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1.
Sci Total Environ ; 931: 172898, 2024 Jun 25.
Article in English | MEDLINE | ID: mdl-38697543

ABSTRACT

The production of short-chain fatty acids (SCFAs) is constrained by substrate availability and the increased fractional pressure of H2 emitted by acidogenic/fermentative bacteria during anaerobic fermentation of waste activated sludge (WAS). This study introduced a novel approach employing zero-valent iron (ZVI)-activated sulfite pretreatment combined with H2-consuming sulfate-reducing bacteria (SRB) mediation to improve SCFAs, especially acetate production from WAS fermentation. Experimental results showed that the combined ZVI-activated sulfite and incomplete-oxidative SRB (io-SRB) process achieved a peak SCFAs production of 868.11 mg COD/L, with acetate accounting for 80.55 %, which was 7.90- and 2.18-fold higher than that obtained from raw WAS fermentation, respectively. This could be firstly attributed to the SO4- and OH generated by ZVI-activated sulfite, which significantly promoted WAS decomposition, e.g., soluble proteins and carbohydrates increased 14.3- and 10.8-fold, respectively, over those in raw WAS. The biodegradation of dissolved organic matter was subsequently enhanced by the synergistic interaction and H2 transfer between anaerobic fermentation bacteria (AFB) and io-SRB. The positive and negative correlations among AFB, nitrate-reducing bacteria (NRB) and the io-SRB consortia were revealed by molecular ecological network (MEN) and Mantel test. Moreover, the expression of functional genes was also improved, for instance, in relation to acetate formation, the relative abundances of phosphate acetyltransferase and acetate kinase was 0.002 % and 0.005 % higher than that in the control test, respectively. These findings emphasized the importance of sulfate radicals-based oxidation pretreatment and the collaborative relationships of multifunctional microbes on the value-added chemicals and energy recovery from sludge fermentation.


Subject(s)
Fatty Acids, Volatile , Fermentation , Sewage , Sulfites , Waste Disposal, Fluid , Sewage/microbiology , Sulfites/metabolism , Fatty Acids, Volatile/metabolism , Waste Disposal, Fluid/methods , Sulfates/metabolism , Hydrogen/metabolism , Bacteria/metabolism , Iron/metabolism
2.
Eur J Med Res ; 29(1): 285, 2024 May 14.
Article in English | MEDLINE | ID: mdl-38745325

ABSTRACT

INTRODUCTION: Hydrogen (H2) is regarded as a novel therapeutic agent against several diseases owing to its inherent biosafety. Bronchopulmonary dysplasia (BPD) has been widely considered among adverse pregnancy outcomes, without effective treatment. Placenta plays a role in defense, synthesis, and immunity, which provides a new perspective for the treatment of BPD. This study aimed to investigate if H2 reduced the placental inflammation to protect the neonatal rat against BPD damage and potential mechanisms. METHODS: We induced neonatal BPD model by injecting lipopolysaccharide (LPS, 1 µg) into the amniotic fluid at embryonic day 16.5 as LPS group. LPS + H2 group inhaled 42% H2 gas (4 h/day) until the samples were collected. We primarily analyzed the neonatal outcomes and then compared inflammatory levels from the control group (CON), LPS group and LPS + H2 group. HE staining was performed to evaluate inflammatory levels. RNA sequencing revealed dominant differentially expressed genes. Bioinformatics analysis (GO and KEGG) of RNA-seq was applied to mine the signaling pathways involved in protective effect of H2 on the development of LPS-induced BPD. We further used qRT-PCR, Western blot and ELISA methods to verify differential expression of mRNA and proteins. Moreover, we verified the correlation between the upstream signaling pathways and the downstream targets in LPS-induced BPD model. RESULTS: Upon administration of H2, the inflammatory infiltration degree of the LPS-induced placenta was reduced, and infiltration significantly narrowed. Hydrogen normalized LPS-induced perturbed lung development and reduced the death ratio of the fetus and neonate. RNA-seq results revealed the importance of inflammatory response biological processes and Toll-like receptor signaling pathway in protective effect of hydrogen on BPD. The over-activated upstream signals [Toll-like receptor 4 (TLR4), nuclear factor kappa-B p65 (NF-κB p65), Caspase1 (Casp1) and NLR family pyrin domain containing 3 (NLRP3) inflammasome] in LPS placenta were attenuated by H2 inhalation. The downstream targets, inflammatory cytokines/chemokines [interleukin (IL)-6, IL-18, IL-1ß, C-C motif chemokine ligand 2 (CCL2) and C-X-C motif chemokine ligand 1 (CXCL1)], were decreased both in mRNA and protein levels by H2 inhalation in LPS-induced placentas to rescue them from BPD. Correlation analysis displayed a positive association of TLR4-mediated signaling pathway both proinflammatory cytokines and chemokines in placenta. CONCLUSION: H2 inhalation ameliorates LPS-induced BPD by inhibiting excessive inflammatory cytokines and chemokines via the TLR4-NFκB-IL6/NLRP3 signaling pathway in placenta and may be a potential therapeutic strategy for BPD.


Subject(s)
Bronchopulmonary Dysplasia , Hydrogen , Inflammation , Lipopolysaccharides , NF-kappa B , NLR Family, Pyrin Domain-Containing 3 Protein , Placenta , Signal Transduction , Toll-Like Receptor 4 , Female , Pregnancy , Lipopolysaccharides/toxicity , Hydrogen/pharmacology , Hydrogen/therapeutic use , Animals , Placenta/metabolism , Placenta/drug effects , Toll-Like Receptor 4/metabolism , Toll-Like Receptor 4/genetics , Signal Transduction/drug effects , Rats , NLR Family, Pyrin Domain-Containing 3 Protein/metabolism , NLR Family, Pyrin Domain-Containing 3 Protein/genetics , NF-kappa B/metabolism , Inflammation/metabolism , Inflammation/drug therapy , Administration, Inhalation , Bronchopulmonary Dysplasia/metabolism , Bronchopulmonary Dysplasia/chemically induced , Bronchopulmonary Dysplasia/drug therapy , Bronchopulmonary Dysplasia/prevention & control , Interleukin-6/metabolism , Interleukin-6/genetics , Rats, Sprague-Dawley , Disease Models, Animal
3.
Nature ; 629(8011): 295-306, 2024 May.
Article in English | MEDLINE | ID: mdl-38720037

ABSTRACT

Fossil fuels-coal, oil and gas-supply most of the world's energy and also form the basis of many products essential for everyday life. Their use is the largest contributor to the carbon dioxide emissions that drive global climate change, prompting joint efforts to find renewable alternatives that might enable a carbon-neutral society by as early as 2050. There are clear paths for renewable electricity to replace fossil-fuel-based energy, but the transport fuels and chemicals produced in oil refineries will still be needed. We can attempt to close the carbon cycle associated with their use by electrifying refinery processes and by changing the raw materials that go into a refinery from fossils fuels to carbon dioxide for making hydrocarbon fuels and to agricultural and municipal waste for making chemicals and polymers. We argue that, with sufficient long-term commitment and support, the science and technology for such a completely fossil-free refinery, delivering the products required after 2050 (less fuels, more chemicals), could be developed. This future refinery will require substantially larger areas and greater mineral resources than is the case at present and critically depends on the capacity to generate large amounts of renewable energy for hydrogen production and carbon dioxide capture.


Subject(s)
Carbon Dioxide , Fossil Fuels , Oil and Gas Industry , Renewable Energy , Carbon Cycle , Carbon Dioxide/adverse effects , Carbon Dioxide/isolation & purification , Coal/adverse effects , Coal/supply & distribution , Fossil Fuels/adverse effects , Fossil Fuels/supply & distribution , Hydrogen/chemistry , Natural Gas/adverse effects , Natural Gas/supply & distribution , Petroleum/adverse effects , Petroleum/supply & distribution , Renewable Energy/statistics & numerical data , Oil and Gas Industry/methods , Oil and Gas Industry/trends
4.
J Mol Graph Model ; 130: 108790, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38749235

ABSTRACT

At present, the hydrogen evolution reaction (HER) of Ni-based electrode has an important influence on water electrolysis hydrogen production technology, involving complex electrochemical process of electrode. In this project, Materials Studio (MS) software was used to design and construct Ni-based electrode surface (NES) models with monatomic Mo, Co, Fe, Cr doping, and the NES models attached 1 H atom and 2H atoms were denoted as the NES-H models and NES-2H model, respectively. Then the first-principles calculation was carried out. The results showed that the doping of different atoms can effectively change the work function of the pure Ni. In the charge transfer process of the four NES-2H models, the distance between the two H atoms is most affected by Mo doping, and they leave the Ni electrode surface as a single H ion, respectively, while the effect on Co, Fe and Cr doping is relatively consistent, and they leave the Ni electrode surface with H2 molecules, respectively. The doping of four single atoms changes the distance of valence band (VB) top and conduction band (CB) bottom from Fermi level in NES, NES-H and NES-2H models, and affects the HER, in which Mo doping has the greatest effect. The TDOS of the above models is mainly derived from the PDOS of the d orbitals of the doped atoms and Ni atoms. The results will provide a theoretical basis for the research and development of Ni-based electrode materials in HER.


Subject(s)
Electrodes , Hydrogen , Nickel , Hydrogen/chemistry , Nickel/chemistry , Surface Properties , Electrons , Models, Molecular
5.
J Environ Manage ; 359: 120961, 2024 May.
Article in English | MEDLINE | ID: mdl-38696851

ABSTRACT

Plastic pollution poses a significant environmental threat, particularly to marine ecosystems, as conventional plastics persist without degradation, accumulating plastic waste in landfills and natural environments. A promising alternative to address this issue involves the use of hydrogen donor solvents in plastic liquefaction, offering a dual benefit of waste reduction and the generation of valuable liquid products with diverse industrial applications. This review delves into plastic recycling methods with a specific focus on liquefaction using hydrogen donating solvents as an innovative approach to waste management. Liquefaction, conducted at moderate to high temperatures (280-450 °C) and pressures (7-30 MPa), yields high oil conversion using various solvents. This study examined the performance of hydrogen-donating solvents, including water, alcohols, decalin, and cyclohexane, in enhancing the oil yield while minimising the oxygen content. Supercritical water, recognised for its effective plastic degradation and chemical production capabilities, and alcohols, with their alkylating and hydrogen-donating properties, have emerged as key solvents in plastic liquefaction. The use of hydrogen donor solvents stabilizes the free radicals, enhancing the conversion of plastic waste into valuable products. In addition, this review addresses the economic efficiency of the liquefaction process.


Subject(s)
Hydrogen , Plastics , Recycling , Solvents , Waste Management , Solvents/chemistry , Waste Management/methods , Plastics/chemistry , Hydrogen/chemistry
6.
Nutrients ; 16(10)2024 May 19.
Article in English | MEDLINE | ID: mdl-38794767

ABSTRACT

(1) Background: Hydrogen (H2) may be a potential therapeutic agent for managing Long COVID symptoms due to its antioxidant and anti-inflammatory properties. However, more scientific literature is needed to describe the effects of H2 administration on treating symptoms. A study aimed to investigate the impact of hydrogen-rich water (HRW) administration on the fatigue and dyspnea of Long-COVID patients for 14 consecutive days. (2) Methods: In this randomized, single-blind, placebo-controlled study, 55 participants were recruited, and 23 of them were excluded. A total of 32 eligible participants were randomized into a hydrogen-rich water (HRW) group (n = 16) and a placebo water (PW) group (n = 16) in which they were instructed to consume hydrogen-rich water or placebo water for 14 days, respectively. The participants completed the Fatigue Severity Scale (FSS), Six-Minute Walk Test (6MWT), 30 s Chair Stand Test (30s-CST), Modified Medical Research Council Dyspnea Rating Scale (mMRC), Pittsburgh Sleep Quality Index (PSQI), and depression anxiety stress scale (DASS-21) before and after the intervention. A linear mixed-effects model was used to analyze the effects of HRW. Cohen's d values were used to assess the effect size when significance was observed. The mean change with 95% confidence intervals (95% CI) was also reported. (3) Results: The effects of HRW on lowering FSS scores (p = 0.046, [95% CI = -20.607, -0.198, d = 0.696] and improving total distance in the 6WMT (p < 0.001, [95% CI = 41.972, 61.891], d = 1.010), total time for the 30s-CST (p = 0.002, [95% CI = 1.570, 6.314], d = 1.190), and PSQI scores (p = 0.012, [95% CI = -5.169, 0.742], d = 1.274) compared to PW were of a significantly moderate effect size, while there was no significant difference in mMRC score (p = 0.556) or DASS-21 score (p > 0.143). (4) Conclusions: This study demonstrates that HRW might be an effective strategy for alleviating fatigue and improving cardiorespiratory endurance, musculoskeletal function, and sleep quality. Still, it does not ameliorate dyspnea among Long-COVID patients.


Subject(s)
COVID-19 , Dyspnea , Fatigue , Hydrogen , Humans , Male , Female , Single-Blind Method , COVID-19/complications , Middle Aged , Pilot Projects , Water , SARS-CoV-2 , Adult , Post-Acute COVID-19 Syndrome , Aged
7.
Drug Des Devel Ther ; 18: 1399-1414, 2024.
Article in English | MEDLINE | ID: mdl-38707612

ABSTRACT

Hydrogen, which is a novel biomedical molecule, is currently the subject of extensive research involving animal experiments and in vitro cell experiments, and it is gradually being applied in clinical settings. Hydrogen has been proven to possess anti-inflammatory, selective antioxidant, and antiapoptotic effects, thus exhibiting considerable protective effects in various diseases. In recent years, several studies have provided preliminary evidence for the protective effects of hydrogen on spinal cord injury (SCI). This paper provides a comprehensive review of the potential molecular biology mechanisms of hydrogen therapy and its application in treating SCI, with an aim to better explore the medical value of hydrogen and provide new avenues for the adjuvant treatment of SCI.


Subject(s)
Hydrogen , Spinal Cord Injuries , Spinal Cord Injuries/drug therapy , Spinal Cord Injuries/metabolism , Hydrogen/pharmacology , Hydrogen/chemistry , Humans , Animals , Antioxidants/pharmacology , Antioxidants/chemistry , Neuroprotective Agents/pharmacology , Neuroprotective Agents/chemistry , Apoptosis/drug effects , Anti-Inflammatory Agents/pharmacology , Anti-Inflammatory Agents/chemistry
8.
Ter Arkh ; 96(3): 260-265, 2024 Apr 16.
Article in Russian | MEDLINE | ID: mdl-38713041

ABSTRACT

Рost-COVID-19 syndrome (PS) is one of the medical and social problem. According to WHO, 10-20% of COVID-19 patients suffer from PS. The use of medical gases - inhaled nitric oxide (iNO) and molecular hydrogen (iH2) - may influence on the mechanisms of development PC. AIM: To evaluate the safety and efficacy of the combined inhalation of NO and H2 (iNO/iH2) in patients with respiratory manifestations of PS. MATERIALS AND METHODS: 34 patients with PS (11 men/23 women, 60.0±11.7 years) were included in the prospective open-label controlled study in parallel groups: the main group (n=17) received iNO/iH2 for 90 minutes once a day for 10 days (concentration of NO 60 ppm, H2<4% in the gas mixture), the control group (n=17) didn't receive inhalations. The period from the confirmation of COVID-19 to the start of the study was 641.8±230.5 days. The groups did not differ in the baseline parameters. The clinical symptoms (from the self-observation diary and mMRC questionnaires, "dyspnea language"), FAS, HADS, SF-36 scores, 6-minute walk test, the blood serum parameters of oxidative stress, the dynamics of the microcirculation in the eye bulbar conjunctiva were evaluated. The individual dose of iNO has chosen during a 15-minute test (the positive dynamics of the microcirculation have indicated that the dose was selected correctly). RESULTS: The decrease the symptoms severity, such as dyspnea, cough, fatigue and palpitations (p<0.005), the increase in SF-36 questionnaire scores (p=0.006) and a reducing of FAS score (p=0.001), as well as the anxiety component of HADS (p=0.02) were revealed at the end of treatment in the main group compared to the control group. We observed an improvement in distance walked (p=0.01) and the values SpO2 (p=0.04) in 6-minute walk test, the increase in the volumetric blood flow velocity in venules (p<0.001), and the date in oxidative damage (p<0.001) and antioxidant activity (p=0.03) parameters in the blood serum. CONCLUSION: The results of the study demonstrate clinical efficacy iNO/iH2 on clinical indicators, parameters of oxidative stress and microcirculation in patients with PS.


Subject(s)
COVID-19 , Hydrogen , Nitric Oxide , Humans , Female , Male , Nitric Oxide/administration & dosage , COVID-19/complications , Hydrogen/administration & dosage , Middle Aged , Administration, Inhalation , Prospective Studies , SARS-CoV-2 , Post-Acute COVID-19 Syndrome , Treatment Outcome , Aged
9.
Nat Commun ; 15(1): 4151, 2024 May 16.
Article in English | MEDLINE | ID: mdl-38755154

ABSTRACT

Atmospheric methane oxidizing bacteria (atmMOB) constitute the sole biological sink for atmospheric methane. Still, the physiological basis allowing atmMOB to grow on air is not well understood. Here we assess the ability and strategies of seven methanotrophic species to grow with air as sole energy, carbon, and nitrogen source. Four species, including three outside the canonical atmMOB group USCα, enduringly oxidized atmospheric methane, carbon monoxide, and hydrogen during 12 months of growth on air. These four species exhibited distinct substrate preferences implying the existence of multiple metabolic strategies to grow on air. The estimated energy yields of the atmMOB were substantially lower than previously assumed necessary for cellular maintenance in atmMOB and other aerobic microorganisms. Moreover, the atmMOB also covered their nitrogen requirements from air. During growth on air, the atmMOB decreased investments in biosynthesis while increasing investments in trace gas oxidation. Furthermore, we confirm that a high apparent specific affinity for methane is a key characteristic of atmMOB. Our work shows that atmMOB grow on the trace concentrations of methane, carbon monoxide, and hydrogen present in air and outlines the metabolic strategies that enable atmMOB to mitigate greenhouse gases.


Subject(s)
Carbon Monoxide , Hydrogen , Methane , Oxidation-Reduction , Methane/metabolism , Carbon Monoxide/metabolism , Hydrogen/metabolism , Atmosphere/chemistry , Air , Nitrogen/metabolism , Greenhouse Gases/metabolism
10.
Sci Rep ; 14(1): 10959, 2024 05 14.
Article in English | MEDLINE | ID: mdl-38745034

ABSTRACT

Molecular hydrogen is an emerging broad-spectrum antioxidant molecule that can be used to treat myocardial infarction (MI). However, with hydrogen inhalation, the concentration that can be reached within target organs is low and the duration of action is short, which makes it difficult to achieve high dose targeted delivery of hydrogen to the heart, seriously limiting the therapeutic potential of hydrogen for MI. As a result of reactions with the internal environment of the body, subcutaneous implantation of magnesium slices leads to continuous endogenous hydrogen production, leading to a higher hydrogen concentration and a longer duration of action in target organs. In this study, we propose magnesium implant-based hydrogen therapy for MI. After subcutaneous implantation of magnesium slices in the dorsum of rats, we measured hydrogen production and efficiency, and evaluated the safety of this approach. Compared with hydrogen inhalation, it significantly improved cardiac function in rats with MI. Magnesium implantation also cleared free radicals that were released as a result of mitochondrial dysfunction, as well as suppressing cardiomyocyte apoptosis.


Subject(s)
Hydrogen , Magnesium , Myocardial Infarction , Animals , Myocardial Infarction/drug therapy , Myocardial Infarction/metabolism , Magnesium/metabolism , Rats , Male , Rats, Sprague-Dawley , Apoptosis/drug effects , Myocytes, Cardiac/metabolism , Myocytes, Cardiac/drug effects , Disease Models, Animal
11.
Molecules ; 29(10)2024 May 16.
Article in English | MEDLINE | ID: mdl-38792198

ABSTRACT

Supercritical water gasification (SCWG) of lignocellulosic biomass is a promising pathway for the production of hydrogen. However, SCWG is a complex thermochemical process, the modeling of which is challenging via conventional methodologies. Therefore, eight machine learning models (linear regression (LR), Gaussian process regression (GPR), artificial neural network (ANN), support vector machine (SVM), decision tree (DT), random forest (RF), extreme gradient boosting (XGB), and categorical boosting regressor (CatBoost)) with particle swarm optimization (PSO) and a genetic algorithm (GA) optimizer were developed and evaluated for prediction of H2, CO, CO2, and CH4 gas yields from SCWG of lignocellulosic biomass. A total of 12 input features of SCWG process conditions (temperature, time, concentration, pressure) and biomass properties (C, H, N, S, VM, moisture, ash, real feed) were utilized for the prediction of gas yields using 166 data points. Among machine learning models, boosting ensemble tree models such as XGB and CatBoost demonstrated the highest power for the prediction of gas yields. PSO-optimized XGB was the best performing model for H2 yield with a test R2 of 0.84 and PSO-optimized CatBoost was best for prediction of yields of CH4, CO, and CO2, with test R2 values of 0.83, 0.94, and 0.92, respectively. The effectiveness of the PSO optimizer in improving the prediction ability of the unoptimized machine learning model was higher compared to the GA optimizer for all gas yields. Feature analysis using Shapley additive explanation (SHAP) based on best performing models showed that (21.93%) temperature, (24.85%) C, (16.93%) ash, and (29.73%) C were the most dominant features for the prediction of H2, CH4, CO, and CO2 gas yields, respectively. Even though temperature was the most dominant feature, the cumulative feature importance of biomass characteristics variables (C, H, N, S, VM, moisture, ash, real feed) as a group was higher than that of the SCWG process condition variables (temperature, time, concentration, pressure) for the prediction of all gas yields. SHAP two-way analysis confirmed the strong interactive behavior of input features on the prediction of gas yields.


Subject(s)
Biomass , Hydrogen , Lignin , Machine Learning , Water , Lignin/chemistry , Water/chemistry , Hydrogen/chemistry , Hydrogen/analysis , Gases/chemistry , Gases/analysis , Algorithms , Neural Networks, Computer , Carbon Dioxide/chemistry , Carbon Dioxide/analysis , Support Vector Machine , Methane/chemistry , Methane/analysis
12.
J Nanobiotechnology ; 22(1): 277, 2024 May 23.
Article in English | MEDLINE | ID: mdl-38783332

ABSTRACT

Spinal Cord Injury (SCI) is a condition characterized by complete or incomplete motor and sensory impairment, as well as dysfunction of the autonomic nervous system, caused by factors such as trauma, tumors, or inflammation. Current treatment methods primarily include traditional approaches like spinal canal decompression and internal fixation surgery, steroid pulse therapy, as well as newer techniques such as stem cell transplantation and brain-spinal cord interfaces. However, the above methods have limited efficacy in promoting axonal and neuronal regeneration. The challenge in medical research today lies in promoting spinal cord neuron regeneration and regulating the disrupted microenvironment of the spinal cord. Studies have shown that gas molecular therapy is increasingly used in medical research, with gasotransmitters such as hydrogen sulfide, nitric oxide, carbon monoxide, oxygen, and hydrogen exhibiting neuroprotective effects in central nervous system diseases. The gas molecular protect against neuronal death and reshape the microenvironment of spinal cord injuries by regulating oxidative, inflammatory and apoptotic processes. At present, gas therapy mainly relies on inhalation for systemic administration, which cannot effectively enrich and release gas in the spinal cord injury area, making it difficult to achieve the expected effects. With the rapid development of nanotechnology, the use of nanocarriers to achieve targeted enrichment and precise control release of gas at Sites of injury has become one of the emerging research directions in SCI. It has shown promising therapeutic effects in preclinical studies and is expected to bring new hope and opportunities for the treatment of SCI. In this review, we will briefly outline the therapeutic effects and research progress of gasotransmitters and nanogas in the treatment of SCI.


Subject(s)
Gasotransmitters , Spinal Cord Injuries , Spinal Cord Injuries/therapy , Humans , Animals , Gasotransmitters/therapeutic use , Gasotransmitters/metabolism , Nitric Oxide/metabolism , Neuroprotective Agents/therapeutic use , Neuroprotective Agents/pharmacology , Hydrogen Sulfide/therapeutic use , Hydrogen Sulfide/metabolism , Hydrogen Sulfide/pharmacology , Carbon Monoxide/metabolism , Carbon Monoxide/therapeutic use , Oxygen/metabolism , Spinal Cord , Hydrogen/therapeutic use , Hydrogen/pharmacology
13.
Anal Chem ; 96(21): 8552-8559, 2024 May 28.
Article in English | MEDLINE | ID: mdl-38741470

ABSTRACT

Long-lived proteins undergo chemical modifications that can cause age-related diseases. Among these chemical modifications, isomerization is the most difficult to identify. Isomerization often occurs at the aspartic acid (Asp) residues. In this study, we used tandem mass spectrometry equipped with a newly developed ion activation method, hydrogen attachment dissociation (HAD), to analyze peptides containing Asp isomers. Although HAD preferentially produces [cn + 2H]+ and [zm + 2H]+ via N-Cα bond cleavage, [cn + 58 + 2H]+ and [zm - 58 + 2H]+ originate from the fragmentation of the isoAsp residue. Notably, [cn + 58 + 2H]+ and [zm - 58 + 2H]+ could be used as diagnostic fragment ions for the isoAsp residue because these fragment ions did not originate from the Asp residue. The detailed fragmentation mechanism was investigated by computational analysis using density functional theory. According to the results, hydrogen attachment to the carbonyl oxygen in the isoAsp residue results in the Cα-Cß bond cleavage. The experimental and theoretical joint study indicates that the present method allows us to discriminate Asp and isoAsp residues, including site identification of the isoAsp residue. Moreover, we demonstrated that the molar ratio of peptide isomers in the mixture could be estimated from their fragment ion abundance. Therefore, tandem mass spectrometry with HAD is a useful method for the rapid discrimination and semiquantitative analysis of peptides containing isoAsp residues.


Subject(s)
Aspartic Acid , Hydrogen , Isoaspartic Acid , Peptides , Tandem Mass Spectrometry , Tandem Mass Spectrometry/methods , Aspartic Acid/chemistry , Aspartic Acid/analysis , Isoaspartic Acid/chemistry , Isoaspartic Acid/analysis , Peptides/chemistry , Peptides/analysis , Hydrogen/chemistry , Isomerism
14.
Bioresour Technol ; 402: 130805, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38718905

ABSTRACT

Catalytic transfer hydrogenation (CTH), that employs protic solvents as hydrogen sources to alleviate the use of molecular hydrogen H2, has gained great attention. This work, reports multifunctional, metallic Cu nanoparticles supported ZIF-8 material for CTH of furfural to a highly valued fuel additive, 2-methylfuran (2-MF) using 2-propanol. Of all as-synthesized xCu(yM)/ZIF-8 catalysts with varied NaBH4 concentration (yM) and Cu loading (x), 11Cu(1.5 M)/ZIF-8 exhibited higher catalytic activity with > 99 % FAL conversion and 93.9 % 2-MF selectivity. This is ascribed to its high specific surface area, and existence of optimum amount of Lewis acid-base sites along with Cu0 species, which are responsible for hydrogenation of furfural to furfuryl alcohol and subsequent hydrogenolysis to produce 2-MF. The present work reports a highly efficient and stable, metal-MOF hybrid material for CTH of FAL to 2-MF, which is one among the best reports available in literature, therewith suggests a promising approach for bio-oil upgradation.


Subject(s)
Copper , Furaldehyde , Furans , Metal Nanoparticles , Zeolites , Furans/chemistry , Catalysis , Hydrogenation , Copper/chemistry , Furaldehyde/chemistry , Furaldehyde/analogs & derivatives , Zeolites/chemistry , Metal Nanoparticles/chemistry , Hydrogen/chemistry
15.
Bioresour Technol ; 402: 130842, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38750828

ABSTRACT

Hydrophilic porous membranes, exemplified by polyvinylidene fluoride (PVDF) membranes, have demonstrated significant potential for replacing ion exchange membranes in microbial electrolysis cells (MECs). Membrane fouling remains a major challenge in MECs, impeding proton transport and consequently limiting hydrogen production. This study aims to investigate a synergistic antifouling strategy for PVDF membrane through the incorporation of a coating composed of polydopamine (PDA), polyethyleneimine (PEI), and silver nanoparticles (AgNPs). The PDA-PEI-Ag@PVDF membrane not only effectively mitigates fouling through steric and electrostatic repulsion forces, but also amplifies ion transport by facilitating water diffusion and electromigration. The PDA-PEI-Ag@PVDF membrane exhibited a reduced membrane resistance of 1.01 mΩ m2 and PDA-PEI-Ag modifying PVDF membrane was found to be effective in enhancing the proton transportation of PVDF membrane. Therefore, the enhanced hydrogen production rate of 2.65 ± 0.02 m3/m3/d was achieved in PDA-PEI-Ag@PVDF-MECs.


Subject(s)
Bioelectric Energy Sources , Biofouling , Electrolysis , Hydrogen , Indoles , Membranes, Artificial , Polyvinyls , Protons , Silver , Polyvinyls/chemistry , Hydrogen/metabolism , Biofouling/prevention & control , Silver/chemistry , Silver/pharmacology , Indoles/metabolism , Indoles/chemistry , Polymers/chemistry , Metal Nanoparticles/chemistry , Polyethyleneimine/chemistry , Fluorocarbon Polymers
16.
Bioresour Technol ; 402: 130844, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38754560

ABSTRACT

In this study, a novel magnetic Ni-Fe2O3-C catalyst combined with electromagnetic induction heating in biomass steam gasification was proposed to enhance H2 production. Better catalytic performance for H2 production was observed with the Ni-Fe2O3-C catalyst under induction heating, resulting in an increase in H2 yield from 735.1 to 2271.2 mL/g-biomass (a 209.1 % enhancement). SEM, TGA and XRD analysis demonstrated a significant decrease in coking deposition, caking, and particle agglomeration of the Ni-Fe2O3-C catalyst under induction heating, while maintaining more active sites. Importantly, the benefits of induction heating were also applicable to different magnetic catalysts like Ni-Al2O3-C, Ni-ZrO2-C, and Ni-MgO-C. Experimental results revealed a logarithmic correlation between the increase in H2 yields due to induction heating and the magnetic saturation (Ms) of the catalysts. The Ni-Fe2O3-C catalyst, with a high Ms of 50.9 emu/g, showed the highest catalytic activity for H2 production under induction heating in this study.


Subject(s)
Biomass , Ferric Compounds , Hydrogen , Nickel , Steam , Catalysis , Hydrogen/chemistry , Nickel/chemistry , Ferric Compounds/chemistry , Hot Temperature , Heating , X-Ray Diffraction , Electromagnetic Phenomena
17.
Adv Microb Physiol ; 84: 51-82, 2024.
Article in English | MEDLINE | ID: mdl-38821634

ABSTRACT

Formic acid (HCOOH) and dihydrogen (H2) are characteristic products of enterobacterial mixed-acid fermentation, with H2 generation increasing in conjunction with a decrease in extracellular pH. Formate and acetyl-CoA are generated by radical-based and coenzyme A-dependent cleavage of pyruvate catalysed by pyruvate formate-lyase (PflB). Formate is also the source of H2, which is generated along with carbon dioxide through the action of the membrane-associated, cytoplasmically-oriented formate hydrogenlyase (FHL-1) complex. Synthesis of the FHL-1 complex is completely dependent on the cytoplasmic accumulation of formate. Consequently, formate determines its own disproportionation into H2 and CO2 by the FHL-1 complex. Cytoplasmic formate levels are controlled by FocA, a pentameric channel that translocates formic acid/formate bidirectionally between the cytoplasm and periplasm. Each protomer of FocA has a narrow hydrophobic pore through which neutral formic acid can pass. Two conserved amino acid residues, a histidine and a threonine, at the center of the pore control directionality of translocation. The histidine residue is essential for pH-dependent influx of formic acid. Studies with the formate analogue hypophosphite and amino acid variants of FocA suggest that the mechanisms of formic acid efflux and influx differ. Indeed, current data suggest, depending on extracellular formate levels, two separate uptake mechanisms exist, both likely contributing to maintain pH homeostasis. Bidirectional formate/formic acid translocation is dependent on PflB and influx requires an active FHL-1 complex. This review describes the coupling of formate and H2 production in enterobacteria.


Subject(s)
Enterobacteriaceae , Fermentation , Formates , Hydrogen , Formates/metabolism , Hydrogen/metabolism , Enterobacteriaceae/metabolism , Enterobacteriaceae/genetics , Enterobacteriaceae/enzymology , Bacterial Proteins/metabolism , Bacterial Proteins/genetics , Formate Dehydrogenases , Hydrogenase , Multienzyme Complexes
18.
Biotechnol Adv ; 73: 108379, 2024.
Article in English | MEDLINE | ID: mdl-38754796

ABSTRACT

Biological production of hydrogen has a tremendous potential as an environmentally sustainable technology to generate a clean fuel. Among the different available methods to produce biohydrogen, dark fermentation features the highest productivity and can be used as a means to dispose of organic waste biomass. Within this approach, Clostridia have the highest theoretical H2 production yield. Nonetheless, most strains show actual yields far lower than the theoretical maximum: improving their efficiency becomes necessary for achieving cost-effective fermentation processes. This review aims at providing a survey of the metabolic network involved in H2 generation in Clostridia and strategies used to improve it through metabolic engineering. Together with current achievements, a number of future perspectives to implement these results will be illustrated.


Subject(s)
Clostridium , Fermentation , Hydrogen , Metabolic Engineering , Hydrogen/metabolism , Metabolic Engineering/methods , Clostridium/metabolism , Clostridium/genetics , Metabolic Networks and Pathways , Biofuels
19.
Food Chem ; 453: 139563, 2024 Sep 30.
Article in English | MEDLINE | ID: mdl-38776791

ABSTRACT

Molecular hydrogen is beneficial for fruits quality improvement. However, the mechanism involved, especially cellular metabolic responses, has not been well established. Here, the integrated widely targeted metabolomics analysis (UPLC-MS/MS) and biochemical evidence revealed that hydrogen-based irrigation could orchestrate, either directly or indirectly, an array of physiological responses in blueberry (Vaccinium spp.) during harvesting stage, especially for the delayed senescence in harvested stage (4 °C for 12 d). The hubs to these changes are wide-ranging metabolic reprogramming and antioxidant machinery. A total of 1208 distinct annotated metabolites were identified, and the characterization of differential accumulated metabolites (DAMs) revealed that the reprogramming, particularly, involves phenolic acids and flavonoids accumulation. These changes were positively matched with the transcriptional profiles of representative genes for their synthesis during the growth stage. Together, our findings open a new window for development of hydrogen-based agriculture that increases the shelf-life of fruits in a smart and sustainable manner.


Subject(s)
Antioxidants , Blueberry Plants , Fruit , Hydrogen , Blueberry Plants/metabolism , Blueberry Plants/chemistry , Blueberry Plants/growth & development , Blueberry Plants/genetics , Hydrogen/metabolism , Hydrogen/analysis , Fruit/metabolism , Fruit/chemistry , Fruit/growth & development , Fruit/genetics , Antioxidants/metabolism , Agricultural Irrigation , Tandem Mass Spectrometry , Metabolomics , Flavonoids/metabolism , Metabolic Reprogramming
20.
Food Chem ; 453: 139694, 2024 Sep 30.
Article in English | MEDLINE | ID: mdl-38776793

ABSTRACT

Previous studies have indicated that hydrogen-rich water (HW) treatment can delay fruit ripening and senescence. However, little is known about the HW-delaying pulp breakdown. In this study, eight physiological characteristics revealed that HW treatment delayed both pericarp browning and pulp breakdown of litchi fruit. To gain a comprehensive understanding of the changes in litchi pulp, a combination of multiple metabolomics and gene expression analyses was conducted, assessing 67 primary metabolites, 103 volatiles, 31 amino acids, and 13 crucial metabolite-related genes. Results showed that HW treatment promoted starch degradation, decelerated cell wall degradation and glycolysis, and maintained the flavor and quality of litchi fruit. Furthermore, HW treatment stimulated the production of volatile alcohols, aldehydes, ketones, olefins, and amino acids, which might play a vital role in HW-delaying pulp breakdown. This study sheds light on the mechanism by which HW delayed pulp breakdown by investigating small molecule metabolites and metabolic pathways.


Subject(s)
Food Storage , Fruit , Hydrogen , Litchi , Water , Fruit/chemistry , Fruit/metabolism , Fruit/growth & development , Litchi/chemistry , Litchi/metabolism , Litchi/growth & development , Hydrogen/metabolism , Hydrogen/analysis , Water/metabolism , Water/analysis , Volatile Organic Compounds/metabolism , Volatile Organic Compounds/chemistry
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