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Summary To understand the role of connate water as a source of hydrogen in oxidation and upgrading of bituminous oil at high temperature, heavy water (D2O) and O-18 enriched water (H2O18) were used as connate water in two different in-situ combustion experiments using a conical tube. Aside from fundamental understanding of the role of such reactions in in-situ combustion, the results could also potentially help in optimizing in-situ hydrogen generation and upgrading of heavy and bituminous oil. The conical tube had previously been used for understanding the impact of air flux (AF) in sustaining the combustion front (Alamatsaz et al. 2011). Significant upgrading was observed in these tests with a produced API gravity of 35 ° compared to the original bitumen gravity of 9 °API. This paper (Part A) deals with the experimental results including a comparison between conical tube and a combustion tube (CT) results. A subsequent paper (Part B) will discuss the upgrading aspects and the mass spectrometry results.

Many cancers are termed immunoevasive due to expression of immunomodulatory ligands. Programmed death ligand-1 (PD-L1) and cluster of differentiation 80/86 (CD80/86) interact with their receptors, programmed death receptor-1 (PD-1) and cytotoxic T-lymphocyte antigen-4 (CTLA-4), respectively, on tumor-infiltrating leukocytes eliciting immunosuppression. Immunotherapies aimed at blocking these interactions are revolutionizing cancer treatments, albeit in an inadequately described patient subset. To address the issue of patient stratification for immune checkpoint intervention, we quantitatively imaged PD-1/PD-L1 interactions in tumor samples from patients, employing an assay that readily detects these intercellular protein–protein interactions in the less than or equal to 10 nm range. These analyses across multiple patient cohorts demonstrated the intercancer, interpatient, and intratumoral heterogeneity of interacting immune checkpoints. The PD-1/PD-L1 interaction was not correlated with clinical PD-L1 expression scores in malignant melanoma. Crucially, among anti-PD-1–treated patients with metastatic non–small cell lung cancer, those with lower PD-1/PD-L1 interaction had significantly worsened survival. It is surmised that within tumors selecting for an elevated level of PD-1/PD-L1 interaction, there is a greater dependence on this pathway for immune evasion and hence, they exhibit more impressive patient response to intervention.Significance:Quantitation of immune checkpoint interaction by direct imaging demonstrates that immunotherapy-treated patients with metastatic NSCLC with a low extent of PD-1/PD-L1 interaction show significantly worse outcome.

Supplementary FRET Methods

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Green fuel hydrogen generation by photoelectric water splitting is one of the best techniques. The chemical route is chosen for achieving good and sustained photocurrent values for distinct nanocubes of di-indium sulfide (In2S3). Nanocomposites with majority of nanocubes of In2S3 were synthesized on the ITO glass in a hydrothermal vessel with hydrated InCl3 and thiourea as initial precursors at 120 °C for 12 h. Raman and XRD analysis has shown the formation of the cubic phase of β-In2S3. FESEM and HRTEM analysis showed highly crystalline nanocubes with an average size of 1 μm. The photocurrent density reached value 0.28 mA/cm2 at 1 V Ag/AgCl under the irradiation of 100 mW/cm2 without specific agent.

The deposition of reduced graphene oxide over layer on the SnS thin films had been shown to be an effective tool to improve its photoelectrochemical response. Pure phase SnS thin films were prepared using simple and inexpensive thermal evaporation method on ITO glass substrate followed by the deposition of reduced graphene oxide (rGO) layer by drop cast method. Samples were characterized using X-ray diffraction, Raman, scanning electron microscopy, UV–Visible absorption spectroscopy and their photoelectrochemical activity has been investigated. The results show the formation of pure phase SnS having orthorhombic crystal structure with optical band gap of 2.0 eV, rGO layer enhances the absorption in visible region. Maximum photocurrent density exhibited by SnS/0.1 wt% rGO was observed to be 1.1 mA/cm2 as compared to pristine SnS (0.3 mA/cm2) at 0.95V Ag/AgCl with enhanced photostability up to 1 h. Graphene oxide over layer acts as protecting layer for SnS in the electrolyte and plays a promising role in enhancing the charge carriers separation at the interface on account of being an electron reservoir to accept the photoexcited electrons. This work highlights the role of rGO and SnS interface on the photoelectrochemical water splitting.

Hot energy carrier filtering as a means to improve the thermoelectric (TE) property in Sb2Te3 thin film samples having size-selected Au nanoparticles (NPs) is investigated in the present study. Nonagglomerated Au NPs with a very narrow size distribution grown by an integrated gas-phase synthesis setup are incorporated into the Sb2Te3 thin film synthesized by RF magnetron sputtering. TE properties have been investigated as a function of size-selected Au NP concentrations and compared with that of a nanocomposite sample having non-size-selected Au NPs. An increase in the Seebeck coefficient and power factor, along with a slight decrease in electrical conductivity, is observed for samples with a NP size of minimum variance. Further, the Kelvin probe force microscopy and conducting atomic force microscopy techniques were employed to understand the nature of the interface and charge transport across the Sb2Te3 matrix and Au NPs. The study provides an opportunity to modulate the TE properties in Sb2Te3 thin films by constructing a metal-semiconductor heterostructure through controlling the concentration and randomness to achieve a high TE performance.

ObjectiveTo evaluate the impact of the ‘Getting it Right First Time’ (GIRFT) national improvement programme in orthopaedics, which started in 2012.DesignMixed-methods study comprising statistical analysis of linked national datasets (National Joint Registry; Hospital Episode Statistics; Patient-Reported Outcomes); economic analysis and qualitative case studies in six National Health Service (NHS) Trusts.SettingNHS elective orthopaedic surgery in England.Participants736 088 patients who underwent primary hip or knee replacement at 126 NHS Trusts between 1 April 2009 and 31 March 2018, plus 50 NHS staff.InterventionImprovement bundle including ‘deep dive’ visits by senior clinician to NHS Trusts, informed by bespoke set of routine performance data, to discuss how improvements could be made locally.Main outcome measuresNumber of procedures conducted by low volume surgeons; use of uncemented hip implants in patients >65; arthroscopy in year prior to knee replacement; hospital length of stay; emergency readmissions within 30 days; revision surgery within 1 year; health-related quality of life and functional status.ResultsNational trends demonstrated substantial improvements beginning prior to GIRFT. Between 2012 and 2018, there were reductions in procedures by low volume surgeons (ORs (95% CI) hips 0.58 (0.53 to 0.63), knees 0.77 (0.72 to 0.83)); uncemented hip prostheses in >65 s (OR 0.56 (0.51 to 0.61)); knee arthroscopies before surgery (OR 0.48 (0.41 to 0.56)) and mean length of stay (hips −0.90 (−1.00 to -0.81), knees −0.74 days (−0.82 to −0.66)). The additional impact of visits was mixed and comprised an overall economic saving of £431 848 between 2012 and 2018, but this was offset by the costs of the visits. Staff reported that GIRFT’s influence ranged from procurement changes to improved regional collaboration.ConclusionNationally, we found substantial improvements in care, but the specific contribution of GIRFT cannot be reliably estimated due to other concurrent initiatives. Our approach enabled additional analysis of the discrete impact of GIRFT visits.

Dihydroxyacetone (DHA) is a three-carbon sugar that is the active ingredient in sunless tanning products and a by-product of electronic cigarette (e-cigarette) combustion. Increased use of sunless tanning products and e-cigarettes has elevated exposures to DHA through inhalation and absorption. Studies have confirmed that DHA is rapidly absorbed into cells and can enter into metabolic pathways following phosphorylation to dihydroxyacetone phosphate (DHAP), a product of fructose metabolism. Recent reports have suggested metabolic imbalance and cellular stress results from DHA exposures. However, the impact of elevated exposure to DHA on human health is currently under-investigated. We propose that exogenous exposures to DHA increase DHAP levels in cells and mimic fructose exposures to produce oxidative stress, mitochondrial dysfunction, and gene and protein expression changes. Here, we review cell line and animal model exposures to fructose to highlight similarities in the effects produced by exogenous exposures to DHA. Given the long-term health consequences of fructose exposure, this review emphasizes the pressing need to further examine DHA exposures from sunless tanning products and e-cigarettes.

The photoelectrochemical performance of a BiVO4 photoanode is limited by its poor charge transport properties, despite other useful optical absorption properties. Modifying the surface charge transport properties by forming heterojunction of BiVO4 with other metal oxides layers having ultralow thickness is a promising route, as it may facilitate charge separation/transport without affecting other properties of BiVO4. In this study, the structural, optical and PEC properties of heterojunction of BiVO4 having ultrathin overlayers of Fe2O3, MoO3 and ZnO has been investigated. The electrochemical impedance (via electrochemical impedance spectra in PEC cell) and surface photovoltage (using KPFM) measurements indicates improved charge transport owing to staggered band alignment and favourable band bending in case of BiVO4/MoO3 heterojunction as compared to pristine BiVO4, BiVO4/Fe2O3 and BiVO4/ZnO heterojunctions. Enhanced photocurrent density in BiVO4/MoO3 of ~0.22 mA/cm2 at 1.23 VRHE which is 6 times as compared to pristine BiVO4 layers has been observed. The results of the present study show that by forming heterojunction with a suitable semiconductor material can be used to enhance the PEC response by modifying the surface charge transfer characteristics and there is a large possibility of using other semiconductor materials for further investigations and improvement.

Many cancers are termed immunoevasive due to expression of immunomodulatory ligands. Programmed death ligand-1 (PD-L1) and cluster of differentiation 80/86 (CD80/86) interact with their receptors, programmed death receptor-1 (PD-1) and cytotoxic T-lymphocyte antigen-4 (CTLA-4), respectively, on tumor-infiltrating leukocytes eliciting immunosuppression. Immunotherapies aimed at blocking these interactions are revolutionizing cancer treatments, albeit in an inadequately described patient subset. To address the issue of patient stratification for immune checkpoint intervention, we quantitatively imaged PD-1/PD-L1 interactions in tumor samples from patients, employing an assay that readily detects these intercellular protein–protein interactions in the less than or equal to 10 nm range. These analyses across multiple patient cohorts demonstrated the intercancer, interpatient, and intratumoral heterogeneity of interacting immune checkpoints. The PD-1/PD-L1 interaction was not correlated with clinical PD-L1 expression scores in malignant melanoma. Crucially, among anti-PD-1–treated patients with metastatic non–small cell lung cancer, those with lower PD-1/PD-L1 interaction had significantly worsened survival. It is surmised that within tumors selecting for an elevated level of PD-1/PD-L1 interaction, there is a greater dependence on this pathway for immune evasion and hence, they exhibit more impressive patient response to intervention. Significance: Quantitation of immune checkpoint interaction by direct imaging demonstrates that immunotherapy-treated patients with metastatic NSCLC with a low extent of PD-1/PD-L1 interaction show significantly worse outcome.

Modern electronic devices increasingly rely on efficient antenna integration strategies for supporting high-speed wireless connectivity. Especially for bezel-less displays, these antennas are generally placed underneath the touch sensor panel (TSP) where they interact strongly with the sensing electrodes. To overcome this problem, we engineer the shapes of these electrodes to facilitate the transmission of electromagnetic waves having frequency identical to the operating frequency of the integrated antenna. We thereby propose a new design methodology for TSP electrodes and demonstrate its advantages with respect to antenna integration. As an example, we present the design of a TSP that has a pass-band at 2.51GHz and 5.66GHz for TE polarization and 3.01GHz for TM polarization. We integrate a printed dipole antenna with the proposed as well as a standard TSP geometry, placing it right underneath rather than beside the panel. Comparing the radiation patterns at 2.5GHz, we show that the pattern is significantly different than its free-space one, when a standard TSP geometry is used. Yet, the proposed one leads to a pattern that is almost identical (improved by 3.93dB as compared to standard TSP) to that in free-space.

The considerable decline of conventional oil and gas reserves and respectively their production introduces new challenges to the energy industry. It resulted in the involvement of hard-to-recover reserves using advanced enhanced oil recovery (EOR) techniques. Thermal methods of EOR are recognized as most technically and commercially developed methods for the highly viscous crude oil. High-Pressure Air Injection (HPAI) is one of the thermal production methods that reduce oil viscosity and increases recovery. HPAI has already been effectively applied for different types of reservoirs development and proven to be economically feasible. The application performance of the HPAI technology strongly depends on the quality of experimental and numerical modeling conducted on the target object basis. Before the field tests, physicochemical and thermodynamic characteristics of the process were studied. Further consequent numerical modeling of laboratory-scale oxidation experiments and field-scale simulation was conducted to estimate HPAI method feasibility based on the results of oxidation studies. A medium pressure combustion tube (MPCT) oxidation experiment was carried out to provide stoichiometry of the reactions and field design parameters. A 3D numerical model of the MPCT experiment was constructed taking into account the multilayer design, thermal properties, heating regimes, and reaction model. The “history” matched parameters such as fluid production masses and volumes, temperature profiles along the tubes at different times and produced gas composition demonstrated good correspondence with experimental results. The results obtained during the experiment and modeling of MPCT (fluid properties, relative phase permeability, kinetic model, technological parameters) were used in field-scale modeling using various thermal EOR scenarios. Air breakthrough into production wells was observed, thus a 2 % oxygen concentration limit where implied. The overall performance of four different scenarios was compared within 30 years timeframe. The development system was also examined to achieve the maximum economic indicators with the identifications of risks and main uncertainties.

In recent years, carbon materials are widely investigated because of they are enormously sensitive to H2 at room temperature conditions. In the present work, the inexpensive candle carbon soot (CCS) is used to detect 0.5% concentration of H2 gas at room temperature. A simple flame of candle is used to synthesize the layers of carbon soot at room temperature conditions. It is observed that, the acid treatment of CCS drastically improved their structural and sensing properties as compared to as-synthesized CCS. The effect of acid functionalization on the CCS structure were investigated by X-ray diffraction (XRD) and Raman spectroscopy. To the best of our knowledge, detection of low concentrations of H2 gas is reported here for the first time using economical CCS at room temperature.

Historically, the air injection literature has stated that the main fuel for the in situ combustion (ISC) process is the carbon-rich, solid-like residue resulting from distillation, oxidation, and thermal cracking of the residual oil near the combustion front, commonly referred to as "coke". At first glance, that assumption may appear sound, since many combustion tube tests reveal a "coke bank" at the point of termination of the combustion front. However, when one examines both the laboratory results from tests conducted on various oils at reservoir conditions, and historical field data from different sources, the conclusion may be different than what has been assumed. For instance, combustion tube tests performed on light oils rarely display any significant sign of coke deposition, which would make them poor candidates for air injection; nevertheless, they have been some of the most successful ISC projects. It is proposed that the main fuel consumed by the ISC process may not be the solid-like residue, but light hydrocarbon fractions that experience combustion reactions in the gas phase. This vapor fuel forms as a result of oxidative and thermal cracking of the original and oxidized oil fractions. An analysis of different oxidation experiments performed on oil samples ranging from 6.5 to 38.8°API, at reservoir pressures, indicates that this behavior is consistent across this wide density spectrum, even in the absence of coke. While coke will form as a result of the low temperature oxidation of heavy oil fractions, and while thermal cracking of those fractions on the pathway to coke may produce vapor components which may themselves burn, the coke itself is not likely the main fuel for the process, particularly for lighter oils. This paper presents a new theory regarding the nature and formation of the main fuel utilized by the ISC process. It discusses the fundamental concepts associated with the proposed theory, and it summarizes the experimental laboratory evidence and the field evidence which support the concept. This new theory does still share much common ground with the current understanding of the ISC process, but with a twist. The new insights result from the analysis of laboratory tests performed on lighter oils at reservoir pressures; data which was not available at the time that the original ISC concepts were developed. This material suggests a complete change to one of the most important paradigms related to the ISC process, which is the nature and source of the fuel. This affects the way we understand the process, but provides a unified and consistent theory, which is important for the modelling efforts and overall development of a technology that has the potential to unlock many reserves from conventional and unconventional reservoirs.