Changes In Relative Intensities Research Articles

Hydrophilicity Dependent Distribution of Water at Ionic Liquids/Metal Interface Monitored by Electrochemical SERS.

The understanding of the interfacial processes is critically important for extending the practical application of ionic liquids, particularly for the role of interfacial water. In the electrochemical system based on ionic liquid electrolytes, small amounts of water at the interface generate a significant change in the electrochemical behaviors of ionic liquids. Therefore, the investigation on the interfacial behavior of water is highly desired in ionic liquids with different anions, water content, and hydrophilicity. Herein, based on the probe strategy, in situ surface enhanced Raman spectroscopy (SERS) combined with electrochemical control (EC-SERS) was developed to investigate the influence of hydrophilicity/hydrophobicity of ionic liquids on the interfacial water. The water-sensitive transformation reaction of 4,4'-dimercaptoazobenzene (DMAB) to para-aminothiophenol (PATP) was employed as a probe reaction for investigating the behavior of interfacial water. The changes of relative SERS intensities of DMAB to PATP served as an indication of the quantity variation of interfacial water. The results show that the transformation reaction efficiencies were critically dependent on the additional water contents, potential, and hydrophilicity of ionic liquids. With a very low molar fraction of additional water (Xw = 0.01), transformation efficiency of DMAB (the amount of interfacial water) followed the sequence of [BMIm]BF4 < [BMIm]PF6 < [BMIm]Tf2N. It was in agreement with the hydrophobicity order of the ionic liquids. With the increase in additional water content, the potential for the full transformation was positively moved, and the efficiency increased significantly. The stronger hydrophobicity allowed more water molecules to migrate to the interface, which was attributed to the difference in interactions between water and the anions of ionic liquids. It demonstrated that the small amount of water tended to gather at the interface in hydrophobic ionic liquids. Compared to traditional cyclic voltammetry, the EC-SERS technique combined with probe reactions is more sensitive to interfacial water. It is anticipated to develop as a promising tool for the investigating water-related issues at interfaces and to provide guidance to screen ionic liquids for practical application.

Source and mask optimization for stability of reticle and wafer stages

The relative motion of the reticle stage and wafer stage caused by vibration during the scanning exposure process of the lithography machine is an important factor that affects the imaging quality under limited lithography ability. In this paper, the influence of the vibration of the lithography stage system on the lithography imaging quality is studied. The lithography model including the vibration error of the stage is taken into account in the framework of source and mask optimization (SMO). For the 193-nm immersion lithography machine, combined with different design patterns with a line width of 40 nm and different vibration states of the stage when the lithography machine is exposed, the SMO joint optimization research is carried out, and the robustness of the stage under the limit process after SMO optimization is explored. The research results show that the contrast and relative light intensity change of the limit design figure under the influence of moving standard deviation (MSD) will greatly affect the linewidth at the light intensity threshold and then affect the process window (PW). The SMO including MSD allows the MSD to change in the range of 0-6 nm without changing the PW.

Experimental investigation on the gas pressure influence laws and mechanical mechanism of coal and gas outbursts

With the increasing frequency and intensity of coal and gas outburst disasters under deep mining conditions, studying the outburst mechanism of occurrence has great significance for outbursts prevention and control. The evolution law of coal and gas outbursts under different gas pressure is proposed. The outbursts law is analyzed utilizing the self-developed simulation experiment system of coal and gas outbursts, and the simulation experiment is carried out under the gas pressure of 0.45, 0.8, and 1.5 MPa. In the experiment, the gas pressure drops curves, the relative intensity change, the interval distribution of coal powder, and the evolution of outburst hole and the migration rate of coal powder are analyzed. The results indicate that (1) the gas pressure detected by the No. 4 gas pressure sensor starts to drop first; (2) the gas pressure is positively proportional to the relative outburst intensity. When the gas pressure increases from 0.45 to 0.80 MPa and then to 1.5 MPa, the farthest outburst distance of coal powder increases from 10 to 15 m and then to 21 m, and the corresponding relative outburst intensity increases from 22.94% to 35.74% and then to 45.73%, respectively. (3) The average proportion of coal particles size less than 0.28 mm and larger than 1 mm under each corresponding outburst interval is 40.75% and 22.53%, respectively. Experimental results show that the gas pressure plays an essential role in the secondary crushing and pulverization of coal samples during the outburst process. (4) The throwing velocity of the pulverized coal is increased with the gas pressure near the outburst hole. When the gas pressure is 0.8 MPa, the throwing velocity of pulverized coal reaches the maximum value of 32.40 m/s. (5) The dimensional characteristics and the location initiation of the outburst hole are obtained. The results showed that the outburst process of coal is mainly in two failure forms: pulverization and spallation. The research results provide a theoretical basis and test data support for the prevention and control of coal and gas outburst disasters.

Combining Nitellopsis obtusa autofluorescence intensity and F680/F750 ratio to discriminate responses to environmental stressors

Detection of autofluorescence parameters is a useful approach to gain insight into the physiological state of plants and algae, but the effect of reabsorption hinders unambiguous interpretation of in vivo data. The exceptional morphological features of Nitellopsis obtusa made it possible to measure autofluorescence spectra along single internodal cells and estimate relative changes in autofluorescence intensity in selected spectral regions at room temperatures, avoiding the problems associated with thick or optically dense samples. The response of algal cells to controlled white light and DCMU herbicide was analyzed by monitoring changes in peak FL intensity at 680 nm and in F680/F750 ratio. Determining the association between the selected spectral FL parameters revealed an exponential relationship, which provides a quantitative description of photoinduced changes. The ability to discern the effect of DCMU not only in the autofluorescence spectra of dark-adapted cells, but also in the case of light-adapted cells, and even after certain doses of excess light, suggests that the proposed autofluorescence analysis of N. obtusa may be useful for detecting external stressors in the field.

Thermally stable Tb3+/Sm3+-doped Lu2O2S phosphors with tunable multicolor luminescence under light and X-ray excitation

Lu2O2S has high density, high melting temperature, and favorable thermal stability, making it an excellent matrix material for rare earth luminescence and X-ray sensitization screens. However, achieving high quality fluorescent powders with high crystal quality on a large scale is still challenging. By employing an optimized solid phase approach, Lu2O2S:Tb3+/Sm3+phosphors with a hexagonal shape and uniform particle size and showing high crystallization have been successfully synthesized. Spectral analysis reveals energy interaction between Sm3+ and Tb3+ in the Lu2O2S system (multistage interaction), indicated by spectral overlap, relative changes in luminescence intensity, and lifetime decay. By changing the excitation wavelength and dopant concentration, multicolor phosphors such as yellow-–green, orange–red, and orange–yellow could be created. Temperature-dependent emission spectroscopy shows that the system shows good luminescence performance even at high temperatures. X-ray excitation spectroscopy further confirm that the phosphors emit different colors (yellow, green and red) depending on the doping concentrations of Tb3+ and Sm3+ ion, indicating that the system has wide application potential in color displays and other relevant fields.

Controllable and reversible electric field tuning of photoluminescence response in lanthanide ions doped ferroelectric films

The rare-earth doped ferroelectric photoluminescence (PL) phosphors are attracting considerable interest because of their flexible structure, wide band gap and high-quality fluorescence signal emission. Although the change of PL performance in different samples have been solved to a certain extent, how to achieve the tuning of PL intensity in one sample sensitively and reversibly is still an issue. In this work, we present an "electric-elastic-optical" coupled structure of 0.94Bi0.5Na0.5TiO3–0.06BaTiO3:1 mol%Eu3+ (BNTBT:Eu)/ 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 (PMN-PT) heterostructures, which transfers strain from the PMN-PT to the BNTBT:Eu film via the converse piezoelectric effect and dynamically modulates the PL response of the epitaxial thin film. Our findings demonstrate that the PL response of the thin film can be effectively and linearly tuned under the influence of an external electric field. The relative change in the PL intensity (ΔI/I) of the BNTBT:Eu film was found to be linearly correlated with the lateral strain of the substrate. We also propose a novel design strategy for detecting strain, with significant implications for using BNTBT:Eu/PMN-PT heterostructures as sensors for integrating piezophotonic devices. This work provides valuable insights into the feasibility of electric field tuning of PL performance, which could inspire future research endeavors in the fields of nanophotonics, optical storage technology and photovoltaics.

Static and dynamic strain-driven photoluminescence tuning in rare-earth doped perovskite oxide thin films

Recently, there have been significant interest in the wide potential of photoluminescence (PL) response of rare-earth doped perovskite oxide thin films in the field of optoelectronics. This work reports an effective method to modulate the PL properties of 0.8 mol%Sm3+-doped BaTiO3 (BTO:Sm) thin films through static and dynamic strain. BTO:Sm films were epitaxially grown on LaAlO3 (LAO), 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 (PMN-PT), MgO, and Mica single-crystal substrates by pulsed laser deposition technique. Compared with the BTO:Sm/PMN-PT heterostructure which experiences minimal lattice mismatch effect, the PL intensity of BTO:Sm/LAO and BTO:Sm/MgO is enhanced by 818.1% and 1014.7%, respectively, due to static tensile/compressive strain (-0.429% and 0.461%) during the epitaxial growth process. In the flexible BTO:Sm/Mica heterostructure, dynamic strain is introduced through mechanical bending. Compared with the unbent state, the u-type and n-type bending modes increase the relative changes in PL intensity (ΔI/I) by 599.0% and 768.5%, respectively. Particularly, BTO:Sm/Mica also exhibits a remarkable optical transmittance exceeding 75% (500–2500 nm). The enhancement of PL intensity is closely related to the adjustment of lattice strain, which changes the crystal field strength of the BTO:Sm and the radiative transition probability. This work provides valuable insights for designing future optoelectronic devices and environmental monitoring equipment. It has the potential to advance photonics and sensor technologies, paving the way for innovation and exploration in these fields.

An exploratory research report on brain mineralization in postoperative delirium and cognitive decline.

Delirium is a severe postoperative complication associated with poor overall and especially neurocognitive prognosis. Altered brain mineralization is found in neurodegenerative disorders but has not been studied in postoperative delirium and postoperative cognitive decline. We hypothesized that mineralization-related hypointensity in susceptibility-weighted magnetic resonance imaging (SWI) is associated with postoperative delirium and cognitive decline. In an exploratory, hypothesis-generating study, we analysed a subsample of cognitively healthy patients ≥65 years who underwent SWI before (N = 65) and 3months after surgery (N = 33). We measured relative SWI intensities in the basal ganglia, hippocampus and posterior basal forebrain cholinergic system (pBFCS). A post hoc analysis of two pBFCS subregions (Ch4, Ch4p) was conducted. Patients were screened for delirium until the seventh postoperative day. Cognitive testing was performed before and 3months after surgery. Fourteen patients developed delirium. After adjustment for age, sex, preoperative cognition and region volume, only pBFCS hypointensity was associated with delirium (regression coefficient [90% CI]: B = -15.3 [-31.6; -0.8]). After adjustments for surgery duration, age, sex and region volume, perioperative change in relative SWI intensities of the pBFCS was associated with cognitive decline 3months after surgery at a trend level (B = 6.8 [-0.9; 14.1]), which was probably driven by a stronger association in subregion Ch4p (B = 9.3 [2.3; 16.2]). Brain mineralization, particularly in the cerebral cholinergic system, could be a pathomechanism in postoperative delirium and cognitive decline. Evidence from our studies is limited because of the small sample and a SWI dataset unfit for iron quantification, and the analyses presented here should be considered exploratory.

Computationally assisted vibrational spectroscopy of nucleic acid bases. 2. Thymine

As in the case of cytosine [Phys. Chem. Chem. Phys. 2023, 25, 24121–24128], Raman and infrared (IR) spectra of aqueous thymine and its N-deuterated derivative, thymine-d2 have been computationally reproduced and interpreted with the use of the recently developed efficient protocol to explicit quantum mechanical modeling of structure and IR spectra of liquids and solutions [J. Phys. Chem. B, 2020, 124, 6664–6670]. A cluster model of a solute surrounded by 30 water molecules is shown to be sufficient to reproduce experimental vibrational frequencies and relative Raman intensities with the use of B3LYP-D3/def2-TZVP or B3LYP-D3/aug-cc-pVDZ simulations. Analogous PBE-D3 computations provided a less good, but still reasonably accurate, modeling of Raman spectra. It is shown that strong changes of frequencies and relative intensities of the Raman bands of thymine, caused by its hydration, can be interpreted mainly as a result of hydrogen bonding with 6 nearest water molecules. Non-negligible improvement of the quality of simulations for larger clusters comprising water molecules that do not have direct contacts with the solute, suggests that spectroscopic effects of hydration should be ascribed to the joined action of solute–solvent and solvent–solvent interactions. Nevertheless, the moderate number of water molecules required for successful simulations of the Raman spectra of aqueous thymine, suggests that the vibrational modes and derivatives of the polarizability of the solute are mainly locally influenced, while the effect of bulk water is rather modest.

Leak-out spectroscopy as alternative method to rare-gas tagging for the Renner-Teller perturbed HCCH+ and DCCD+ ions.

Infrared messenger-tagging predissociation action spectroscopy (IRPD) is a well-established technique to record vibrational spectra of reactive molecular ions. One of its major drawbacks is that the spectrum of the messenger-ion complex is taken instead of that of the bare ion. In particular for small open-shell species, such as the Renner-Teller (RT) affected HCCH+ and DCCD+, the attachment of the tag may have a significant impact on the spectral features. Here we present the application of the novel leak-out spectroscopy (LOS) as a tag-free method to record the cis-bending of the HCCH+ (∼700 cm-1) and DCCD+ cations (∼520 cm-1), using a cryogenic ion trap end user station at the FELIX laboratory. We demonstrate that the obtained LOS spectrum is equivalent to a previously recorded laser-induced reactions (LIR) spectrum of HCCH+. The bending modes are the energetically lowest-lying vibrational modes targeted with LOS so far, showing its potential as a universal broadband spectroscopic technique. Furthermore, we have investigated the effect of the rare gas attachment by recording the vibrational spectra of Ne- and Ar-tagged HCCH+. We found that the Ne-attachment led to a shift in band positions and change in relative intensities, while the Ar-attachment even led to a complete quenching of the RT splitting, showing the importance of using a tag-free method for RT affected systems. The results are interpreted with the help of high-level ab initio calculations in combination with an effective Hamiltonian approach.

Learning a Deep Demosaicing Network for Spike Camera With Color Filter Array.

For capturing dynamic scenes with ultra-fast motion, neuromorphic cameras with extremely high temporal resolution have demonstrated their great capability and potential. Different from the event cameras that only record relative changes in light intensity, spike camera fires a stream of spikes according to a full-time accumulation of photons so that it can recover the texture details for both static areas and dynamic areas. Recently, color spike camera has been invented to record color information of dynamic scenes using a color filter array (CFA). However, demosaicing for color spike cameras is an open and challenging problem. In this paper, we develop a demosaicing network, called CSpkNet, to reconstruct dynamic color visual signals from the spike stream captured by the color spike camera. Firstly, we develop a light inference module to convert binary spike streams to intensity estimates. In particular, a feature-based channel attention module is proposed to reduce the noises caused by quantization errors. Secondly, considering both the Bayer configuration and object motion, we propose a motion-guided filtering module to estimate the missing pixels of each color channel, without undesired motion blur. Finally, we design a refinement module to improve the intensity and details, utilizing the color correlation. Experimental results demonstrate that CSpkNet can reconstruct color images from the Bayer-pattern spike stream with promising visual quality.

Shedding light on the ageing of extra virgin olive oil: Probing the impact of temperature with fluorescence spectroscopy and machine learning techniques

This work systematically investigates the oxidation of extra virgin olive oil (EVOO) under accelerated storage conditions with UV absorption and total fluorescence spectroscopy. With the large amount of data collected, it proposes a method to monitor the oil's quality based on machine learning (ML) applied to highly-aggregated data.EVOO is a high-quality vegetable oil that has earned worldwide reputation for its numerous health benefits and excellent taste. Despite its outstanding quality, EVOO degrades over time due to oxidation, which can affect both its health qualities and flavour. Therefore, it is highly relevant to quantify the effects of oxidation on EVOO and develop methods to assess it that can be easily implemented under field conditions, rather than in specialized analytical laboratories.The ML approach indicates that the two excitation wavelengths (480 nm) and (300 nm) exhibit the maximum relative change in fluorescence intensity during the ageing for the majority of the oils, thus identifying the wavelengths which are more informative for quality prediction. Also, the paper proposes a method for the prediction of olive oil quality using highly-aggregated data. Such a method is of interest because it paves the way to the realization of a low-cost, portable device for in-field quality control.The following study demonstrates that fluorescence spectroscopy has the capability to monitor the effect of oxidation and assess the quality of EVOO, even when the data are highly aggregated. It shows that complex laboratory equipment is not necessary to exploit fluorescence spectroscopy using the proposed method and that cost-effective solutions, which can be used in-field by non-scientists, could provide an easily-accessible assessment of the quality of EVOO.

Self-calibrated pulse oximetry algorithm based on photon pathlength change and the application in human freedivers.

Pulse oximetry estimates the arterial oxygen saturation of hemoglobin () based on relative changes in light intensity at the cardiac frequency. Commercial pulse oximeters require empirical calibration on healthy volunteers, resulting in limited accuracy at low oxygen levels. An accurate, self-calibrated method for estimating is needed to improve patient monitoring and diagnosis. Given the challenges of calibration at low levels, we pursued the creation of a self-calibrated algorithm that can effectively estimate across its full range. Our primary objective was to design and validate our calibration-free method using data collected from human subjects. We developed an algorithm based on diffuse optical spectroscopy measurements of cardiac pulses and the modified Beer-Lambert law (mBLL). Recognizing that the photon mean pathlength () varies with related absorption changes, our algorithm aligns/fits the normalized (across wavelengths) obtained from optical measurements with its analytical representation. We tested the algorithm with human freedivers performing breath-hold dives. A continuous-wave near-infrared spectroscopy probe was attached to their foreheads, and an arterial cannula was inserted in the radial artery to collect arterial blood samples at different stages of the dive. These samples provided ground-truth via a blood gas analyzer, enabling us to evaluate the accuracy of estimation derived from the NIRS measurement using our self-calibrated algorithm. The self-calibrated algorithm significantly outperformed the conventional method (mBLL with a constant ratio) for estimation through the diving period. Analyzing 23 ground-truth data points ranging from 41% to 100%, the average absolute difference between the estimated and the ground truth is for our algorithm, significantly lower than the observed with the conventional approach. By factoring in the variations in the spectral shape of relative to , our self-calibrated algorithm enables accurate estimation, even in subjects with low levels.

Abstract 13395: Dapagliflozin Reduces Myocardial Sodium Content and Correlates With Reverse Cardiac Remodeling in Nondiabetic Patients With Heart Failure and Preserved Ejection Fraction (Dapa-Sodium)

Introduction: Myocardial sodium overload is a major determinant of adverse cardiac remodeling in heart failure (HF). Sodium tissue content by 23Na magnetic resonance imaging (23Na-MRI) has been validated in human studies. SGLT-2 inhibition blocks sodium reabsorption in renal proximal tubular cells with remarkable cardiovascular outcomes in HF due to mechanisms not yet fully understood. Hypothesis: SGLT-2 inhibition will decrease myocardial sodium content and it will correlate with reverse remodeling in HFpEF. Aim: To determine whether Dapagliflozin leads to decreased myocardial sodium content and reverses pathological hypertrophy in HFpEF. Methods: Prospective, single-center, open-label study of sixty nondiabetic outpatients with HFpEF underwent baseline 23Na-MRI and initiated with dapagliflozin 10 mg once daily according to GDMT. Absolute changes in myocardium relative sodium signal intensity (rSSI) and left ventricular mass index (LVMi) were analyzed from baseline and at 3-month follow-up with 23Na-MRI. Results: All patients exhibited significantly high baseline myocardium rSSI [0.32 (0.28, 0.34)]; 66% above median [0.24 (0.20, 0.27), P = 0.004], decreasing -30% to [0.27 (0.22, 0.30), P&lt;0.001] at 3 months with Dapagliflozin therapy. These changes were correlated with a significant reduction in LVMi of -13 g/m 2 [from 84 g/m 2 (72, 120) to 71 g/m 2 (63, 95), P&lt;0.001]. Conclusions: Dapagliflozin reduces myocardial sodium content and reverses pathological hypertrophy in patients with HFpEF. These findings suggest that SGLT-2 inhibition acts directly on cardiomyocytes and explains the cardioprotective effects demonstrated though large randomized trials.

Electronic properties of MnO(110) film grown on Cu (111)

In this study, we investigated MnO thin films grown on Cu(111) using a soft x-ray and UV based spectroscopy, low energy electron diffraction (LEED), scanning tunneling (STM) and scanning transmission electron microscopy (STEM). MnO thin film assumes (110) preferential plane orientation organized in different spatial domains to better adapt to Cu(111) surface and an in-plane/out-of-plane lattice parameter variation up to 11% with respect to bulk counterpart originating a sizeable XLD signal at Mn L2,3 edges. The formation of oxidized Cu region during the MnO thin film growth is not avoidable due to the copper reactivity to oxygen and at the interface the coexistence of MnO islands alternated with Cu2O regions was observed by STM. Mn 2p and Mn 3s core level photoemission line shapes present a slight change in multiplet peak relative intensity with respect bulk MnO counterpart due to the role of Cu substrate in the core level relaxation process. The photon energy dependent photoemission spectra of valence band discriminate the MnO states and indicate a weak influence of the substrate once the film thickness is reduced to 1 nm. These findings open new route in the tuning oxide thin film properties.

Anticoagulant drug-drug interactions with cannabinoids: Asystematic review.

This systematic review evaluates the extent to which the effect of anticoagulants may be altered in the presence of cannabinoids. The following databases were searched: EMBASE, PubMed, Web of Science, Scopus, PscycINFO, and CINAHL from database inception through May 2023. Search terms included cannabis AND anticoagulant AND drug interactions and related keywords. The major outcome was hemorrhage or thrombosis and if available the relative change in quantitative intensity of anticoagulation after cannabinoid exposure. The search generated 959 citations. After the removal of 440 duplicates, 519 citations were screened. Overall, with the exception of warfarin, evidence supporting an interaction between cannabinoids and anticoagulants is non-existent. Seven case reports evaluating an interaction with warfarin were reported. Cannabis doses involved were either extremely high (e.g., >260 mg/day of delta-9-tetrahydrocannabidiol [THC] or >600 mg/day of cannabidiol [CBD]) or were not known. Hemorrhage was identified in 14.2% (1/7) of reports and thrombosis in 0%. Quantitative anticoagulation levels were increased in patients on warfarin (elevated International Normalized Ratio [INR]) in six of seven cases. A maximum INR change was available in five of seven reports, ranging from +0.4 to +9.61. One report found no change in INR after 4 days of medical cannabis exposure. Another report outlined two separate episodes of INR elevation associated with bleeding requiring hospitalization and reversal after marijuana smoking. Four cases involved reduction in weekly warfarin dose ranging from 22% to 31%. The Drug Information Probability Score was calculated in six cases, with a score of probable for five cases and possible for one. Very low-quality data support a potential drug-drug interaction with warfarin and both THC and CBD. Clinician recognition of this potential interaction is important. Available evidence supports the need to conduct a drug interaction study between cannabinoids and warfarin to clarify the existence of an interaction.

Green production of tunable multicolor nanoparticles with diamond structure from long-flame coal by a one-step mild oxidation

The complex compositions and structural features of low-rank coal obstruct its wide use in materials applications directly. Graphene nanocarbon hydrosol with uniform particle size and containing nanodiamond structures were prepared from long-flame coal by a simple H2O2 oxidation, achieving the highest extraction rate of 30.86%, and the depolymerization degree was 80.21% when the temperature was 80 °C. The average diameter of the carbon nanoparticles was 1.86 ± 0.62 nm with 2–3 graphite flake layers, and these graphite flake layers were derived from the stable crystalline domains in the raw coal. Carbon nanoparticles exhibited good excitation wavelength-dependent and concentration-dependent fluorescence, which can be tunable from blue to green fluorescence by adjusting the concentration (0.19–1.5 g/L) and excitation wavelength (340–460 nm), the reason may be due to the combined effect of the relative intensity changes of various types of oxygenous groups, low-lying effects resulting from n(OH)→π*(CO) interactions between the hydroxyl groups and carbonyl groups, and the aggregation of particle. The post-reaction residue has a similar structural composition to that of humic acid and could be used for developing functional materials and agricultural restoration. Therefore, preparing carbon nanoparticles and humic acid by mild oxidation of hydrogen peroxide for the high-value utilization of long-flame coal has good application prospects.

The Relative Dose Intensity Changes during Cycles of Standard Regimens in Patients with Diffuse Large B-Cell Lymphoma.

No studies have focused on the trajectory of the average relative dose intensity (ARDI) during cycles of first-line chemotherapy for patients with diffuse large B-cell lymphoma. To evaluate the impact of attenuating ARDI during cycles on overall survival, we conducted a multi-centre, longitudinal, observational retrospective study. A total of 307 analysable patients were enrolled. Multivariate Cox hazards modelling with restricted cubic spline models revealed prognostic benefits of higher ARDI up to, but not after, cycle 6. According to group-based trajectory modelling, patients were classified into five groups depending on the pattern of ARDI changes. Among these, two groups in which ARDI had fallen significantly to less than 50% by cycles 4-6 displayed significantly poorer prognosis, despite increased ARDI in the second half of the treatment period (log-rank p = 0.02). The Geriatric Nutritional Risk Index offered significant prediction of unfavourable ARDI changes (odds ratio 2.540, 95% confidence interval 1.020-6.310; p = 0.044). Up to cycle 6, maintenance of ARDI in all cycles (but particularly in the early cycles) is important for prognosis. Malnutrition is a significant factor that lets patients trace patterns of ARDI changes during cycles of chemotherapy associated with untoward prognosis.

Digital traces of offline mobilization.

Since 2009, there has been an increase in global protests and related online activity. Yet, it is unclear how and why online activity is related to the mobilization of offline collective action. One proposition is that online polarization (or a relative change in intensity of posting mobilizing content around a salient grievance) can mobilize people offline. The identity-norm nexus and normative alignment models of collective action further argue that to be mobilizing, these posts need to be socially validated. To test these propositions, across two analyses, we used digital traces of online behavior and data science techniques to model people's online and offline behavior around a mass protest. In Study 1a, we used Twitter behavior posted on the day of the protest by attendees or nonattendees (759 users; 7,592 tweets) to train and test a classifier that predicted, with 80% accuracy, who participated in offline collective action. Attendees used their mobile devices to plan logistics and broadcast their presence at the protest. In Study 1b, using the longitudinal Twitter data and metadata of a subset of users from Study 1a (209 users; 277,556 tweets), we found that participation in the protest was not associated with an individual's online polarization over the year prior to the protest, but it was positively associated with the validation ("likes") they received on their relevant posts. These two studies demonstrate that rather than being low cost or trivial, socially validated online interactions about a grievance are actually key to the mobilization and enactment of collective action. (PsycInfo Database Record (c) 2023 APA, all rights reserved).

Toward Understanding Interfacial Phenomena of Anion Exchange Membrane Water Electrolyzers: Investigating the Role of Electrolyte pH Gradient with Operando Raman Spectroscopy

There is growing industrial appeal of anion exchange membrane water electrolyzers (AEMWEs) to produce hydrogen. A significant challenge remains that AEMWE durability testing is not standardized, and more minute interfacial degradation mechanisms between ionomer, catalyst, membrane, and electrolyte are not well characterized. Of particular interest is the impact of electrolyte selection on the polarization performance. There is a general desire to achieve reliable operation with environmentally obtained saltwater as the electrolyte, although this presents numerous challenges manifesting in typically poor long-term durability. Saltwater presents complexities in determining electrolyzer component interfacial phenomena.Performance of AEMWEs is typically benchmarked with hydroxide or carbonate solutions, therefore providing more direct opportunities to study fundamental mechanisms with regards to interactions between surfaces. Of particular interest is the presence of electrolyte anion concentration gradients that depend on the polarization state of the oxygen evolution reaction electrode (OER). We demonstrated in our early work with operando Raman probing of a custom designed spectroelectrochemical cell that there is initial evidence of spatially resolved anion gradients from the OER electrode surface into bulk electrolyte in a half cell configuration. We hypothesize that local pH changes near an electrode surface may impact the polarization via transport limited ion exchange and the relative overpotential of the overall cell, ultimately leading to an iterative and long-term contribution to decaying cell durability.We continue our work with a series of in-situ Raman experiments with a full cell configuration: OER electrode with PGM free catalyst, hydrogen evolution reaction (HER) electrode with PGM free catalyst, and anion conductive polymer membrane. Both electrodes also contain an ionically conductive polymer, or ionomer, that serves as a binder. By increasing the complexity of the system to match that of an industrially relevant configuration, we aim to probe the spatially resolved pH gradient with both potassium hydroxide and potassium carbonate solutions of varying concentrations. We utilized a custom, 3D printed, flow cell design comprising a sapphire observation window and isolated electrolyte flow chambers.Operando Raman spectroscopy measurements were conducted primarily with potassium carbonate solutions by tracking the spatially resolved changes in relative peak intensity of carbonate and bicarbonate signatures. With regards to the carbonate-bicarbonate equilibrium, we calculate changes in pH as the probe approaches the surface of an electrode. We finally connect our findings to a proposed mechanism for the interfacial phenomena relative to cell durability as a function of concentration changes and operating voltages.