Biogenic Palladium Improved Perchlorate Reduction during Nitrate Co-Reduction by Diverting Electron Flow in a Hydrogenotrophic Biofilm.

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.

Coupling of biogas residue biochar and low-magnitude electric fields promotes anaerobic co-digestion of sewage sludge and food waste.

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.

Layered High-Entropy Metallic Glasses for Photothermal CO2 Methanation.

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.

Reduction and precipitation of chromium(VI) using a palladized membrane biofilm reactor.

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.

Analysis of Hazy Ga- and Zr-Co-Doped Zinc Oxide Films Prepared with Atmospheric Pressure Plasma Jet Systems.

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.

Infected calcium oxalate stone leading to pyogenic spondylodiscitis and bilateral lower limb weakness: a case report.

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.

Optimal lattice depth on lifetime of D-band ultracold atoms in a triangular optical lattice.

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.

Wi-Breath: A WiFi-Based Contactless and Real-Time Respiration Monitoring Scheme for Remote Healthcare.

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.

In vivo characterization of glutamine metabolism identifies therapeutic targets in clear cell renal cell carcinoma.

Targeting metabolic vulnerabilities has been proposed as a therapeutic strategy in renal cell carcinoma (RCC). Here, we analyzed the metabolism of patient-derived xenografts (tumorgrafts) from diverse subtypes of RCC. Tumorgrafts from VHL-mutant clear cell RCC (ccRCC) retained metabolic features of human ccRCC and engaged in oxidative and reductive glutamine metabolism. Genetic silencing of isocitrate dehydrogenase-1 or isocitrate dehydrogenase-2 impaired reductive labeling of tricarboxylic acid (TCA) cycle intermediates in vivo and suppressed growth of tumors generated from tumorgraft-derived cells. Glutaminase inhibition reduced the contribution of glutamine to the TCA cycle and resulted in modest suppression of tumorgraft growth. Infusions with [amide-15N]glutamine revealed persistent amidotransferase activity during glutaminase inhibition, and blocking these activities with the amidotransferase inhibitor JHU-083 also reduced tumor growth in both immunocompromised and immunocompetent mice. We conclude that ccRCC tumorgrafts catabolize glutamine via multiple pathways, perhaps explaining why it has been challenging to achieve therapeutic responses in patients by inhibiting glutaminase.

Atomic Ramsey interferometry with S- and D-band in a triangular optical lattice.

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.

Dissimilatory and Cytoplasmic Antimonate Reductions in a Hydrogen-Based Membrane Biofilm Reactor.

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.

Synergistic Inorganic Carbon and Denitrification Genes Contributed to Nitrite Accumulation in a Hydrogen-Based Membrane Biofilm Reactor.

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.

A kinetic model for 2,4-dichlorophenol adsorption and hydrodechlorination over a palladized biofilm.

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.

Co-removal of 2,4-dichlorophenol and nitrate using a palladized biofilm: Denitrification-promoted microbial mineralization following catalytic dechlorination.

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.

Validation of SV2A-Targeted PET Imaging for Noninvasive Assessment of Neuroendocrine Differentiation in Prostate Cancer.

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.

The Association of Ovarian Teratoma and Anti-N-Methyl-D-Aspartate Receptor Encephalitis: An Updated Integrative Review.

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.

Imaging of Actively Proliferating Bacterial Infections by Targeting the Bacterial Metabolic Footprint with d-[5-11C]-Glutamine.

Since most d-amino acids (DAAs) are utilized by bacterial cells but not by mammalian eukaryotic hosts, recently DAA-based molecular imaging strategies have been extensively explored for noninvasively differentiating bacterial infections from the host's inflammatory responses. Given glutamine's pivotal role in bacterial survival, cell growth, biofilm formation, and even virulence, here we report a new positron emission tomography (PET) imaging approach using d-5-[11C]glutamine (d-[5-11C]-Gln) for potential clinical assessment of bacterial infection through a comparative study with its l-isomer counterpart, l-[5-11C]-Gln. In both control and infected mice, l-[5-11C]-Gln had substantially higher uptake levels than d-[5-11C]-Gln in most organs except the kidneys, showing the expected higher use of l-[5-11C]-Gln by mammalian tissues and more efficient renal excretion of d-[5-11C]-Gln. Importantly, our work demonstrates that PET imaging with d-[5-11C]-Gln is capable of detecting infections induced by both Escherichia coli (E. coli) and methicillin-resistant Staphylococcus aureus (MRSA) in a dual-infection murine myositis model with significantly higher infection-to-background contrast than with l-[5-11C]-Gln (in E. coli, 1.64; in MRSA, 2.62, p = 0.0004). This can be attributed to the fact that d-[5-11C]-Gln is utilized by bacteria while being more efficiently cleared from the host tissues. We confirmed the bacterial infection imaging specificity of d-[5-11C]-Gln by comparing its uptake in active bacterial infections versus sterile inflammation and with 2-deoxy-2-[18F]fluoroglucose ([18F]FDG). These results together demonstrate the translational potential of PET imaging with d-[5-11C]-Gln for the noninvasive detection of bacterial infectious diseases in humans.

Radiolabeling strategies and pharmacokinetic studies for metal based nanotheranostics.

Radiolabeled metal-based nanoparticles (MNPs) have drawn considerable attention in the fields of nuclear medicine and molecular imaging, drug delivery, and radiation therapy, given the fact that they can be potentially used as diagnostic imaging and/or therapeutic agents, or even as theranostic combinations. Here, we present a systematic review on recent advances in the design and synthesis of MNPs with major focuses on their radiolabeling strategies and the determinants of their in vivo pharmacokinetics, and together how their intended applications would be impacted. For clarification, we categorize all reported radiolabeling strategies for MNPs into indirect and direct approaches. While indirect labeling simply refers to the use of bifunctional chelators or prosthetic groups conjugated to MNPs for post-synthesis labeling with radionuclides, we found that many practical direct labeling methodologies have been developed to incorporate radionuclides into the MNP core without using extra reagents, including chemisorption, radiochemical doping, hadronic bombardment, encapsulation, and isotope or cation exchange. From the perspective of practical use, a few relevant examples are presented and discussed in terms of their pros and cons. We further reviewed the determinants of in vivo pharmacokinetic parameters of MNPs, including factors influencing their in vivo absorption, distribution, metabolism, and elimination, and discussed the challenges and opportunities in the development of radiolabeled MNPs for in vivo biomedical applications. Taken together, we believe the cumulative advancement summarized in this review would provide a general guidance in the field for design and synthesis of radiolabeled MNPs towards practical realization of their much desired theranostic capabilities. This article is categorized under: Nanotechnology Approaches to Biology > Nanoscale Systems in Biology Diagnostic Tools > Diagnostic Nanodevices Therapeutic Approaches and Drug Discovery > Nanomedicine for Oncologic Disease.

Dechlorination of 2,4-dichlorophenol in a hydrogen-based membrane palladium-film reactor: Performance, mechanisms, and model development.

We created a hydrogen-based membrane palladium-film reactor (MPfR) by depositing palladium nanoparticles (PdNPs) on hollow-fiber membranes via autocatalytic hydrogenation to form a Pd-film. The MPfR was used for hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP). HDC performances and mechanisms were systematically evaluated, and a continuous-flow dechlorination model was established. Approximately 87% of the input 2,4-DCP was reduced to the end-product phenol (P), while 2-chlorophenol (2-CP) was an intermediate, but only at 2%. Selective adsorption of the 2,4-DCP onto the Pd-film and fast desorption of P facilitated efficient dechlorination. Modeling results represented well the concentrations of 2,4-DCP and its intermediates. It demonstrated three dechlorination pathways: The majority of 2,4-DCP was completely dechlorinated to P in an adsorbed state without release of monochlorphenol, some 2,4-DCP was degraded to 2-CP that was released and subsequently adsorbed and reduced to P, and a small amount was reduced to 4-CP that was released and subsequently adsorbed and reduced to P. Analysis based on Density Functional Theory suggests that the pathway of full dechlorination was dominant due to its thermodynamically favorable adsorption configuration, with both Cl atoms bonded to Pd. This study documents full dechlorination of 2,4-DCP in the MPfR and the interacting roles of adsorption and HDC.

Real-time hyperpolarized 13C magnetic resonance detects increased pyruvate oxidation in pyruvate dehydrogenase kinase 2/4-double knockout mouse livers.

The pyruvate dehydrogenase complex (PDH) critically regulates carbohydrate metabolism. Phosphorylation of PDH by one of the pyruvate dehydrogenase kinases 1-4 (PDK1-4) decreases the flux of carbohydrates into the TCA cycle. Inhibition of PDKs increases oxidative metabolism of carbohydrates, so targeting PDKs has emerged as an important therapeutic approach to manage various metabolic diseases. Therefore, it is highly desirable to begin to establish imaging tools for noninvasive measurements of PDH flux in rodent models. In this study, we used hyperpolarized (HP) 13C-magnetic resonance spectroscopy to study the impact of a PDK2/PDK4 double knockout (DKO) on pyruvate metabolism in perfused livers from lean and diet-induced obese (DIO) mice and validated the HP observations with high-resolution 13C-nuclear magnetic resonance (NMR) spectroscopy of tissue extracts and steady-state isotopomer analyses. We observed that PDK-deficient livers produce more HP-bicarbonate from HP-[1-13C]pyruvate than age-matched control livers. A steady-state 13C-NMR isotopomer analysis of tissue extracts confirmed that flux rates through PDH, as well as pyruvate carboxylase and pyruvate cycling activities, are significantly higher in PDK-deficient livers. Immunoblotting experiments confirmed that HP-bicarbonate production from HP-[1-13C]pyruvate parallels decreased phosphorylation of the PDH E1α subunit (pE1α) in liver tissue. Our findings indicate that combining real-time hyperpolarized 13C NMR spectroscopy and 13C isotopomer analysis provides quantitative insights into intermediary metabolism in PDK-knockout mice. We propose that this method will be useful in assessing metabolic disease states and developing therapies to improve PDH flux.