of synthesized calcium carbonate particles within the polyelectrolyte complex. This groundbreaking work not only deepens the insights into polyelectrolyte complexation but also significantly enhances the overall stability of these complexes, opening up new avenues for expanding the range of applications involving polyelectrolyte complex-related materials.


Assuntos
Carbonato de Cálcio , Cápsulas , Polieletrólitos , Carbonato de Cálcio/química , Cápsulas/química , Polieletrólitos/química , Precipitação Química , Eletrólitos/química
8.
Biotechnol Bioeng ; 121(3): 1076-1089, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38151908

RESUMO

Chemically defined mineral media are widely used in bioprocesses, as these show less batch to batch variation compared with complex media. Nonetheless, the recommended media formulations often lead to the formation of precipitants at elevated pH values. These precipitates are insoluble and reduce the availability of macronutrients to the cells, which can result in limiting growth rates and lower productivity. They can also damage equipment by clogging pipes, hoses, and spargers in stirred tank fermenters. In this study, the observed precipitate was analyzed via X-ray fluorescence spectroscopy and identified as the magnesium ammonium phosphate salt struvite (MgNH4 PO4 × 6H2 O). The solubility of struvite crystals is known to be extremely low, causing the macronutrients magnesium, phosphate, and ammonium to be bound in the struvite crystals. Here, it was shown that struvite precipitates can be redissolved under common fermentation conditions. Furthermore, it was found that the struvite particle size distribution has a significant effect on the dissolution kinetics, which directly affects macronutrient availability. At a certain particle size, struvite crystals rapidly dissolved and provided unlimiting growth conditions. Therefore, struvite formation should be considered during media and bioprocess development, to ensure that the dissolution kinetics of struvite are faster than the growth kinetics.


Assuntos
Compostos de Magnésio , Fosfatos , Estruvita , Compostos de Magnésio/química , Fermentação , Magnésio/química , Precipitação Química
9.
Mol Pharm ; 21(6): 2854-2864, 2024 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-38718215

RESUMO

The purpose of the present study was to clarify whether the precipitation profile of a drug in bicarbonate buffer (BCB) may differ from that in phosphate buffer (PPB) by a well-controlled comparative study. The precipitation profiles of structurally diverse poorly soluble drugs in BCB and PPB were evaluated by a pH-shift precipitation test or a solvent-shift precipitation test (seven weak acid drugs (pKa: 4.2 to 7.5), six weak base drugs (pKa: 4.8 to 8.4), one unionizable drug, and one zwitterionic drug). To focus on crystal precipitation processes, each ionizable drug was first completely dissolved in an HCl (pH 3.0) or NaOH (pH 11.0) aqueous solution (450 mL, 50 rpm, 37 °C). A 10-fold concentrated buffer solution (50 mL) was then added to shift the pH value to 6.5 to initiate precipitation (final volume: 500 mL, buffer capacity (ß): 4.4 mM/ΔpH (BCB: 10 mM or PPB: 8 mM), ionic strength (I): 0.14 M (adjusted by NaCl)). The pH, ß, and I values were set to be relevant to the physiology of the small intestine. For an unionizable drug, a solvent-shift method was used (1/100 dilution). To maintain the pH value of BCB, a floating lid was used to avoid the loss of CO2. The floating lid was applied also to PPB to precisely align the experimental conditions between BCB and PPB. The solid form of the precipitants was identified by powder X-ray diffraction and differential scanning microscopy. The precipitation of weak acids (pKa ≤ 5.1) and weak bases (pKa ≥ 7.3) was found to be slower in BCB than in PPB. In contrast, the precipitation profiles in BCB and PPB were similar for less ionizable or nonionizable drugs at pH 6.5. The final pH values of the bulk phase were pH 6.5 ± 0.1 after the precipitation tests in all cases. All precipitates were in their respective free forms. The precipitation of ionizable weak acids and bases was slower in BCB than in PPB. The surface pH of precipitating particles may have differed between BCB and PPB due to the slow hydration process of CO2 specific to BCB. Since BCB is a physiological buffer in the small intestine, it should be considered as an option for precipitation studies of ionizable weak acids and bases.


Assuntos
Bicarbonatos , Precipitação Química , Cristalização , Fosfatos , Soluções Tampão , Concentração de Íons de Hidrogênio , Bicarbonatos/química , Fosfatos/química , Solubilidade , Concentração Osmolar , Química Farmacêutica/métodos , Difração de Raios X/métodos
10.
PLoS Biol ; 19(4): e3001198, 2021 04.
Artigo em Inglês | MEDLINE | ID: mdl-33909608

RESUMO

Transactive response DNA-binding Protein of 43 kDa (TDP-43) assembles various aggregate forms, including biomolecular condensates or functional and pathological amyloids, with roles in disparate scenarios (e.g., muscle regeneration versus neurodegeneration). The link between condensates and fibrils remains unclear, just as the factors controlling conformational transitions within these aggregate species: Salt- or RNA-induced droplets may evolve into fibrils or remain in the droplet form, suggesting distinct end point species of different aggregation pathways. Using microscopy and NMR methods, we unexpectedly observed in vitro droplet formation in the absence of salts or RNAs and provided visual evidence for fibrillization at the droplet surface/solvent interface but not the droplet interior. Our NMR analyses unambiguously uncovered a distinct amyloid conformation in which Phe-Gly motifs are key elements of the reconstituted fibril form, suggesting a pivotal role for these residues in creating the fibril core. This contrasts the minor participation of Phe-Gly motifs in initiation of the droplet form. Our results point to an intrinsic (i.e., non-induced) aggregation pathway that may exist over a broad range of conditions and illustrate structural features that distinguishes between aggregate forms.


Assuntos
Proteínas de Ligação a DNA/química , Proteínas de Ligação a DNA/metabolismo , Dipeptídeos/química , Agregados Proteicos , Sequência de Aminoácidos , Amiloide/química , Amiloide/metabolismo , Precipitação Química , Dipeptídeos/fisiologia , Humanos , Concentração de Íons de Hidrogênio , Agregação Patológica de Proteínas/metabolismo , Agregação Patológica de Proteínas/patologia , Domínios e Motivos de Interação entre Proteínas/fisiologia , Solventes/química , Solventes/farmacologia
11.
Protein Expr Purif ; 224: 106578, 2024 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-39153561

RESUMO

Current biological research requires simple protein bioseparation methods capable of purifying target proteins in a single step with high yields and purities. Conventional affinity tag-based approaches require specific affinity resins and expensive proteolytic enzymes for tag removal. Purification strategies based on self-cleaving aggregating tags have been previously developed to address these problems. However, these methods often utilize C-terminal cleaving contiguous inteins which suffer from premature cleavage, resulting in significant product loss during protein expression. In this work, we evaluate two novel mutants of the Mtu RecA ΔI-CM mini-intein obtained through yeast surface display for improved protein purification. When used with the elastin-like-polypeptide (ELP) precipitation tag, the novel mutants - ΔI-12 and ΔI-29 resulted in significantly higher precursor content, product purity and process yield compared to the original Mtu RecA ΔI-CM mini-intein. Product purities ranging from 68 % to 94 % were obtained in a single step for three model proteins - green fluorescent protein (GFP), maltose binding protein (MBP) and beta-galactosidase (beta-gal). Further, high cleaving efficiency was achieved after 5 h under most conditions. Overall, we have developed improved self-cleaving precipitation tags which can be used for purifying a wide range of proteins cheaply at laboratory scale.


Assuntos
Inteínas , Proteínas Ligantes de Maltose , Recombinases Rec A , beta-Galactosidase , Inteínas/genética , beta-Galactosidase/genética , beta-Galactosidase/química , beta-Galactosidase/isolamento & purificação , beta-Galactosidase/metabolismo , Proteínas Ligantes de Maltose/genética , Proteínas Ligantes de Maltose/química , Proteínas Ligantes de Maltose/metabolismo , Recombinases Rec A/genética , Recombinases Rec A/química , Recombinases Rec A/metabolismo , Proteínas de Fluorescência Verde/genética , Proteínas de Fluorescência Verde/química , Proteínas de Fluorescência Verde/metabolismo , Proteínas Recombinantes de Fusão/genética , Proteínas Recombinantes de Fusão/química , Proteínas Recombinantes de Fusão/isolamento & purificação , Proteínas Recombinantes de Fusão/metabolismo , Elastina/química , Elastina/genética , Elastina/isolamento & purificação , Precipitação Química , Escherichia coli/genética , Escherichia coli/metabolismo , Saccharomyces cerevisiae/genética , Saccharomyces cerevisiae/metabolismo , Saccharomyces cerevisiae/química
12.
Biomacromolecules ; 25(6): 3596-3606, 2024 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-38754095

RESUMO

Poly(vinyl alcohol)s (PVAs) are very popular dispersants for the construction of colloids and common shell-constituents of microcapsules but remain mostly unexplored as building blocks for the design of nanocapsules through nanoprecipitation or other processes. Herein, we first show that model commercial PVAs and oils can be concomitantly engaged in solvent-shifting procedures to give rise to oil-filled nanocapsules in one step. Next, we report the synthesis of precisely defined water-soluble glyco-PVAs by reversible addition-fragmentation chain transfer (RAFT) copolymerization of 6-O-vinyladipoyl-d-glucopyranose and vinyl chloroacetate and selective alcoholysis reactions. We finally demonstrate that these glycopolymers are excellent candidates for the straightforward conception of oil- and drug-filled, surface- and/or core-tagged, stealth, and degradable nanocapsules by nanoprecipitation.


Assuntos
Nanocápsulas , Álcool de Polivinil , Nanocápsulas/química , Álcool de Polivinil/química , Polimerização , Precipitação Química
13.
Microb Cell Fact ; 23(1): 168, 2024 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-38858761

RESUMO

BACKGROUND: Microbially induced calcium carbonate precipitation has been extensively researched for geoengineering applications as well as diverse uses within the built environment. Bacteria play a crucial role in producing calcium carbonate minerals, via enzymes including carbonic anhydrase-an enzyme with the capability to hydrolyse CO2, commonly employed in carbon capture systems. This study describes previously uncharacterised carbonic anhydrase enzyme sequences capable of sequestering CO2 and subsequentially generating CaCO3 biominerals and suggests a route to produce carbon negative cementitious materials for the construction industry. RESULTS: Here, Bacillus subtilis was engineered to recombinantly express previously uncharacterised carbonic anhydrase enzymes from Bacillus megaterium and used as a whole cell catalyst allowing this novel bacterium to sequester CO2 and convert it to calcium carbonate. A significant decrease in CO2 was observed from 3800 PPM to 820 PPM upon induction of carbonic anhydrase and minerals recovered from these experiments were identified as calcite and vaterite using X-ray diffraction. Further experiments mixed the use of this enzyme (as a cell free extract) with Sporosarcina pasteurii to increase mineral production whilst maintaining a comparable level of CO2 sequestration. CONCLUSION: Recombinantly produced carbonic anhydrase successfully sequestered CO2 and converted it into calcium carbonate minerals using an engineered microbial system. Through this approach, a process to manufacture cementitious materials with carbon sequestration ability could be developed.


Assuntos
Bacillus subtilis , Carbonato de Cálcio , Dióxido de Carbono , Anidrases Carbônicas , Sporosarcina , Carbonato de Cálcio/metabolismo , Carbonato de Cálcio/química , Bacillus subtilis/metabolismo , Bacillus subtilis/genética , Bacillus subtilis/enzimologia , Dióxido de Carbono/metabolismo , Anidrases Carbônicas/metabolismo , Anidrases Carbônicas/genética , Sporosarcina/metabolismo , Sporosarcina/enzimologia , Sporosarcina/genética , Bacillus megaterium/metabolismo , Bacillus megaterium/genética , Bacillus megaterium/enzimologia , Sequestro de Carbono , Precipitação Química , Proteínas de Bactérias/metabolismo , Proteínas de Bactérias/genética
14.
Environ Sci Technol ; 58(2): 1199-1210, 2024 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-38173390

RESUMO

The hydration of CO2 suffers from kinetic inefficiencies that make its natural trapping impractically sluggish. However, CO2-fixing carbonic anhydrases (CAs) remarkably accelerate its equilibration by 6 orders of magnitude and are, therefore, "ideal" catalysts. Notably, CA has been detected in ureolytic bacteria, suggesting its potential involvement in microbially induced carbonate precipitation (MICP), yet the dynamics of the urease (Ur) and CA genes remain poorly understood. Here, through the use of the ureolytic bacteriumSporosarcina pasteurii, we investigate the differing role of Ur and CA in ureolysis, CO2 hydration, and CaCO3 precipitation with increasing CO2(g) concentrations. We show that Ur gene up-regulation coincides with an increase in [HCO3-] following the hydration of CO2 to HCO3- by CA. Hence, CA physiologically promotes buffering, which enhances solubility trapping and affects the phase of the CaCO3 mineral formed. Understanding the role of CO2 hydration on the performance of ureolysis and CaCO3 precipitation provides essential new insights, required for the development of next-generation biocatalyzed CO2 trapping technologies.


Assuntos
Dióxido de Carbono , Anidrases Carbônicas , Carbonato de Cálcio , Urease , Anidrases Carbônicas/genética , Ureia , Precipitação Química
15.
Environ Sci Technol ; 58(19): 8501-8509, 2024 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-38696244

RESUMO

Iron/chromium hydroxide coprecipitation controls the fate and transport of toxic chromium (Cr) in many natural and engineered systems. Organic coatings on soil and engineered surfaces are ubiquitous; however, mechanistic controls of these organic coatings over Fe/Cr hydroxide coprecipitation are poorly understood. Here, Fe/Cr hydroxide coprecipitation was conducted on model organic coatings of humic acid (HA), sodium alginate (SA), and bovine serum albumin (BSA). The organics bonded with SiO2 through ligand exchange with carboxyl (-COOH), and the adsorbed amounts and pKa values of -COOH controlled surface charges of coatings. The adsorbed organic films also had different complexation capacities with Fe/Cr ions and Fe/Cr hydroxide particles, resulting in significant differences in both the amount (on HA > SA(-COOH) ≫ BSA(-NH2)) and composition (Cr/Fe molar ratio: on BSA(-NH2) ≫ HA > SA(-COOH)) of heterogeneous precipitates. Negatively charged -COOH attracted more Fe ions and oligomers of hydrolyzed Fe/Cr species and subsequently promoted heterogeneous precipitation of Fe/Cr hydroxide nanoparticles. Organic coatings containing -NH2 were positively charged at acidic pH because of the high pKa value of the functional group, limiting cation adsorption and formation of coprecipitates. Meanwhile, the higher local pH near the -NH2 coatings promoted the formation of Cr(OH)3. This study advances fundamental understanding of heterogeneous Fe/Cr hydroxide coprecipitation on organics, which is essential for successful Cr remediation and removal in both natural and engineered settings, as well as the synthesis of Cr-doped iron (oxy)hydroxides for material applications.


Assuntos
Cromo , Hidróxidos , Ferro , Hidróxidos/química , Ferro/química , Cromo/química , Soroalbumina Bovina/química , Adsorção , Substâncias Húmicas , Água/química , Precipitação Química , Alginatos/química
16.
Environ Sci Technol ; 58(21): 9283-9291, 2024 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-38752583

RESUMO

The concerns about the fate of per- and polyfluoroalkyl substances (PFAS) in the atmosphere are continuously growing. In this study, size-fractionated particles, gas, and rainwater samples were simultaneously collected in Shijiazhuang, China, to investigate the multiphase distribution of PFAS in the atmosphere. Perfluoroalkyl carboxylic acids (PFCAs) dominated the total concentration of PFAS in atmospheric media. A strong positive relationship (0.79 < R2 < 0.99) was observed between the concentration of PFCAs and organic matter fraction (fOM) in different particle size fractions, while no such relationship for perfluoroalkyl sulfonic acids (PFSAs) and fOM, suggesting fOM may be an important factor influencing the size-dependent distribution of PFCAs. Temperature played a key role in the gas-particle partitioning of PFAS, while it did not significantly affect their particle-size-dependent distribution. The associative concentration fluctuation of particle and particle-bound PFAS during precipitation suggested that precipitation scavenging was an important mechanism for the removal of PFAS from the atmosphere. Furthermore, temporary increases in atmospheric PFAS concentrations were observed during the precipitation. Fugacity ratios of PFAS in rainwater and gas phase (log fR/fG ranged between 2.0 and 6.6) indicated a strong trend for PFAS to diffuse from the rainwater to the gas phase during the precipitation, which may explain that the concentration of PFAS in the gas phase continued to increase even at the end of the precipitation.


Assuntos
Atmosfera , Fluorocarbonos , Tamanho da Partícula , Fluorocarbonos/análise , Atmosfera/química , Poluentes Atmosféricos/análise , Chuva/química , China , Monitoramento Ambiental , Gases , Precipitação Química
17.
J Appl Microbiol ; 135(1)2024 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-38111211

RESUMO

AIM: This study aimed to understand the morphological effects of (in)organic additives on microbially induced calcium carbonate precipitation (MICP). METHODS AND RESULTS: MICP was monitored in real time in the presence of (in)organic additives: bovine serum albumin (BSA), biofilm surface layer protein A (BslA), magnesium chloride (MgCl2), and poly-l-lysine. This monitoring was carried out using confocal microscopy to observe the formation of CaCO3 from the point of nucleation, in comparison to conditions without additives. Complementary methodologies, namely scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction, were employed to assess the visual morphology, elemental composition, and crystalline structures of CaCO3, respectively, following the crystals' formation. The results demonstrated that in the presence of additives, more CaCO3 crystals were produced at 100 min compared to the reaction without additives. The inclusion of BslA resulted in larger crystals than reactions containing other additives, including MgCl2. BSA induced a significant number of crystals from the early stages of the reaction (20 min) but did not have a substantial impact on crystal size compared to conditions without additives. All additives led to a higher content of calcite compared to vaterite after a 24-h reaction, with the exception of MgCl2, which produced a substantial quantity of magnesium calcite. CONCLUSIONS: The work demonstrates the effect of several (in)organic additives on MICP and sets the stage for further research to understand additive effects on MICP to achieve controlled CaCO3 precipitation.


Assuntos
Carbonato de Cálcio , Sporosarcina , Carbonato de Cálcio/metabolismo , Cloreto de Magnésio/metabolismo , Sporosarcina/metabolismo , Precipitação Química , Microscopia Eletrônica de Varredura
18.
Environ Res ; 250: 118500, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38387492

RESUMO

Arsenic pollution is a challenging environmental issue caused by arsenic-bearing wastes from nonferrous metallurgy. Oxidative precipitation via introducing O2 into an ionic Fe(II)-As(V) solution is an advanced method for arsenic immobilization. However, the underlying mechanism is still not well understood. This study proposed a mechanism for scorodite formation by oxidative precipitation, and its thermodynamics were calculated using Gaussian software. Scorodite formation was divided into three stages: precursor formation (3-90 min), oxidative conversion (90-270 min) and crystallization (270-720 min) from the variation in precipitates and solution characterization and parameters such as initial pH, arsenic concentration, and ferrous dosage. In the scorodite formation mechanism, the precursors originate from the coordination polymerization of aqueous Fe(H2O)62+ and H2AsO4-, which contributes to the oxidative conversion of coordinated polymers ([Fe(H2O)4(H2O)]nn+) to basic Fe(H2O)2AsO4 until regular octahedral crystals are formed via nucleation and growth during crystallization. The ΔrGmθ for polymerization varied from -491.96 kJ mol-1 to -33.30 kJ mol-1, and the ΔrGmθ of oxidative conversion changed from -982.16 kJ mol-1 to -224.82 kJ mol-1, demonstrating the feasibility in scorodite formation. This research is significant for understanding scorodite formation in As(V) solutions. It can provide schemes for controlling and modifying the conditions of arsenic-bearing waste immobilization in the laboratories and industries.


Assuntos
Arsênio , Precipitação Química , Oxirredução , Termodinâmica , Arsênio/química , Arsênio/análise , Poluentes Químicos da Água/química , Poluentes Químicos da Água/análise , Concentração de Íons de Hidrogênio
19.
Environ Res ; 259: 119534, 2024 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-38960361

RESUMO

This study presents a novel blend of synthesis techniques for shape-controlled ZnS nanoparticles. Zinc sulfide (ZnS) nanoparticles with distinct morphologies cauliflower-like microstructures (∼4.5 µm) and uniform nanospheres (200-700 nm) were synthesized through an innovative blend of precipitation and hydrothermal techniques. Capping with polyvinylpyrrolidone (PVP) significantly decreased crystallite size (3.93 nm-2.36 nm), modulated the band gap (3.57 eV-3.71 eV), and dramatically influenced morphology, highlighting the novelty of shape-controlled synthesis and its impact on optoelectronic and functional properties. X-ray diffraction confirmed crystallinity and revealed the size-controlling influence of PVP. UV-vis spectroscopy suggested potential tuning of optical properties due to band gap widening upon PVP capping. Field-emission scanning electron microscopy (FESEM) unveiled distinct morphologies: cauliflower-like microstructures for ZnS and uniform nanospheres (200-700 nm) for PVP-ZnS. Both structures were composed of smaller spherical nanoparticles, demonstrating the role of PVP in promoting controlled growth and preventing agglomeration. High-resolution transmission electron microscope (HRTEM) images depicted that the majority of nanoparticles maintain a spherical shape, though slight deviations from perfect sphericity can be discerned. Fourier-transform infrared (FTIR) spectroscopy confirmed that successful PVP encapsulation is crucial for shaping nanospheres and minimizing aggregation through steric hindrance. Photocatalytic activity evaluation using methylene blue (MB) dye degradation revealed significantly faster degradation by PVP-ZnS under ultraviolet (UV) irradiation (within 60 min as compared to 120 min for ZnS), showcasing its superior performance. This improvement can be attributed to the smaller size, higher surface area, and potentially optimized band gap of PVP-ZnS. Additionally, PVP-ZnS exhibited promising antibacterial activity against S. aureus and P. aeruginosa, with increased activity at higher nanoparticle concentrations.


Assuntos
Antibacterianos , Sulfetos , Compostos de Zinco , Compostos de Zinco/química , Sulfetos/química , Antibacterianos/química , Antibacterianos/farmacologia , Águas Residuárias/química , Precipitação Química , Povidona/química , Purificação da Água/métodos , Nanoestruturas/química
20.
Curr Microbiol ; 81(11): 387, 2024 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-39367076

RESUMO

Microbially induced calcium carbonate precipitation (MICP) is a soil remediation method that has emerged as a viable and long-term solution for enhancing soil mechanical qualities. The technique of MICP that has been extensively researched is urea hydrolysis, which occurs naturally in the environment by urease-producing bacteria as part of their fundamental metabolic processes. The objectives of the current study include screening and identifying native ureolytic bacteria from soil in Uttarakhand, optimizing growth factors for increased urease activity, and calcite precipitation by the bacteria using response surface methodology. Additionally, it was assessed how well the isolated bacteria in the medium biomineralized when using synthetic media and cheaper alternatives such as cow urine and eggshell as sources of urea and Ca2+, respectively. The isolated strain identified as Lysinibacillus sp. was found to be the very active strain after soil samples were screened for ureolytic bacteria. It was discovered that optimization studies with values of pH 8, urea concentration (0.8 M), inoculum concentration (3%), and incubation time (48 h) yielded a higher activity of 33.7 U/mL (threefold increase), and a higher calcium carbonate precipitation (enzyme activity: 10.96 U/mL, pH: 8.92, soluble Ca2⁺: 25.53 mM and insoluble Ca2⁺: 0.856 g). The calcite precipitation in broth media supplemented with ready-made substrates and alternative sources demonstrated a similar result of increased pH and ammonia release. Thus, the current study successfully paves the way for several possibilities to stabilize the slopy soils prone to landslides and erosion in Uttarakhand and pinpoint an economic approach through biomineralization.


Assuntos
Bacillaceae , Carbonato de Cálcio , Precipitação Química , Microbiologia do Solo , Solo , Ureia , Urease , Carbonato de Cálcio/metabolismo , Carbonato de Cálcio/química , Ureia/metabolismo , Urease/metabolismo , Bacillaceae/metabolismo , Solo/química , Concentração de Íons de Hidrogênio
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