High Pd Research Articles

Electrodeposition Decoration of Pd0 on F‐Co(OH)2 Nanoarrays with Intentionally Introduced Pd2+ Species for Efficient Electrocatalytic Hydrodechlorination of 2,4‐Dichlorophenol

AbstractDeveloping a Pd‐based catalyst possessing high efficiency and low mass loading remains a big obstacle for the large‐scale application of electrocatalytic hydrodechlorination (EHDC) of chlorophenols (CPs). Herein, high dispersion Pd nanoparticles imbedded in Pd2+ hydroxide species are decorated on the surface of F−Co(OH)2 nanowire arrays with a newly developed electrodeposition and hydrolysis coupled process. EHDC of 2,4‐dichlorophenol (2,4‐DCP) with the as‐obtained Pd/F−Co(OH)2/NF‐a exhibits superior performance than other control samples in this work and literature reports. A 100 % removal of 2,4‐DCP is accomplished within 120 min, featuring fast reaction kinetics (kobs=5.0×10−2 min−1) and mass activity (MA=22.2 min−1 g−1Pd). Mechanism investigation shows that the intentionally introduced Pd2+ sites play a pivotal role in the adsorption of 2,4‐DCP, while high dispersion of Pd facilitates the generation of active H*, thus promoting the catalytic performance. This work presents a valuable example for designing high‐performance Pd‐based EHDC catalysts by composition tuning.

Implementation and Experimental Analysis of Finding Partial Discharge Source between a Transformer and its Peripheral High Voltage Devices using Several Heterogeneous PD Sensors

Monitoring the transformer’s condition and fault diagnosis are essential to maintain the reliable operation of the transformer and maximize its lifespan. Usually, detecting PD signal from UHF PD sensor installed in a transformer is a method for monitoring the transformer conditions. However, the PD The PD signals leaked from Transformer will be detected by PD sensors due to peripheral high voltage. And it could be mistaken for as PD signal occurred in the transformer. In this paper, through experimental analysis, we propose a technology that installs several heterogeneous PD sensors in a transformer and a peripheral high voltage device and processes PD signals simultaneously to distinguish between PD signals generated inside a transformer and PD signals generated in peripheral high voltage devices. Several heterogeneous PD sensors, such as UHF sensors, TEV sensors, and HFCT sensors, are installed in transformers and peripheral high voltage devices, and the normalized amplitude of PD signals received from each sensor are compared and analyzed on a synchronized time and phase axis. For example, if the PD signals detected by the transformer and the peripheral high voltage device are on the same time and phase axis, and the normalized amplitude of PD signal from transformer is larger than the normalized amplitude of PD signal from the peripheral high voltage device. At this time, this PD signal is determined to have occurred inside the transformer. Whereas, if the normalized amplitude of the PD signal introduced from peripheral high voltage devices is larger than the normalized amplitude of the PD signal introduced from the transformer, it is determined to be PD signal introduced from the peripheral high voltage devices. With the results of experimental analysis, this technology can be effectively used to determine whether the detected PD signal from transformer PD sensor is originated from inside of the transformer or from peripheral high voltage device.

Prediction of epileptogenicity in patients with tuberous sclerosis complex using multimodal cerebral MRI

ObjectiveEpilepsy is the most common complication and cause of morbidity and mortality in tuberous sclerosis complex (TSC). Surgery is associated with an increased probability of achieving seizure-freedom. However, the preoperative noninvasive localisation of epileptogenic tubers remains challenging. This study aimed to identify multimodal magnetic resonance imaging (MRI) biomarkers of epilepsy in patients with TSC and develop a prediction model of epileptogenicity in these patients. MethodsPatients with TSC, with or without epilepsy, were recruited. All patients underwent MRI scanning, including T1WI, T2WI, T2W-FLAIR, DTI, and multi-parametric MR with a flexible design (MULTIPLEX). We compared the multimodal cerebral MRI characteristics of the cortical tubers, subependymal nodules, and perilesional tissue between patients with TSC with or without epilepsy and developed a prediction model for epileptogenicity. ResultsAmong the patients with TSC, 32 with and 16 without epilepsy underwent MRI. Higher proton-density mapping (PD) of cortical tubers and decreased fractional anisotropy (FA), increased mean diffusivity (MD), and increased radial diffusivity (RD) of subependymal nodules were associated with epileptogenicity in both the centre and perilesional tissue, independent of TSC gene variation. Based on the above findings, we developed a prediction model for epileptogenicity with an area under the curve of 0.973, specificity of 0.909, and sensitivity of 0.963 (P < 0.001). ConclusionIn patients with TSC, high PD of the cortical tubers, decreased FA, and elevated MD/RD of the subependymal nodules were significantly associated with epileptogenicity. A prediction model based on multimodal cerebral MRI characteristics has the potential to evaluate the likelihood of epilepsy in patients with TSC.

N─N Bond Oxidative Addition‐Promoted Diaziridinone Activation: A Mechanistic Study

AbstractDensity functional theory (DFT) calculation has been used to reveal palladium‐catalyzed mode of diaziridinone ring activation. Our theoretical studies found that oxidative addition of di‐tert‐butyldiaziridinone to Pd(II) can give a high valent Pd(IV) intermediate, along with the cleavage of N─N bond in di‐tert‐butyldiaziridinone through a concerted three‐membered‐cyclic transition state. Subsequent transformations via reductive elimination and β‐N elimination give the desired indolo[3,2‐b]indole product. The competitive activation modes such as metathesis and migratory insertion can be excluded in our selected model reaction. The rate‐determining step of this reaction is the oxidative addition of di‐tert‐butyldiaziridinone step. Distortion‐interaction analysis was conducted to reveal that the oxidative addition mode of di‐tert‐butyldiaziridinone is superior to the metathesis mode due to the lower interaction energy.

Bird Phylogenetic Diversity Increases With Temperature Worldwide

ABSTRACTAimTemperature significantly influences the composition and structure of biotic communities at large scales. While its role in shaping taxonomic diversity is well‐documented, its relationship with other facets of biodiversity, like phylogenetic diversity, remains poorly known. Understanding how and to which extent temperature contributes to global patterns of phylogenetic diversity compared to other biodiversity‐structuring factors is crucial for comprehending how bird assemblages are structured worldwide, predicting their response to global‐change drivers and supporting conservation policies focused on preserving bird genetic diversity and evolutionary history.LocationWorldwide.MethodsWe analyse the role of temperature in predicting bird regional phylogenetic richness (PD) and divergence (MPD) worldwide, before and after controlling for the effect of species richness (SR). We also assess the shape of this relationship in different biogeographic realms and compare its explanatory power with other key biodiversity‐structuring factors such as elevation, human impact index, net primary productivity and land use diversity.ResultsOur findings underscore the high significance and consistency of temperature as a key predictor positively associated with bird PD and MPD across the six main biogeographic realms, even after accounting for SR and latitude, suggesting that temperature modulates the intrinsic capacity of environments to support a diverse array of lineages. In addition, PD and MPD tended to increase at low elevations, but the human‐impact index did not effectively predict bird phylogenetic diversity at this scale. Furthermore, high PD was linked to regions with high primary productivity and high land‐use diversity, although both of these relationships were strongly mediated by SR.ConclusionsThis study unveils the key role of temperature in explaining bird phylogenetic diversity worldwide over other key biodiversity‐structuring factors and points to the profound implications that climate change will have on the amount of evolutionary history held in bird assemblages, beyond species extinctions or range shifts alone.

Conjugated Porous Organic Polymers Featuring Both Soft-Hard Combined Coordination Sites and Photoelectrochemical Properties for Palladium Capture and Subsequent Photocatalysis.

Palladium (Pd) capture from high-level liquid waste for subsequent photocatalytic applications is desirable for the development of nuclear energy and the reutilization of valuable resources. Herein, we approach our design with a unique porous organic polymer containing thiazolo[5,4-d]thiazole units (denoted as TzPOP-OH). It possesses two potential soft-hard (N-O and S-O) combined coordination sites for Pd(II) coordination and features strong donor-acceptor repeating units and high planarity of linkage enforced by hydrogen bonds for subsequent photocatalysis. Accordingly, TzPOP-OH with three hydroxyl groups on the linkage exhibits a high Pd(II) capacity of 369 mg g-1 at 3 M HNO3, considerably surpassing those of the controlled polymer TzPOP without hydroxyl groups and most other reported materials. Additionally, TzPOP-OH boasts other merits, including outstanding acid tolerance, extraordinary radiation stability, good reusability, and remarkable selectivity. After palladium adsorption, Pd@TzPOP-OH demonstrates impressive photodegradation efficiency to reduce the concentration of rhodamine B in contaminated urban water from 10 to less than 0.1 ppm. This work provides a feasible approach to designing materials with both suitable coordination microenvironments and semiconductor properties for metal separation and photocatalysis.

Spectroscopic, anti-cancer, anti-bacterial and theoretical studies of new bivalent Schiff base complexes derived from 4-bromo-2,6-dichloroaniline

In this paper, four new mono-nuclear Ni(II), Pd(II), Pt(II) and Zn(II) complexes were prepared by using a bi-dentate Schiff base ligand, (E)-2-(((4-bromo-2,6-dichlorophenyl)imino)methyl)-5-chlorophenol (BrcOH), with bivalent ions in a methanol and distil water mixture as solvent in presence of NaOH as base. The structures of the prepared compounds were characterized by spectroscopic techniques (IR and 1H NMR), CHN analysis, and molar conductivity. The M(II) (Ni, Pd and Pt) ions are four-coordinated by a bi-dentate N2O2 donor ligand, forming square planar geometry, whereas the Zn(II) is coordinated as a tetrahedral geometry. The newly synthesized compounds, which include the Schiff base ligand and its complexes, underwent antibacterial screening against E. coli and S. aureus. The results demonstrated a remarkable and noteworthy biological activity of these compounds against these pathogenic bacterial strains. Different binding energies showed good correlation, with Pd showing the strongest binding. Small energy differences indicated high reactivity, with Ni and Pd complexes being the most reactive. Electrophilicity index exhibited electron-accepting properties, with Zn showing the highest reactivity. The dipole moments showed polarity and charge separation, with Pt having the highest polarity. We evaluated the pharmacokinetic properties (ADME) of a ligand and its metal complexes using the Swiss ADME website. The results of the in-silico prediction of physicochemical properties revealed that ten compounds in total adhered to Lipinski's rule.

Eftilagimod Alpha (a Soluble LAG-3 Protein) Combined With Pembrolizumab in Second-Line Metastatic NSCLC Refractory to Anti–Programmed Cell Death Protein 1/Programmed Death-Ligand 1-Based Therapy: Final Results from a Phase 2 Study

IntroductionEftilagimod alpha (efti), a soluble lymphocyte activation gene-3 protein, triggers antigen-presenting cell and T-cell (CD4+ and CD8+) activation and helps overcome resistance to programmed cell death protein 1 or programmed cell death-ligand 1 (PD-(L)1) inhibitors. We assessed efti plus pembrolizumab in second-line anti–PD-(L)1-refractory metastatic patients with NSCLC. MethodsAfter confirmed progression on anti-PD-(L)1-based first-line therapy, patients received efti (30 mg subcutaneously every 2 weeks for eight 3-week cycles and then every 3 weeks for up to 54 weeks) plus pembrolizumab (200 mg intravenously every 3 weeks for up to 105 weeks). The primary endpoint was the objective response rate by modified Response Evaluation Criteria in Solid Tumors version 1.1 for immune-based therapies. Secondary endpoints included disease control rate, progression-free survival, overall survival (OS), and tolerability. Exploratory endpoints included tumor growth kinetics and predefined subgroup analyses. Programmed cell death-ligand 1 tumor proportion score was assessed centrally. ResultsThirty-six patients were enrolled from April 2019 to August 2021 using Simon’s two-stage design. Most patients (81.8%) had low or negative (<50%) PD-(L)1 tumor proportion score. First-line therapy was anti–PD-(L)1-based for all patients, combined with chemotherapy for 66.7%. The confirmed objective response and disease control rates were 8.3% and 33.3%. The median progression-free survival was 2.1 months and the median OS was 9.9 months. Patients exhibiting high PD-(L)1 expression or acquired resistance to PD-(L)1 inhibitors revealed superior response and survival outcomes, and OS was closely correlated with disease control. No treatment-emergent adverse event led to permanent discontinuation of study treatment. ConclusionsEfti plus pembrolizumab was well-tolerated and revealed signs of antitumor activity in patients with NSCLC resistant to PD-(L)1 inhibitors, warranting further investigation. Trial registration number: NCT03625323.

Development of Flexible High‐Efficient Aluminum ion Supercapacitors With 2D Niobium MXene Electrode

ABSTRACTA high‐performance aluminum‐ion supercapacitor is fabricated using 2D few‐layered Nb2CTx MXene, as an active electrode material and Al2(SO4)3 electrolyte for efficient energy storage. Nb2CTx MXene has been synthesized from Nb2AlC MAX phase using HF. Nb2CTx MXene coated on carbon cloth (Nb@CC) displays a capacitance of 307 F g−1 with 90% coulombic efficiency. The specific capacitance of Nb@CC in Al2(SO4)3 electrolyte is exceptionally high compared to those (≤32.2 F g−1) in H2SO4, Na2SO4, and MgSO4 electrolytes. Both symmetric and asymmetric aluminum ion supercapacitors are fabricated with Nb@CC electrode. The Nb@CC//Nb@CC symmetric device exhibits a capacitance of 122 F g−1 with a high energy density (Ed) of 33.2 Wh kg−1 at 1.41 kW kg−1 power density (Pd). An asymmetric supercapacitor device (ASC), Nb@CC//CNT@CC, with carbon nanotube (CNT@CC) cathode delivers a maximum Ed of 24.7 Wh kg−1 at 3.41 kW kg−1 Pd and excellent stability with 90% capacitance retention after 4000 cycles. A remarkably high Pd of 34 kW kg−1 is maintained with 13.2 Wh kg−1 Ed, and the rate capability is 53% for a 10‐fold increase in current density. These results offer the feasibility of efficient aqueous supercapacitors with Al‐ion as guest species, presenting new possibilities for supercapacitors.

Modifying the Substrate-Dependent Pd/Fe2O3 Catalyst-Support Synergism with ZnO Atomic Layer Deposition.

Low-loading Pd supported on Fe2O3 nanoparticles was synthesized. A common nanocatalyst system with previously reported synergistic enhancement of reactivity that is attributed to the electronic interactions between Pd and the Fe2O3 support. Fe2O3-selective precoalescence overcoating with ZnO atomic layer deposition (ALD), using Zn(CH2CH3)2 and H2O as precursors, dampens competitive hydrogenation reactivity at Fe2O3-based sites. The result is enhanced efficiency at the low-loading but high reactivity Pd sites. While this increases catalyst efficiency toward most aqueous redox reactions tested, it suppresses reactivity toward polyaromatic core substrates. X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) show minimal electronic impacts for the ZnO overcoat on the Pd particles, implying a predominantly physical site blocking effect as the reason for the modified reactivity. This serves as a proof-of-concept of not only stabilizing supported nanocatalysts but also altering reactivity with ultrathin ALD overcoats. The results point to a facile ALD route for selective enhancement of reactivity for low-loading Pd-based supported nanocatalysts.

High responsive Pd decorated low temperature α-MoO3 hydrogen gas sensor

The H2 gas adsorption properties, which are the most crucial concept for a gas sensor, of the 2-dimensional (2D) MoS2 are limited compared to its oxide form of 2D α-MoO3. On the other hand, it is straightforward to form high surface-to-volume ratio nanostructures with MoS2. In order to get the benefits of the large surface and better H2 adsorption properties for the H2 gas sensor, MoS2 film grown by the chemical vapor deposition (CVD) method was converted into MoO3 with a thermal oxidation process at 380 °C under oxygen-ambient conditions. The grown MoS2 film has indicated that it is formed from the coalesced MoS2 flakes. An ultra-high response of 3 × 106 at a relatively low temperature of 100 °C was achieved for as low as 800 ppm hydrogen concentration. The hydrogen gas sensing mechanism has been discussed in depth using the double injection model, similar to the electrochromic mechanism.

Hysteresis between gas breakdown and plasma discharge

In direct-current (DC) discharge, it is well known that hysteresis is observed between the Townsend (gas breakdown) and glow regimes. Forward and backward voltage sweep is performed using a one-dimensional particle-in-cell Monte Carlo collision (PIC-MCC) model considering a ballast resistor. When increasing the applied voltage after reaching the breakdown voltage (Vb), transition from Townsend to glow discharges is observed. When decreasing the applied voltage from the glow regime, the discharge voltage (Vd) between the anode–cathode gap can be smaller than the breakdown voltage, resulting in a hysteresis, which is consistent with experimental observations. Next, the PIC-MCC model is used to investigate the self-sustaining voltage (Vs) in the presence of finite initial plasma densities between the anode and cathode gap. It is observed that the self-sustaining voltage coincides with the discharge voltage obtained from the backward voltage sweep. In addition, the self-sustaining voltage decreases with increased initial plasma density and saturates above a certain initial plasma density, which indicates a change in plasma resistivity. The decrease in self-sustaining voltage is associated with the electron heat loss at the anode for the low pd (rarefied) regime. In the high pd (collisional) regime, the ion energy loss toward the cathode due to the cathode fall and the inelastic collision loss of electrons in the bulk discharge balance out. Finally, it is demonstrated that the self-sustaining voltage collapses to a singular value, despite the presence of a initial plasma, for microgaps when field emission is dominant, which is also consistent with experimental observations.

Easily recyclable pd-decorated hierarchically porous nanofibers for the selective hydrogenation of phenol

The electrospun nanofibers are good candidates for the catalyst carriers, however the fabrication of electrospun nanofibers with well-developed porous structures is still a big challenge. Herein, the SiO2 nanofibers obtained by electrospinning and pyrolysis are functionalized with polydopamine (PDA) and UiO-66-NH2, and after Pd loading the hierarchically porous Pd/UiO-SiO2 nanofiber catalysts were developed. The surface properties and microstructures of the Pd/UiO-SiO2 nanofiber catalysts were regulated by adjusting the concentrations of dopamine (DA) and zirconium tetrachloride (ZrCl4), and the catalytic performance was tested in the selective hydrogenation of phenol to cyclohexanone. The as-prepared Pd/UiO-SiO2-3–21.44 has abundant hierarchical pores and amino groups, high Pd content with good dispersion, and rich Pd(0), thus exhibiting a superior specific activity of 47.3 h−1 higher than most Pd-based catalysts. Most importantly, the Pd/UiO-SiO2-3–21.44 nanofiber catalyst can be directly taken out from the reaction solution and used for the next run, and has good catalytic stability.

Dimensional Reduction of Metal-Organic Frameworks for Photocatalytic Synthesis of Fused Tetracyclic Heterocycles.

Heterogeneous palladium catalysts with high efficiency, high Pd atom utilization, simplified separation, and recycle have attracted considerable attention in the field of synthetic chemistry. Herein, we reported a zirconium-based two-dimensional metal-organic framework (2D-MOF)-based Pd(II) photocatalyst (Zr-Ir-Pd) by merging the Ir photosensitizers and Pd(II) species into the skeletons of the 2D-MOF for the Pd(II)-catalyzed oxidation reaction. Morphological and structural characterization identified that Zr-Ir-Pd with a specific nanoflower-like structure consists of ultrathin 2D-MOF nanosheets (3.85 nm). Due to its excellent visible-light response and absorption capability, faster transfer and separation of photogenerated carriers, more accessible Pd active sites, and low mass transfer resistance, Zr-Ir-Pd exhibited boosted photocatalytic activity in catalyzing sterically hindered isocyanide insertion of diarylalkynes for the construction of fused tetracyclic heterocycles, with up to 12 times the Pd catalyst turnover number than the existing catalytic systems. In addition, Zr-Ir-Pd inhibited the competitive agglomeration of Pd(0) species and could be reused at least five times, owing to the stabilization of 2D-MOF on the single-site Pd and Ir sites. Finally, a possible mechanism of the photocatalytic synthesis of fused tetracyclic heterocycles catalyzed by Zr-Ir-Pd was proposed.

Theoretically predicted innovative palladium stripe dopingcobalt(1 1 1) surface with excellent catalytic performance for carbon monoxide oxidative coupling to dimethyl oxalate

Pd-based catalysts are extensively employed to catalyze CO oxidative coupling to generate DMO, while the expensive price and high usage of Pd hinder its massive application in industrial production. Designing Pd-based catalysts with high efficiency and low Pd usage as well as expounding the catalytic mechanisms are significant for the reaction. In this study, we theoretically predict that Pd stripe doping Co(1 1 1) surface exhibits excellent performance than pure Pd(1 1 1), Pd monolayer supporting on Co(1 1 1) and Pd single atom doping Co(1 1 1) surface, and clearly expound the catalytic mechanisms through the density functional theory (DFT) calculation and micro-reaction kinetic model analysis. It is obtained that the favorable reaction pathway is COOCH3–COOCH3 coupling pathway over these four catalysts, while the rate-controlling step is COOCH3+CO+OCH3→2COOCH3 on Pd stripe doping Co(1 1 1) surface, which is different from the case (2COOCH3→DMO) on pure Pd(1 1 1), Pd monolayer supporting on Co(1 1 1) and Pd single atom doping Co(1 1 1) surface. This study can contribute a certain reference value for developing Pd-based catalysts with high efficiency and low Pd usage for CO oxidative coupling to DMO.

Mid-term safety and efficacy in small intracranial aneurysm coiling: results from TARGET® nano prospective independent core lab adjudicated multicenter registry.

The primary objective is to evaluate the safety and effectiveness of Stryker second generation Target® Nano Coils in the treatment of ruptured and unruptured small (<7 mm) intracranial aneurysms. The TARGET Registry is a prospective, two-arm study with independent medical event monitoring and core-lab adjudication. This paper describes the second arm of the TARGET registry. Patients with de novo intracranial aneurysms were embolized with 2nd generation TARGET Nano coils in 12 US centers. The primary efficacy outcome was adequate aneurysm occlusion (RR occlusion grade I-II) on follow-up. Primary safety outcome was treatment-related morbidity and mortality. Secondary outcomes included aneurysm packing density immediately post-procedure, immediate adequate occlusion, aneurysm re-access rate, retreatment rate and clinical outcomes using modified ranking scale. A secondary analysis investigated the influence of using Nano-predominant coils (≥2/3 of total coil-length) vs. non-Nano-predominant coils (<2/3 of total length). 150 patients with 155 aneurysms met the inclusion and exclusion criteria. (31%) patients with ruptured and (69%) with unruptured aneurysms were treated using TARGET coils. Median age was 58.8 (SD 12.7), 74.7% were females, and 80% were Caucasians. Mean follow-up was 5.23 (SD 2.27) months. Peri-procedural mortality was seen in 2.0% of patients. Good outcome at discharge (mRS 0-2) was seen in 81.3% of the cohort. The median packing density (SD) was 29.4% (14.9). Mid-term complete/near complete occlusion rate was seen in 96% of aneurysms and complete obliteration was seen in 75.2% of aneurysms. Patients treated predominantly with Nano coils had higher PD (32.6% vs. 26.1%, p < 0.001). There was no significant difference in clinical and angiographic outcomes. The mid-term mRS0-2 was achieved in 106/109 (97.2%) patients. All-cause mortality was 5/115 (4.3%). In the multicenter TARGET Registry, 75.8% of aneurysms achieved mid-term complete occlusion, and 96% achieved complete/near complete occlusion with excellent independent functional outcome.

Identification of CNKSR1 as a biomarker for “cold” tumor microenvironment in lung adenocarcinoma: An integrative analysis based on a novel workflow

BackgroundTherapies targeting PD1/PD-L1 pathway have revolutionized the treatment of lung cancer. However, anti-PD1/PD-L1 therapies have proven beneficial for only a select group of lung adenocarcinoma (LUAD) patients and generally do not work for immuno-cold tumors characterized by a lack of immune cell infiltration. Identifying novel biomarkers is vital to broad therapeutic options for LUAD patients with no response to anti-PD1/PD-L1 immunotherapies. MethodsOur study has developed a novel strategy to identify a promising biomarker that addresses the limitations of anti-PD1/PD-L1 immunotherapy in treating immunological cold tumors. We exacted LUAD RNA-seq data from the Cancer Genome Atlas database (TCGA). Using several machine learning methods, we identified the candidate biomarker. Based on the expression level of PD-L1 and the identified biomarker, samples were categorized into four groups. We further used ESTIMATE, ssGSEA, and CIBERSORT algorithms to calculate the immune infiltration level of each group. The results were validated in three independent bulk datasets and one scRNA-seq dataset. Immunohistochemistry (IHC) assessments were performed in clinical samples to further evaluate the coexpression of CNKSR1 and PD-L1, and to compare CD8 + T cell infiltration among groups. ResultsAfter comprehensive analyses, CNKSR1 was identified as a novel promising biomarker for immuno-cold LUAD. CNKSR1 mRNA expression levels exhibited a negative correlation with both PD-L1 mRNA expression and the extent of immune cell infiltration in LUAD. Besides, in contrast to the significant association between the expression of PD-L1 and the majority of other well-established or widely studied immune checkpoint molecules, a mutually exclusive expression pattern is observed between CNKSR1 and these molecules. The aforementioned results were consistent in validation datasets. The prognostic model built based on the CNKSR1 coexpression module also showed robust predictive performance. Additionally, IHC assessments have confirmed that the coexpression of CNKSR1 and PD-L1 is rare in LUAD samples. Notably, LUADs in the high-CNKSR1 group, characterized by high CNKSR1 but low PD- L1 expression, demonstrated reduced infiltration of CD8+ T cells. ConclusionsIn summary, CNKSR1 emerges as a promising biomarker for immune-cold LUADs, and the study into CNKSR1 modulating T-cell infiltration may lead to the identification of compensatory molecules to enhance the effectiveness of current immunotherapy for LUAD.

Experimental investigation to understand the effect of fracturing fluid on the geomechanical behavior of mowry shale

Hydraulic fracturing of shale reservoirs is one of the important technologies in the oil and gas industry. To ensure the safe operation of oil and gas recovery, it is important to study the shale-fluid interactions on the geomechanical behavior of shale. This study investigated the effect of fracturing fluid treatment on the mechanical and elastic properties of the Mowry Shale formation, Wyoming, USA. Cylindrical Mowry Shale specimens with a diameter of 12.5 mm collected from the United States Geological Survey (USGS) and School of Energy Resources (SER) of the University of Wyoming were treated with brine and brine + stimulation fluid for one month each at pressures of 9 and 11.7 MPa and temperatures of 96 and 66 °C, respectively. Triaxial compression experiments were conducted on the specimens. Results showed that all Mowry Shale specimens experienced an increase in maximum volumetric strain with the increase in effective confining pressure (Pd). Regardless of aging fluids, the maximum deviatoric stress (Δσd) of most Mowry Shale specimens increases with the increase in Pd. At a lower Pd, the USGS specimen aged with brine and stimulation fluid exhibits higher maximum Δσd than those aged with brine only. However, at a higher Pd, the USGS specimen aged with brine exhibits a higher maximum Δσd. SER specimens aged with brine and stimulation fluid exhibit higher maximum Δσd values than those aged with brine for all three Pd values. Regardless of the aging fluids, most USGS specimens experience a brittle failure mode, while SER specimens aged with brine and stimulation fluid experienced a more ductile behavior.

Degradation of bisphenol F by peroxymonosulfate activated with palladium-based catalysts

In this study, supported Pd catalysts were prepared and used as heterogeneous catalysts for the activation of peroxymonosulfate (PMS) which successfully degrade bisphenol F (BPF). Among the supported catalysts (i.e., Pd/SiO2, Pd/CeO2, Pd/TiO2 and Pd/Al2O3), Pd/TiO2 exhibited the highest catalytic activity due to the high isoelectric point and high Pd0 content. Pd/TiO2 prepared by the deposition method leads to high Pd dispersion, which are the key factors for efficient BPF degradation. The influencing factors were investigated during the reaction process and two possible degradation pathways were proposed. Density functional theory (DFT) calculations demonstrate that stronger BPF adsorption and BPF degradation with lower reaction barrier occurs on smaller Pd particles. The catalytic activities are strongly dependent on the structural features of the catalysts. Both experiments and theoretical calculations prove that the reaction is actuated by electron transfer rather than radicals.

Hydrogenation of olefinic bonds in nitrile butadiene rubber on single-atom Pd1/CeO2−x catalysts with ultrahigh mass activity and stability

As pivotal high-performance elastomers, hydrogenated nitrile butadiene rubber (HNBR) was commonly manufactured by selective hydrogenation of nitrile butadiene rubber (NBR). Nevertheless, the high cost and poor stability of current noble metal-based catalysts seriously limit their large-scale applications. Herein, we report single-atom Pd supported by oxygen vacancies-rich CeO2−x nanorods (Pd1/CeO2−x) as a novel catalyst for selectively hydrogenating the NBR. As a result of strong interaction between single-atom Pd and CeO2−x support, the electrophilicity of Pd sites, and the nucleophilicity of olefinic bonds in NBR, the Pd1/CeO2−x show a very high hydrogenated degree of 97.6 %, an unprecedentedly high Pd mass activity of 93.9 gNBR gPd−1h−1, and outstanding cycling stability, which considerably outperform those for previously reported catalysts. Therefore, this work will promote the low-cost manufacture of HNBR and the exploration of single-atom catalysts for selective hydrogenation.