Freezing-enhanced degradation of azo dyes in the chloride-peroxymonosulfate system.

In this study, we investigated the freezing-induced acceleration of dye bleaching by chloride-activated peroxymonosulfate (PMS). It has been observed that the oxidation of chloride by PMS generates a free chlorine species, such as hypochlorous acid (HOCl), under mild acidic and circumneutral pH condition. This process is the major reason for the enhanced oxidation capacity for electron-rich organic compounds (e.g., phenol) in the chloride-PMS system. However, we demonstrated that the chloride-PMS system clearly reduced the total organic carbon concentration (TOC), whereas the HOCl system did not lead to decrease in TOC. Overall, the chemical reaction is negligible in an aqueous condition if the concentrations of reagents are low, and freezing the solution accelerates the degradation of dye pollutants remarkably. Most notably, the pseudo-first order kinetic rate constant for acid orange 7 (AO7) degradation is approximately 0.252 h-1 with 0.5 mM PMS, 1 mM NaCl, initial pH 3, and a freezing temperature of -20 °C. AO7 degradation is not observed when the solution is not frozen. According to a confocal Raman-microscope analysis and an experiment that used an extremely high dose of reactants, the freeze concentration effect is the main reason for the acceleration phenomenon. Because the freezing phenomenon is spontaneous at high latitudes and at mid-latitudes in winter, and the chloride is ubiquitous elsewhere, the frozen chloride-PMS system has potential as a method for energy-free and eco-friendly technology for the degradation of organic pollutants in cold environments.

Targeted deletion of CD244 on monocytes promotes differentiation into anti-tumorigenic macrophages and potentiates PD-L1 blockade in melanoma.

BACKGROUND: In the myeloid compartment of the tumor microenvironment, CD244 signaling has been implicated in immunosuppressive phenotype of monocytes. However, the precise molecular mechanism and contribution of CD244 to tumor immunity in monocytes/macrophages remains elusive due to the co-existing lymphoid cells expressing CD244. METHODS: To directly assess the role of CD244 in tumor-associated macrophages, monocyte-lineage-specific CD244-deficient mice were generated using cre-lox recombination and challenged with B16F10 melanoma. The phenotype and function of tumor-infiltrating macrophages along with antigen-specific CD8 T cells were analyzed by flow cytometry and single cell RNA sequencing data analysis, and the molecular mechanism underlying anti-tumorigenic macrophage differentiation, antigen presentation, phagocytosis was investigated ex vivo. Finally, the clinical feasibility of CD244-negative monocytes as a therapeutic modality in melanoma was confirmed by adoptive transfer experiments. RESULTS: CD244fl/flLysMcre mice demonstrated a significant reduction in tumor volume (61% relative to that of the CD244fl/fl control group) 14 days after tumor implantation. Within tumor mass, CD244fl/flLysMcre mice also showed higher percentages of Ly6Clow macrophages, along with elevated gp100+IFN-γ+ CD8 T cells. Flow cytometry and RNA sequencing data demonstrated that ER stress resulted in increased CD244 expression on monocytes. This, in turn, impeded the generation of anti-tumorigenic Ly6Clow macrophages, phagocytosis and MHC-I antigen presentation by suppressing autophagy pathways. Combining anti-PD-L1 antibody with CD244-/- bone marrow-derived macrophages markedly improved tumor rejection compared to the anti-PD-L1 antibody alone or in combination with wild-type macrophages. Consistent with the murine data, transcriptome analysis of human melanoma tissue single-cell RNA-sequencing dataset revealed close association between CD244 and the inhibition of macrophage maturation and function. Furthermore, the presence of CD244-negative monocytes/macrophages significantly increased patient survival in primary and metastatic tumors. CONCLUSION: Our study highlights the novel role of CD244 on monocytes/macrophages in restraining anti-tumorigenic macrophage generation and tumor antigen-specific T cell response in melanoma. Importantly, our findings suggest that CD244-deficient macrophages could potentially be used as a therapeutic agent in combination with immune checkpoint inhibitors. Furthermore, CD244 expression in monocyte-lineage cells serve as a prognostic marker in cancer patients.

Postoperative alterations in ventriculoarterial coupling are an indicator of cardiovascular outcomes in liver transplant recipients.

BACKGROUND: Liver transplantation (LT) increases the heart and vessel workload in patients with cirrhotic cardiomyopathy. While the interaction of the left ventricle (LV) with the arterial system (ventriculoarterial coupling, VAC) is a key determinant of cardiovascular performance, little is known about changes in VAC after LT. Therefore, we evaluated the relationship between VAC after LT and cardiovascular outcomes. METHODS: 344 consecutive patients underwent echocardiographic assessments before and within 30 days after LT. Non-invasive arterial elastance (Ea), LV end-systolic elastance (Ees), and LV end-diastolic elastance (Eed) were calculated. The postoperative outcomes included the development of major adverse cardiovascular events (MACE) and the length of stay in the intensive care unit and hospital. RESULTS: A total of 240 patients were included in the analyses. After LT, Ea increased by 16% (P < 0.001), and Ees and contractility index of systolic velocity (S') increased by 18% (P < 0.001) and 7% (P < 0.001), respectively. The Eed increased by 6% (P < 0.001). The VAC remained unchanged (0.56 to 0.56, P = 0.912). Of these patients, 29 had MACE, and those with MACE had significantly higher postoperative VAC. Additionally, a higher postoperative VAC was an independent risk factor for a longer postoperative hospital stay (P = 0.038). CONCLUSIONS: These data suggest that ventriculoarterial decoupling is associated with poor postoperative outcomes after LT.

Responsive parental support buffers the link between chronic stress and cardiometabolic risk among adolescents.

Youth exposed to chronic stress exhibit increased cardiometabolic risk which parental social support may attenuate. Notably, theories emphasize that support should be delivered responsively for it to exert buffering effects, but this has not been thoroughly tested empirically. This study examined whether timing of support is an important but unrecognized element of responsiveness during adolescence in buffering the link between chronic stress and cardiometabolic risk. Participants were 242 adolescents aged 15 years (63 % female, 38 % Black). Adolescents completed assessments of chronic stress (Life Stress Interview), and trained personnel collected anthropometric measures and blood samples to assess cardiometabolic risk (reflected in low-grade inflammation and metabolic syndrome). Adolescents also completed an eight-day diary assessment to report daily stressor exposure and parental support. Using the diary data, responsiveness of parental support was operationalized as the within-individual difference in parental support received on stressor (vs. non-stressor) days, such that increased parental support on stressor days reflected more timely support. Results suggest that responsive parental support buffered the link between chronic stress and cardiovascular risk. Specifically, chronic stress was associated with greater risk only when parental support was not temporally aligned with stress exposure, but this association was not observed among adolescents who received timely parental support. These findings shed light on why parental support may not always exert buffering effects during adolescence, highlighting the importance of taking a developmental approach to understanding protective effects.

Peer support as moderator of association between socioeconomic status and low-grade inflammation in adolescents.

OBJECTIVE: Individuals who grow up in low-socioeconomic status (SES) families are at an increased risk of health problems across the lifespan. Although supportive social relationships are postulated to be a protective factor for the health of these individuals, the role of friend support in adolescence is not well understood. Given that low-grade inflammation is one key biological mechanism proposed to explain links between family SES and health outcomes, we examined whether adolescents' friend support buffers the association between family SES and low-grade inflammation among adolescents. METHOD: 277 dyads of adolescents (63.5% female; 39.4% White, 38.3% Black, and 32.1% Hispanic; Mage = 13.92 years) and one of their parents participated in this longitudinal study (two waves approximately 2 years apart). Parents reported family objective SES (i.e., income, savings, and education) and family subjective SES (i.e., subjective social status). Adolescents reported perceived friend support. Fasting antecubital blood was drawn from adolescents at both visits. Low-grade inflammatory activity was represented by a composite of inflammatory biomarkers and numbers of classical monocytes. RESULTS: Adolescents' friend support moderated the associations of family subjective SES with both the inflammation composite and classical monocyte counts across cross-sectional, longitudinal, and prospective change (only significant for the inflammation composite) analyses. Specifically, lower family subjective SES was associated with higher levels of low-grade inflammation only among adolescents lower, but not higher, in friend support. No moderation was observed for objective SES. CONCLUSION: Supportive peer relationships buffer the link between family subjective, but not objective, SES and low-grade inflammation in adolescence. (PsycInfo Database Record (c) 2024 APA, all rights reserved).

Femtosecond-resolution optical pulse interleaving time error detector.

Pulse repetition rate multiplier (PRRM) is an essential component of microwave photonics systems, designed not only to alleviate photodiode saturation but also to provide more frequent pulses. However, the presence of interleaving time errors is known to compromise the advantages of PRRM. In this study, we present a high-sensitivity detection method for identifying these time errors using an electro-optic sampling-based timing detector (EOS-TD). We utilize two EOS-TDs: one for generating precise timing ruler signals and the other as a high-precision timing detector. In comparison to the conventional power ratio comparison method, our approach demonstrates sensitivity improvement by two orders of magnitude. This enhancement facilitates the measurement of femtosecond-level time errors. By enabling higher pulse rates while maintaining the ultralow jitter, this method can be useful for building higher-speed photonic systems.

Frozen Clay Minerals as a Potential Source of Bioavailable Iron and Magnetite.

Iron (Fe) is an essential micronutrient that affects biological production. Iron-containing clay minerals are an important source of bioavailable iron. However, the dissolution of iron-containing clay minerals at temperatures below the freezing point has not been investigated. Here, we demonstrate the enhanced reductive dissolution of iron from a clay mineral in ice in the presence of iodide (I-) as the electron donor. The accelerated production of dissolved iron in the frozen state was irreversible, and the freeze concentration effect was considered the main driving force. Furthermore, the formation of magnetite (Fe3O4) after the freezing process was observed using transmission electron microscopy analysis. Our results suggest a new mechanism of accelerated abiotic reduction of Fe(III) in clay minerals, which may release bioavailable iron, Fe(II), and reactive iodine species into the natural environment. We also propose a novel process for magnetite formation in ice. The freezing process can serve as a source of bioavailable iron or act as a sink, leading to the formation of magnetite.

Synthesis of α-Branched Enones via Chloroacylation of Terminal Alkenes.

Here, we show the conversion of unactivated alkenes into α-branched enones via regioselective chloroacylation with acyl chlorides. The method relies upon the initial in situ generation of chlorine radicals directly from the acyl chloride precursor under cooperative nickel/photoredox catalysis. Subsequent HCl elimination provides enones and α,ß-unsaturated esters that are not accessible via the conventional acylation approaches that provide the other, linear constitutional isomer.

Catalytic behavior of nitrous acid for acetaminophen transformation during the freezing process.

This study demonstrates the transformation of acetaminophen by reactive nitrous acid in a frozen solution and its abnormal stoichiometry. The chemical reaction between acetaminophen and nitrous acid (AAP/NO2- system) was negligible in the aqueous solution; however, the reaction rapidly progressed if the solution started to freeze. The ultrahigh performance liquid chromatography-electrospray ionization tandem mass spectrometry measurements showed that polymerized acetaminophen and nitrated acetaminophen were formed in the proceeding reaction. Electron paramagnetic resonance spectroscopy measurements showed that nitrous acid oxidized acetaminophen via a one-electron transfer reaction producing acetaminophen-derived radical species, which is the cause of acetaminophen polymerization. We demonstrated that a relatively smaller dose of nitrite than acetaminophen caused significant acetaminophen degradation in the frozen AAP/NO2- system and revealed that the dissolved oxygen content notably affected acetaminophen degradation. We showed that the reaction occurs in a natural Arctic lake matrix (nitrite and acetaminophen spiked). Considering that the freezing phenomenon is common in the natural environment, our research provides a possible scenario for the freezing chemistry of nitrite and pharmaceuticals in environmental chemistry.

Femtosecond-precision electronic clock distribution in CMOS chips by injecting frequency comb-extracted photocurrent pulses.

A clock distribution network (CDN) is a ubiquitous on-chip element that provides synchronized clock signals to all different circuit blocks in the chip. To maximize the chip performance, today's CDN demands lower jitter, skew, and heat dissipation. Conventionally, on-chip clock signals have been distributed in the electric voltage domain, resulting in increased jitter, skew, and heat dissipation due to clock drivers. While low-jitter optical pulses have been locally injected in the chip, research on effective distribution of such high-quality clock signals has been relatively sparse. Here, we demonstrate femtosecond-precision distribution of electronic clocks using driver-less CDNs injected by photocurrent pulses extracted from an optical frequency comb source. Femtosecond-level on-chip jitter and skew can be achieved for gigahertz-rate clocking of CMOS chips by combining ultralow comb-jitter, multiple driver-less metal-meshes, and active skew control. This work shows the potential of optical frequency combs for distributing high-quality clock signals inside high-performance integrated circuits, including 3D integrated circuits.

Production of Molecular Iodine via a Redox Reaction between Iodate and Organic Compounds in Ice.

The abiotic mechanism of molecular iodine (I2) production from iodate (IO3-) remains largely unknown. Here, we demonstrate the production of I2 in the presence of IO3- and organic compounds in ice. When the solution containing IO3- (100 µM) and furfuryl alcohol (100 µM) at pH 3.0 was frozen at -20 °C, 13.1 µM of I2 was produced with complete degradation of furfuryl alcohol after 20 min. However, there was little change in the IO3- and furfuryl alcohol concentrations in water at 25 °C. The production of I2 in ice is due to the freeze concentration effect, which induces the accumulation of IO3-, furfuryl alcohol, and protons in the ice grain boundaries. This behavior facilitated the production of I2 via a redox reaction between IO3- and organic compounds. The production of I2 increased with increasing furfuryl alcohol concentration and decreasing pH. However, freezing temperature had a minor effect on the maximum production of I2. The production of I2 is highly dependent on the type of organic compounds. It was higher for organic compounds with higher electron-donating properties. This study suggests a new mechanism for I2 production, which is helpful for predicting precisely the atmospheric I2 budget in cold regions.

Massively parallel electro-optic sampling of space-encoded optical pulses for ultrafast multi-dimensional imaging.

High-speed and high-resolution imaging of surface profiles is critical for the investigation of various structures and mechanical dynamics of micro- and nano-scale devices. In particular, recent emergence of various nonlinear, transient and complex mechanical dynamics, such as anharmonic vibrations in mechanical resonators, has necessitated real-time surface deformation imaging with higher axial and lateral resolutions, speed, and dynamic range. However, real-time capturing of fast and complex mechanical dynamics has been challenging, and direct time-domain imaging of displacements and mechanical motions has been a missing element in studying full-field structural and dynamic behaviours. Here, by exploiting the electro-optic sampling with a frequency comb, we demonstrate a line-scan time-of-flight (TOF) camera that can simultaneously measure the TOF changes of more than 1000 spatial coordinates with hundreds megapixels/s pixel-rate and sub-nanometre axial resolution over several millimetres field-of-view. This unique combination of performances enables fast and precise imaging of both complex structures and dynamics in three-dimensional devices and mechanical resonators.

Substrate-Free Thermoelectric 25 µm-Thick Ag2Se Films with High Flexibility and In-Plane zT of 0.5 at Room Temperature.

Thermoelectric inorganic films are flexible when sufficiently thin. By removing the substrate, that is, making them free-standing, the flexibility of thermoelectric films can be enhanced to the utmost extent. However, studies on the flexibility of free-standing thermoelectric inorganic films have not yet been reported. Herein, the high thermoelectric performance and flexibility of free-standing thermoelectric Ag2Se films are reported. Free-standing Ag2Se films with a thickness of 25.0 ± 3.9 µm exhibited an in-plane zT of 0.514 ± 0.060 at room temperature. These films exhibited superior flexibility compared to Ag2Se films constrained on a substrate. The flexibility of the Ag2Se films was systematically investigated in terms of bending strain, bending radius, thickness, and elastic modulus. Using free-standing Ag2Se films, a substrate-free, flexible thermoelectric generator was fabricated. The energy-harvesting capacity of the thermoelectric generator was also demonstrated.

Ice-templated synthesis of tungsten oxide nanosheets and their application in arsenite oxidation.

Tungsten oxide (WO3) nanosheets were prepared as catalysts to activate hydrogen peroxide (H2O2) in arsenite (As(III)) oxidation. Ice particles were employed as templates to synthesize the WO3 nanosheets, enabling easy template removal via melting. Transmission electron microscopy and atomic force microscopy revealed that the obtained WO3 nanosheets were plate-like, with lateral sizes ranging from dozens of nanometers to hundreds of nanometers and thicknesses of <10 nm. Compared to that of the WO3 nanoparticle/H2O2 system, a higher efficiency of As(III) oxidation was observed in the WO3 nanosheet/H2O2 system. Electron spin resonance spectroscopy, radical quenching studies, and As(III) oxidation experiments under anoxic conditions suggested that the hydroperoxyl radical (HO2●) acted as the primary oxidant. The WO3 nanosheets possessed numerous surface hydroxyl groups and electrophilic metal centers, enhancing the production of HO2● via H2O2 activation. Various anions commonly present in As(III)-contaminated water exhibited little effect on As(III) oxidation in the WO3 nanosheet/H2O2 system. The high oxidation efficiency was maintained by adding H2O2 when it was depleted, suggesting that the catalytic activity of the WO3 nanosheets did not deteriorate after multiple catalytic cycles.

Technetium-99m hand perfusion scintigraphy (Raynaud's scan) as a method of verification in hand arm vibration syndrome: a review.

It is important to assess the blood flow of fingers in the verification of hand-arm vibration syndrome. In the Republic of Korea, most assessments of the blood flow in the fingers are performed using a cold provocation test with finger skin color change. However, this test is a non-objective method with a relatively low sensitivity, leading to possible social and legal problems. Thus, we reviewed the characteristics of several tests that assess the blood flow in the fingers. Among these tests, using the radioactive isotope method, Raynaud's scan has a relatively higher sensitivity and specificity than other tests, provides objective results, and is approachable in many hospitals. So we suggest using Raynaud's scan as an alternative test when cold provocation test with finger skin color change is negative in vibration exposed worker.

Highly Bright Silica-Coated InP/ZnS Quantum Dot-Embedded Silica Nanoparticles as Biocompatible Nanoprobes.

Quantum dots (QDs) have outstanding optical properties such as strong fluorescence, excellent photostability, broad absorption spectra, and narrow emission bands, which make them useful for bioimaging. However, cadmium (Cd)-based QDs, which have been widely studied, have potential toxicity problems. Cd-free QDs have also been studied, but their weak photoluminescence (PL) intensity makes their practical use in bioimaging challenging. In this study, Cd-free QD nanoprobes for bioimaging were fabricated by densely embedding multiple indium phosphide/zinc sulfide (InP/ZnS) QDs onto silica templates and coating them with a silica shell. The fabricated silica-coated InP/ZnS QD-embedded silica nanoparticles (SiO2@InP QDs@SiO2 NPs) exhibited hydrophilic properties because of the surface silica shell. The quantum yield (QY), maximum emission peak wavelength, and full-width half-maximum (FWHM) of the final fabricated SiO2@InP QDs@SiO2 NPs were 6.61%, 527.01 nm, and 44.62 nm, respectively. Moreover, the brightness of the particles could be easily controlled by adjusting the amount of InP/ZnS QDs in the SiO2@InP QDs@SiO2 NPs. When SiO2@InP QDs@SiO2 NPs were administered to tumor syngeneic mice, the fluorescence signal was prominently detected in the tumor because of the preferential distribution of the SiO2@InP QDs@SiO2 NPs, demonstrating their applicability in bioimaging with NPs. Thus, SiO2@InP QDs@SiO2 NPs have the potential to successfully replace Cd-based QDs as highly bright and biocompatible fluorescent nanoprobes.

Calcipotriol, a synthetic Vitamin D analog, promotes antitumor immunity via CD4+T-dependent CTL/NK cell activation.

To overcome the hurdles of immunotherapy, we investigated whether calcipotriol, a synthetic vitamin D analog, could overcome the immune evasion of glioblastoma multiforme (GBM) by modulating immune responses and the immunosuppressive tumor microenvironment. Administration of calcipotriol considerably reduced tumor growth. Both in vivo and in vitro studies revealed that CD8+T and natural killer (NK) cell gene signatures were enriched and activated, producing high levels of IFN-γ and granzyme B. In contrast, regulatory T cells (Treg) were significantly reduced in the calcipotriol-treated group. The expression of CD127, the receptor for thymic stromal lymphopoietin (TSLP), is elevated in CD4+T cells and potentially supports T-cell priming. Depleting CD4+T cells, but not NK or CD8+T cells, completely abrogated the antitumor efficacy of calcipotriol. These data highlight that the calcipotriol/TSLP/CD4+T axis can activate CD8+T and NK cells with a concomitant reduction in the number of Tregs in GBM. Therefore, calcipotriol can be a novel therapeutic modality to overcome the immune resistance of GBM by converting immunologically "cold" tumors into "hot" tumors. DATA AVAILABILITY: Data are available upon reasonable request. The RNA-seq dataset comparing the transcriptomes of control and calcipotriol-treated GL261 tumors is available from the corresponding author upon request.

Chip-scale power booster for light.

A miniature amplifier with high power is realized with an ion-doped waveguide.

Targeting TCTP sensitizes tumor to T cell-mediated therapy by reversing immune-refractory phenotypes.

Immunotherapy has emerged as a powerful approach to cancer treatment. However, immunotherapeutic resistance limits its clinical application. Therefore, identifying immune-resistant factors, which can be targeted by clinically available drugs and it also can be a companion diagnostic marker, is needed to develop combination strategies. Here, using the transcriptome data of patients, and immune-refractory tumor models, we identify TCTP as an immune-resistance factor that correlates with clinical outcome of anti-PD-L1 therapy and confers immune-refractory phenotypes, decreased T cell trafficking to the tumor and resistance to cytotoxic T lymphocyte-mediated tumor cell killing. Mechanistically, TCTP activates the EGFR-AKT-MCL-1/CXCL10 pathway by phosphorylation-dependent interaction with Na, K ATPase. Furthermore, treatment with dihydroartenimsinin, the most effective agent impending the TCTP-mediated-refractoriness, synergizes with T cell-mediated therapy to control immune-refractory tumors. Thus, our findings suggest a role of TCTP in promoting immune-refractoriness, thereby encouraging a rationale for combination therapies to enhance the efficacy of T cell-mediated therapy.