ABSTRACT
Microbial reduction of perchlorate (ClO4-) is emerging as a cost-effective strategy for groundwater remediation. However, the effectiveness of perchlorate reduction can be suppressed by the common co-contamination of nitrate (NO3-). We propose a means to overcome the limitation of ClO4- reduction: depositing palladium nanoparticles (Pd0NPs) within the matrix of a hydrogenotrophic biofilm. Two H2-based membrane biofilm reactors (MBfRs) were operated in parallel in long-term continuous and batch modes: one system had only a biofilm (bio-MBfR), while the other incorporated biogenic Pd0NPs in the biofilm matrix (bioPd-MBfR). For long-term co-reduction, bioPd-MBfR had a distinct advantage of oxyanion reduction fluxes, and it particularly alleviated the competitive advantage of NO3- reduction over ClO4- reduction. Batch tests also demonstrated that bioPd-MBfR gave more rapid reduction rates for ClO4- and ClO3- compared to those of bio-MBfR. Both biofilm communities were dominated by bacteria known to be perchlorate and nitrate reducers. Functional-gene abundances reflecting the intracellular electron flow from H2 to NADH to the reductases were supplanted by extracellular electron flow with the addition of Pd0NPs.
Subject(s)
Biofilms , Nitrates , Palladium , Perchlorates , Palladium/chemistry , Nitrates/metabolism , Perchlorates/metabolism , Oxidation-Reduction , Electrons , Groundwater/chemistryABSTRACT
Biochar-assisted anaerobic digestion (AD) remains constrained due to the inefficient decomposition of complex organics, even with the direct interspecies electron transfer (DIET) pathway. The coupling of electrochemistry with the anaerobic biological treatment could shorten lengthy retention time in co-digestion by improving electron transfer rates and inducing functional microbial acclimation. Thus, this work investigated the potential of improving the performance of AD by coupling low-magnitude electric fields with biochar derived from the anaerobically digested biogas residue. Different voltages (0.3, 0.6, and 0.9 V) were applied at various stages to assess the impact on biochar-assisted AD. The results indicate that an external voltage of 0.3 V, coupled with 5 g/L of biochar, elevates CH4 yield by 45.5% compared to biogas residue biochar alone, and the coupled approach increased biogas production by up to 143% within 10 days. This finding may be partly explained by the enhanced utilization of substrates and the increased amounts of specific methanogens such as Methanobacterium and Methanosarcina. The abundance of the former increased from 4.0 to 11.3%, which enhances the DIET between microorganisms. Furthermore, the coupling method shows better potential for enhancing AD compared to preparing iron-based biochar, and these results present potential avenues for its broader applications.
Subject(s)
Biofuels , Charcoal , Sewage , Charcoal/chemistry , Anaerobiosis , Sewage/chemistry , Bioreactors , Electricity , Methane/metabolism , Food Loss and WasteABSTRACT
Ultracold atoms in optical lattices are a flexible and effective platform for quantum precision measurement, and the lifetime of high-band atoms is an essential parameter for the performance of quantum sensors. In this work, we investigate the relationship between the lattice depth and the lifetime of D-band atoms in a triangular optical lattice and show that there is an optimal lattice depth for the maximum lifetime. After loading the Bose-Einstein condensate into D band of optical lattice by shortcut method, we observe the atomic distribution in quasi-momentum space for the different evolution time, and measure the atomic lifetime at D band with different lattice depths. The lifetime is maximized at an optimal lattice depth, where the overlaps between the wave function of D band and other bands (mainly S band) are minimized. Additionally, we discuss the influence of atomic temperature on lifetime. These experimental results are in agreement with our numerical simulations. This work paves the way to improve coherence properties of optical lattices, and contributes to the implications for the development of quantum precision measurement, quantum communication, and quantum computing.
ABSTRACT
Ramsey interferometers have wide applications in science and engineering. Compared with the traditional interferometer based on internal states, the interferometer with external quantum states has advantages in some applications for quantum simulation and precision measurement. Here, we develop a Ramsey interferometry with Bloch states in S- and D-band of a triangular optical lattice for the first time. The key to realizing this interferometer in two-dimensionally coupled lattice is that we use the shortcut method to construct π/2 pulse. We observe clear Ramsey fringes and analyze the decoherence mechanism of fringes. Further, we design an echo π pulse between S- and D-band, which significantly improves the coherence time. This Ramsey interferometer in the dimensionally coupled lattice has potential applications in the quantum simulations of topological physics, frustrated effects, and motional qubits manipulation.
ABSTRACT
A hydrogen-based membrane biofilm reactor (H2-MBfR) was operated to investigate the bioreduction of antimonate [Sb(V)] in terms of Sb(V) removal, the fate of Sb, and the pathways of reduction metabolism. The MBfR achieved up to 80% Sb(V) removal and an Sb(V) removal flux of 0.55 g/m2·day. Sb(V) was reduced to Sb(III), which mainly formed Sb2O3 precipitates in the biofilm matrix, although some Sb(III) was retained intracellularly. High Sb(V) loading caused stress that deteriorated performance that was not recovered when the high Sb(V) loading was removed. The biofilm community consisted of DSbRB (dissimilatory Sb-reduction bacteria), SbRB (Sb-resistant bacteria), and DIRB (dissimilatory iron-reducing bacteria). Dissimilatory antimonate reduction, mediated by the respiratory arsenate reductase ArrAB, was the main reduction route, but respiratory reduction coexisted with cytoplasmic Sb(V)-reduction mediated by arsenate reductase ArsC. Increasing Sb(V) loading caused stress that led to increases in the expression of arsC gene and intracellular accumulation of Sb(III). By illuminating the roles of the dissimilatory and cytoplasmic Sb(V) reduction mechanism in the biofilms of the H2-MBfR, this study reveals that the Sb(V) loading should be controlled to avoid stress that deteriorates Sb(V) reduction.
Subject(s)
Arsenate Reductases , Hydrogen , Bacteria/genetics , Biofilms , Bioreactors/microbiology , IronABSTRACT
Ovarian teratomas are by far the most common ovarian germ cell tumor. Most teratomas are benign unless a somatic transformation occurs. The designation of teratoma refers to a neoplasm that differentiates toward somatic-type cell populations. Recent research shows a striking association between ovarian teratomas and anti-N-methyl-D-aspartate receptor (anti-NMDAR) encephalitis, a rare and understudied paraneoplastic neurological syndrome (PNS). Among teratomas, mature teratomas are thought to have a greater relevance with those neurological impairments. PNS is described as a neurologic deficit triggered by an underlying remote tumor, whereas anti-NMDAR encephalitis is characterized by a complex neuropsychiatric syndrome and the presence of autoantibodies in cerebral spinal fluid against the GluN1 subunit of the NMDAR. This review aims to summarize recent reports on the association between anti-NMDAR encephalitis and ovarian teratoma. In particular, the molecular pathway of pathogenesis and the updated mechanism and disease models would be discussed. We hope to provide an in-depth review of this issue and, therefore, to better understand its epidemiology, diagnostic approach, and treatment strategies.
Subject(s)
Anti-N-Methyl-D-Aspartate Receptor Encephalitis/metabolism , Ovarian Neoplasms/psychology , Signal Transduction , Teratoma/psychology , Animals , Anti-N-Methyl-D-Aspartate Receptor Encephalitis/etiology , Autoantibodies/metabolism , Disease Models, Animal , Female , Humans , Ovarian Neoplasms/metabolism , Teratoma/metabolismABSTRACT
Neuroendocrine prostate cancer (NEPC) is an aggressive and lethal variant of prostate cancer (PCa), and it remains a diagnostic challenge. Herein we report our findings of using synaptic vesicle glycoprotein 2 isoform A (SV2A) as a promising marker for positron emission tomography (PET) imaging of neuroendocrine differentiation (NED). The bioinformatic analyses revealed an amplified SV2A gene expression in clinical samples of NEPC versus castration-resistant PCa with adenocarcinoma characteristics (CRPC-Adeno). Importantly, significantly upregulated SV2A protein levels were found in both NEPC cell lines and tumor tissues. PET imaging studies were carried out in NEPC xenograft models with 18F-SynVesT-1. Although 18F-SynVesT-1 is not a cancer imaging agent, it showed a significant uptake level in the SV2A+ tumor (NCI-H660: 0.70 ± 0.14 %ID/g at 50-60 min p.i.). The SV2A blockade resulted in a significant reduction of tumor uptake (0.25 ± 0.03 %ID/g, p = 0.025), indicating the desired SV2A imaging specificity. Moreover, the comparative PET imaging study showed that the DU145 tumors could be clearly visualized by 18F-SynVesT-1 but not 68Ga-PSMA-11 nor 68Ga-DOTATATE, further validating the role of SV2A-targeted imaging for noninvasive assessment of NED in PCa. In conclusion, we demonstrated that SV2A, highly expressed in NEPC, can serve as a promising target for noninvasive imaging evaluation of NED.
Subject(s)
Carcinoma, Neuroendocrine/diagnostic imaging , Membrane Glycoproteins/analysis , Nerve Tissue Proteins/analysis , Positron-Emission Tomography/methods , Prostatic Neoplasms/diagnostic imaging , Animals , Carcinoma, Neuroendocrine/metabolism , Cell Line, Tumor , Humans , Male , Mice , Organometallic Compounds , Prostatic Neoplasms/metabolism , Xenograft Model Antitumor AssaysABSTRACT
The pyruvate dehydrogenase complex (PDC) is a key control point of energy metabolism and is subject to regulation by multiple mechanisms, including posttranslational phosphorylation by pyruvate dehydrogenase kinase (PDK). Pharmacological modulation of PDC activity could provide a new treatment for diabetic cardiomyopathy, as dysregulated substrate selection is concomitant with decreased heart function. Dichloroacetate (DCA), a classic PDK inhibitor, has been used to treat diabetic cardiomyopathy, but the lack of specificity and side effects of DCA indicate a more specific inhibitor of PDK is needed. This study was designed to determine the effects of a novel and highly selective PDK inhibitor, 2((2,4-dihydroxyphenyl)sulfonyl) isoindoline-4,6-diol (designated PS10), on pyruvate oxidation in diet-induced obese (DIO) mouse hearts compared with DCA-treated hearts. Four groups of mice were studied: lean control, DIO, DIO + DCA, and DIO + PS10. Both DCA and PS10 improved glucose tolerance in the intact animal. Pyruvate metabolism was studied in perfused hearts supplied with physiological mixtures of long chain fatty acids, lactate, and pyruvate. Analysis was performed using conventional 1H and 13C isotopomer methods in combination with hyperpolarized [1-13C]pyruvate in the same hearts. PS10 and DCA both stimulated flux through PDC as measured by the appearance of hyperpolarized [13C]bicarbonate. DCA but not PS10 increased hyperpolarized [1-13C]lactate production. Total carbohydrate oxidation was reduced in DIO mouse hearts but increased by DCA and PS10, the latter doing so without increasing lactate production. The present results suggest that PS10 is a more suitable PDK inhibitor for treatment of diabetic cardiomyopathy.
Subject(s)
Carbohydrates/chemistry , Diet/adverse effects , Heart/physiology , Obesity/metabolism , Protein Kinase Inhibitors/pharmacology , Protein Serine-Threonine Kinases/antagonists & inhibitors , Pyruvic Acid/metabolism , Animals , Energy Metabolism , Heart/drug effects , Male , Mice , Mice, Inbred C57BL , Mice, Obese , Obesity/drug therapy , Obesity/etiology , Obesity/pathology , Oxidation-Reduction , Protein Kinase Inhibitors/chemistry , Pyruvate Dehydrogenase Acetyl-Transferring Kinase , Pyruvate Dehydrogenase Complex/antagonists & inhibitorsABSTRACT
Pyruvate dehydrogenase kinase isoforms (PDKs 1-4) negatively regulate activity of the mitochondrial pyruvate dehydrogenase complex by reversible phosphorylation. PDK isoforms are up-regulated in obesity, diabetes, heart failure, and cancer and are potential therapeutic targets for these important human diseases. Here, we employed a structure-guided design to convert a known Hsp90 inhibitor to a series of highly specific PDK inhibitors, based on structural conservation in the ATP-binding pocket. The key step involved the substitution of a carbonyl group in the parent compound with a sulfonyl in the PDK inhibitors. The final compound of this series, 2-[(2,4-dihydroxyphenyl)sulfonyl]isoindoline-4,6-diol, designated PS10, inhibits all four PDK isoforms with IC50 = 0.8 µM for PDK2. The administration of PS10 (70 mg/kg) to diet-induced obese mice significantly augments pyruvate dehydrogenase complex activity with reduced phosphorylation in different tissues. Prolonged PS10 treatments result in improved glucose tolerance and notably lessened hepatic steatosis in the mouse model. The results support the pharmacological approach of targeting PDK to control both glucose and fat levels in obesity and type 2 diabetes.
Subject(s)
Diabetes Mellitus, Type 2/drug therapy , Enzyme Inhibitors , Fatty Liver/drug therapy , Isoindoles/chemistry , Isoindoles/pharmacology , Obesity/drug therapy , Protein Serine-Threonine Kinases/antagonists & inhibitors , Sulfones/chemistry , Sulfones/pharmacology , Animals , Diabetes Mellitus, Type 2/enzymology , Diabetes Mellitus, Type 2/genetics , Diabetes Mellitus, Type 2/pathology , Drug Delivery Systems , Drug Design , Enzyme Inhibitors/chemistry , Enzyme Inhibitors/pharmacology , Fatty Liver/enzymology , Fatty Liver/genetics , Fatty Liver/pathology , HSP90 Heat-Shock Proteins , Humans , Isoenzymes/antagonists & inhibitors , Isoenzymes/chemistry , Isoenzymes/genetics , Isoenzymes/metabolism , Male , Mice , Mice, Obese , Obesity/enzymology , Obesity/genetics , Obesity/pathology , Protein Serine-Threonine Kinases/chemistry , Protein Serine-Threonine Kinases/genetics , Protein Serine-Threonine Kinases/metabolism , Pyruvate Dehydrogenase Acetyl-Transferring KinaseABSTRACT
The mitochondrial branched-chain α-ketoacid dehydrogenase complex (BCKDC) is negatively regulated by reversible phosphorylation.BCKDC kinase (BDK) inhibitors that augment BCKDC flux have been shown to reduce branched-chain amino acid (BCAA) concentrations in vivo. In the present study, we employed high-throughput screens to identify compound 3,6- dichlorobenzo[b]thiophene-2-carboxylic acid (BT2) as a novel BDK inhibitor (IC(50) = 3.19 µM). BT2 binds to the same site in BDK as other known allosteric BDK inhibitors, including (S)-α-cholorophenylproprionate ((S)-CPP). BT2 binding to BDK triggers helix movements in the N-terminal domain, resulting in the dissociation of BDK from the BCKDC accompanied by accelerated degradation of the released kinase in vivo. BT2 shows excellent pharmacokinetics (terminal T(1/2) = 730 min) and metabolic stability (no degradation in 240 min), which are significantly better than those of (S)-CPP. BT2, its analog 3-chloro-6-fluorobenzo[ b]thiophene-2-carboxylic acid (BT2F), and a prodrug of BT2 (i.e. N-(4-acetamido-1,2,5-oxadiazol-3-yl)-3,6-dichlorobenzo[ b]thiophene-2-carboxamide (BT3)) significantly increase residual BCKDC activity in cultured cells and primary hepatocytes from patients and a mouse model of maple syrup urine disease. Administration of BT2 at 20 mg/kg/day to wild-type mice for 1 week leads to nearly complete dephosphorylation and maximal activation of BCKDC in heart, muscle, kidneys, and liver with reduction in plasma BCAA concentrations. The availability of benzothiophene carboxylate derivatives as stable BDK inhibitors may prove useful for the treatment of metabolic disease caused by elevated BCAA concentrations.
Subject(s)
Enzyme Inhibitors/pharmacology , Hepatocytes/enzymology , Ketoglutarate Dehydrogenase Complex/antagonists & inhibitors , Ketoglutarate Dehydrogenase Complex/metabolism , Proteolysis/drug effects , Thiophenes/pharmacology , Allosteric Regulation/drug effects , Animals , Cell Line , Dose-Response Relationship, Drug , Enzyme Stability/drug effects , Enzyme Stability/genetics , Hepatocytes/pathology , Humans , Ketoglutarate Dehydrogenase Complex/genetics , Mice , Mice, Knockout , Thiophenes/pharmacokineticsABSTRACT
H2-driven reduction of hexavalent chromium (Cr(VI)) using precious-metal catalysts is promising, but its implementation in water treatment has been restricted by poor H2-transfer efficiency and high catalyst loss. We investigated the reduction of Cr(VI) through hydrogenation catalyzed by elemental-palladium nanoparticles (PdNPs) generated in-situ within biofilm of a membrane biofilm reactor (MBfR), creating a Pd-MBfR. Experiments were conducted using a Pd-MBfR and a non-Pd MBfR. The Pd-MBfR achieved Cr(VI) (1000 µg L-1) reduction of >99 % and reduced the concentration of total Cr to below 50 µg L-1, much lower than the total Cr concentration in the non-Pd MBfR effluent (290 µg L-1). The Pd-MBfR also had a lower concentration of dissolved organic compounds compared to the non-Pd MBfR, which minimized the formation of soluble organo-Cr(III) complexes and promoted precipitation of Cr(OH)3. Solid-state characterizations documented deposition of Cr(OH)3 as the product of Cr(VI) reduction in the Pd-MBfR. Metagenomic analyses revealed that the addition and reduction of Cr(VI) had minimal impact on the microbial community (dominated by Dechloromonas) and functional genes in the biofilm of the Pd-MBfR, since the PdNP-catalyzed reduction process was rapid. This study documented efficient Cr(VI) reduction and precipitation of Cr(OH)3 by the Pd-MBfR technology.
Subject(s)
Metal Nanoparticles , Oxidation-Reduction , Palladium , Chromium , BiofilmsABSTRACT
Anaerobic co-digestion using an anaerobic dynamic membrane bioreactor (AnDMBR) can separate the sludge retention time and hydraulic retention time, retaining the biomass for efficient degradation and the use of less expensive large pore-size membrane materials and more sustainable dynamic membranes (DMs). Therefore, anaerobic co-digestion of toilet blackwater (BW) and kitchen waste (KW) using an AnDMBR was hypothesized to increase the potential for co-digestion. Here, the efficiency and stability of AnDMBR in anaerobic co-digestion of toilet BW and KW were investigated. DM morphology and structural characteristics, filtration properties, and composition, as well as membrane contamination and membrane regeneration mechanisms, were investigated. Average daily biogas yields of the reactor in two membrane cycles before and after cleaning were 788.67 and 746.09 ml/g volatile solids, with average methane content of 66.64% and 67.27% and average COD removal efficiencies of 82.03% and 80.96%, respectively. The results showed that the bioreactor obtained good performance and stability. During the stabilization phase of the DM operation, the flux was maintained between 43.65 and 65.15 L/m2/h. DM was mainly composed of organic and inorganic elements. Off-line cleaning facilitated DM regulation and regeneration, restoring new Anaerobic morphology and structure. PRACTITIONER POINTS: High efficiency co-digestion of BW and KW was realized in the DMBR system. Average daily biogas yields before and after membrane cleaning were 788.67 and 746.09 ml/g volatile solids. Off-line cleaning facilitated DM regulation and regeneration as well as system stability. The flux was maintained between 43.65 and 65.15 L/m2/h during operation.
Subject(s)
Bioreactors , Membranes, Artificial , Waste Disposal, Fluid , Anaerobiosis , Waste Disposal, Fluid/methods , Wastewater/chemistryABSTRACT
High entropy alloys and metallic glasses, as two typical metastable nanomaterials, have attracted tremendous interest in energy conversion catalysis due to their high reactivity in nonequilibrium states. Herein, a novel nanomaterial, layered high entropy metallic glass (HEMG), in a higher energy state than low-entropy alloys and its crystalline counterpart due to both the disordered elemental and structural arrangements, is synthesized. Specifically, the MnNiZrRuCe HEMG exhibits highly enhanced photothermal catalytic activity and long-term stability. An unprecedented CO2 methanation rate of 489 mmol g-1 h-1 at 330 °C is achieved, which is, to the authors' knowledge, the highest photothermal CO2 methanation rate in flow reactors. The remarkable activity originates from the abundant free volume and high internal energy state of HEMG, which lead to the extraordinary heterolytic H2 dissociation capacity. The high-entropy effect also ensures the excellent stability of HEMG for up to 450 h. This work not only provides a new perspective on the catalytic mechanism of HEMG, but also sheds light on the great catalytic potential in future carbon-negative industry.
ABSTRACT
Introduction and importance: It is rare for calcium oxalate renal stone, presented mainly in sterile urine, to result in urinary tract infection. The stone-related infection could develop spondylodiscitis, causing neurological deficits. To date, there are no reports about calcium oxalate partial staghorn stone and spondylodiscitis. Case presentation: A 62-year-old male suffered from haematuria, fever, and flank pain. He came to the urology outpatient department, where acute pyelonephritis was diagnosed, and a left partial staghorn stone was seen on computed tomography. Oral antibiotics were prescribed with improvement. Two weeks after antibiotics treatment, he developed bilateral lower limb weakness and numbness under the nipple level. He was brought to the emergency department, where the spine MRI revealed T2-T3 spondylodiscitis with epidural abscess and spinal cord compression. He underwent T2-T3 spine operation with improvement in muscle power and hypesthesia. The culture of the surgical lesion yielded Citrobacter koseri, the same as the urine culture obtained at his first visit. Left-side percutaneous nephrolithotomy was performed 1 month after with successful stone removal and resolution of pyuria. Stone analyses reported calcium oxalate. Follow-up MRI showed marked improvement with resolution of spondylodiscitis. Clinical discussion: Urinary tract infection resulting from partial staghorn stone, with additional hematogenous spread causing spondylodiscitis, is scarcely discussed. The authors illustrated a case with calcium oxalate stone, belonging to sterile Jensen's classification type 1. However, a urinary tract infection could be seen in urine stasis or obstruction. Conclusion: With accurate diagnosis and essential interventions, the patient had immediate neurological improvement and reached disease-free status.
ABSTRACT
Respiration rate is an important healthcare indicator, and it has become a popular research topic in remote healthcare applications with Internet of Things. Existing respiration monitoring systems have limitations in terms of convenience, comfort, and privacy, etc. This paper presents a contactless and real-time respiration monitoring system, the so-called Wi-Breath, based on off-the-shelf WiFi devices. The system monitors respiration with both the amplitude and phase difference of the WiFi channel state information (CSI), which is sensitive to human body micro movement. The phase information of the CSI signal is considered and both the amplitude and phase difference are used. For better respiration detection accuracy, a signal selection method is proposed to select an appropriate signal from the amplitude and phase difference based on a support vector machine (SVM) algorithm. Experimental results demonstrate that the Wi-Breath achieves an accuracy of 91.2% for respiration detection, and has a 17.0% reduction in average error in comparison with state-of-the-art counterparts.
Subject(s)
Algorithms , Respiratory Rate , Humans , Monitoring, Physiologic , Wireless Technology , Delivery of Health CareABSTRACT
Co-doped ZnO thin films have attracted much attention in the field of transparent conductive oxides (TCOs) in solar cells, displays, and other transparent electronics. Unlike conventional single-doped ZnO, co-doped ZnO utilizes two different dopant elements, offering enhanced electrical properties and more controllable optical properties, including transmittance and haze; however, most previous studies focused on the electrical properties, with less attention paid to obtaining high haze using co-doping. Here, we prepare high-haze Ga- and Zr-co-doped ZnO (GZO:Zr or ZGZO) using atmospheric pressure plasma jet (APPJ) systems. We conduct a detailed analysis to examine the interplay between Zr concentrations and film properties. UV-Vis spectroscopy shows a remarkable haze factor increase of 7.19% to 34.8% (+384%) for the films prepared with 2 at% Zr and 8 at% Ga precursor concentrations. EDS analysis reveals Zr accumulation on larger and smaller particles, while SIMS links particle abundance to impurity uptake and altered electrical properties. XPS identifies Zr mainly as ZrO2 because of lattice stress from Zr doping, forming clusters at lattice boundaries and corroborating the SEM findings. Our work presents a new way to fabricate Ga- and Zr-co-doped ZnO for applications that require low electrical resistivity, high visible transparency, and high haze.
ABSTRACT
Psymberin is the only member of the pederin natural product family that contains a dihydroisocoumarin side chain. Structural modifications of psymberin uncoupled inhibition of protein translation from cytotoxicity, suggesting that psymberin has more than one bioactivity. A forward genetic screen in Caenorhabditis elegans was conducted to identify the molecular target(s) of psymberin. Multiple independent psymberin-resistant mutants were isolated, each containing the same point mutation in a gene encoding a ribosomal protein. However, a psymberin-resistant mutant strain bearing this mutation was not cross-resistant to the pederin family member mycalamide A, which binds to the archaeal form of the same protein. Thus, two pederin family members likely differ in how they bind the same molecular target. The accumulation of psymberin in cells was sensitive to the stereochemistry of the amide side chain at C4 or C8 and the presence of the dihydroisocoumarin side chain. The observation that psymberin diastereomers or dihydroisocoumarin-truncated analogs lose all cytotoxic activity while retaining the ability to inhibit protein translation in a cell-free in vitro assay can be explained in the context of these differential cell uptake issues. Finally, we also demonstrate that the blistering activity associated with pederin and other members of the family is not due to their protein synthesis inhibiting activity. Unlike pederin and mycalamide, psymberin does not display irritant or blistering activity.
Subject(s)
Pyrones/chemistry , Pyrones/pharmacology , Coumarins , HeLa Cells , Humans , Structure-Activity RelationshipABSTRACT
The effects of nitrate on 2,4-dichlorophenol (2,4-DCP) dechlorination and biodegradation in a hydrogen (H2)-based palladized membrane biofilm reactor (Pd-MBfR) were studied. The Pd-MBfR was created by synthesizing palladium nanoparticle (Pd0NPs) that spontaneously associated with the biofilm to form a Pd0-biofilm. Without input of nitrate, the Pd-MBfR had rapid and stable catalytic hydrodechlorination: 93% of the 100-µM influent 2,4-DCP was continuously converted to phenol, part of which was then fermented via acetogenesis and methanogenesis. Introduction of nitrate enabled phenol mineralization via denitrification with only a minor decrease in catalytic hydrodechlorination. Phenol-degrading bacteria capable of nitrate respiration were enriched in the Pd0-biofilm, which was dominated by the heterotrophic genera Thauera and Azospira. Because the heterotrophic denitrifiers had greater yields than autotrophic denitrifiers, phenol was a more favorable electron donor than H2 for denitrification. This feature facilitated phenol mineralization and ameliorated denitrification inhibition of catalytic dechlorination through competition for H2. Increased nitrite loading eventually led to deterioration of the dechlorination flux and selectivity toward phenol. This study documents simultaneous removal of 2,4-DCP and nitrate in the Pd-MBfR and interactions between the two reductions.
Subject(s)
Denitrification , Nitrates , Biofilms , Bioreactors , Chlorophenols , PhenolsABSTRACT
Adsorption and catalytic hydrodechlorination (HDC) of aqueous 2,4-DCP by palladium nanoparticles (Pd0NPs) associated with a biofilm (i.e., a Pd0-biofilm) was investigated in terms of the removal efficiency of 2,4-DCP, dechlorinated product selectivity, and reduction kinetics. Experiments were executed with Pd0-biofilm and with abiotic Pd0NPs-film alone. The 2,4-DCP-adsorption capacity of Pd0-biofilm was 2- to 5-fold greater than that of abiotic Pd0NPs-film, and the adsorption accelerated dechlorination by Pd0-biofilm, including selectivity to phenol instead of mono-chlorophenols. A mechanistic kinetic model was developed to represent the sequential adsorption and reduction processes. Modeling results represented well the removal of 2,4-DCP and quantified that Pd0-biofilm had a strong affinity for adsorbing 2,4-DCP. The strong adsorption increased the volume-averaged concentration of 2,4-DCP concentration inside the Pd0-biofilm, compared to the concentration in the bulk liquid. This increase in the local concentration of 2,4-DCP led to a 2- to 4-fold increase in the reduction rate of 2,4-DCP in Pd0-biofilm, compared to abiotic Pd0NPs-film. Thus, coupling Pd0NPs with the biofilm promoted 2,4-DCP removal and full dechlorination despite its low concentration in bulk water.
ABSTRACT
Partial denitrification, the termination of NO3--N reduction at nitrite (NO2--N), has received growing interest for treating wastewaters with high ammonium concentrations, because it can be coupled to anammox for total-nitrogen removal. NO2- accumulation in the hydrogen (H2)-based membrane biofilm reactor (MBfR) has rarely been studied, and the mechanisms behind its accumulation have not been defined. This study aimed at achieving the partial denitrification with H2-based autotrophic reducing bacteria in a MBfR. Results showed that by increasing the NO3- loading, increasing the pH, and decreasing the inorganic-carbon concentration, a nitrite transformation rate higher than 68% was achieved. Community analysis indicated that Thauera and Azoarcus became the dominant genera when partial denitrification was occurring. Functional genes abundances proved that partial denitrification to accumulate NO2- was correlated to increases of gene for the form I RuBisCo enzyme (cbbL). This study confirmed the feasibility of autotrophic partial denitrification formed in the MBfR, and revealed the inorganic carbon mechanism in MBfR denitrification.