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At least 235 records · Page 13

Programmable hydrogels by combining persistent and transient dynamic bonds

Out-of-equilibrium chemistry is currently being applied to polymer systems to mimic the autonomous behavior of biological materials. In this study, hydrogels with self-healing properties were developed that combine persistent crosslinks from dynamic metal-ligand coordination with transient crosslinks from dynamic anhydride bonds. Polymers containing terpyridine ligands and carboxylic acid groups were synthesized and crosslinked with divalent metal ions (Fe 2+ , Ni 2+ , Co 2+ , Zn 2+ , Cu 2+ ). The coordination bonds from terpyridine–metal coordination impart persistent stability, while transient anhydrides formed on treatment with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) temporarily increase crosslink density. Distinct behaviors are observed depending on the choice of metal, with Ni 2+ forming robust, stable networks; Zn 2+ creating moderately dynamic gels; and Cu 2+ yielding highly dynamic, soft materials. Treatment with EDC increased storage moduli significantly, with transient effects lasting up to 280 min depending on the metal ion. Self-healing experiments demonstrated independent contributions from metal coordination and transient anhydrides, enabling recovery of stress and strain under varying conditions. Additionally, complex and reversible 2D stiffness patterns were generated by spatially controlled EDC treatment of Zn 2+ and Cu 2+ hydrogel films, demonstrating programmability and reusability.

Rajawasam, Chamoni W. H. [Miami University, Oxford↗

Prenatal exposure to mixtures of persistent endocrine disrupting chemicals and postnatal body size in British girls

Endocrine disrupting chemical (EDC) exposure is ubiquitous. EDC exposure during critical windows of development may interfere with the body's endocrine system, affecting growth. Previous human studies have examined one EDC at a time in relation to infant growth. By studying mixtures, the human experience can be better approximated. We investigated the association of prenatal exposure to persistent EDCs (per- and polyfluoroalkyl substances (PFAS), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs)) as mixtures with postnatal body size among female offspring. We used a sub-sample of the Avon Longitudinal Study of Parents and Children (N = 425), based in the United Kingdom. We quantified 52 EDCs in maternal serum collected during pregnancy. We used Bayesian kernel machine regression with a random intercept to examine the association of prenatal concentrations of EDC mixtures with longitudinal postnatal body size measures for each EDC class separately (PFAS, PCBs, and OCPs) and for all three classes combined. Weight and height measures at 0, 2, 9, and 19 months were obtained by health professionals as part of routine child health surveillance. The mixture representing all three classes combined (31 chemicals) (n = 301) was inversely associated with postnatal body size. Holding all EDCs in the 31-chemical mixture at the 75th percentile compared to the 50th percentile was associated with 0.15 lower weight-for-age z-score (95% credible interval –0.26, –0.03). Weak inverse associations were also seen for height-for-age and body mass index-for-age scores. Furthermore, these results suggest that prenatal exposure to mixtures of persistent EDCs may affect postnatal body size.

59 BASIC BIOLOGICAL SCIENCES↗

Significant accumulation of persistent organic pollutants and dysregulation in multiple DNA damage repair pathways in the electronic-waste-exposed populations

Electronic waste (e-waste) has created a worldwide environmental and health problem, by generating a diverse group of hazardous compounds such as persistent organic pollutants (POPs). Our previous studies demonstrated that populations from e-waste exposed region have a significantly higher level of chromosomal aberrancy and incidence of DNA damage. In this study, we further demonstrated that various POPs persisted at a significantly higher concentration in the exposed group than those in the unexposed group. The level of reactive oxygen species and micronucleus rate were also significantly elevated in the exposed group. RNA sequencing analysis revealed 31 genes in DNA damage responses and repair pathways that were differentially expressed between the two groups (Log 2 ratio >1 or <−1). Our data demonstrated that both females and males of the exposed group have activated a series of DNA damage response genes; however many important DNA repair pathways have been dysregulated. Expressions of NEIL1/3 and RPA3, which are critical in initiating base pair and nucleotide excision repairs respectively, have been downregulated in both females and males of the exposed group. In contrast, expression of RNF8, an E3 ligase involved in an error prone non-homologous end joining repair for DNA double strand break, was upregulated in both genders of the exposed group. The other genes appeared to be differentially expressed only when the males or females of the two groups were compared respectively. Importantly, the expression of cell cycle regulatory gene CDC25A that has been implicated in multiple kinds of malignant transformation was significantly upregulated among the exposed males while downregulated among the exposed females. In conclusion, our studies have demonstrated significant correlations between e-waste disposing and POPs accumulation, DNA lesions and dysregulation of multiple DNA damage repair mechanisms in the residents of the e-waste exposed region. - Highlights: • We compared concentration of POPs, ROS and micronucleus rate in POPs exposed area. • Significant accumulation of POPs homologous in the e-waste exposed residents. • DNA damage and DNA damage repair pathways have been differentially activated. • Females and males in the exposed group have different responses to the DNA damage. • Exposed males may be more prone to undergo malignant transformation.

54 ENVIRONMENTAL SCIENCES↗

Bioaccumulation of persistent and emerging pollutants in wild sea urchin Paracentrotus lividus

Highlights: • Bioaccumulation of 99 organic contaminants were assessed in wild sea urchin. • 40 emerging and persistent organic contaminants were detected, generally at low levels. • Differences were found between sampling sites, Carreço being the least impacted area. Marine pollution has been increasing as a consequence of anthropogenic activities. The preservation of marine ecosystems, as well as the safety of harvested seafood, are nowadays a global concern. Here, we report for the first time the contamination levels of a large set of 99 emerging and persistent organic contaminants (butyltins (BTs), polycyclic aromatic hydrocarbons (PAHs), pesticides including pyrethroids, pharmaceuticals and personal care products (PCPs) and flame retardants) in roe/gonads of sea urchin Paracentrotus lividus. Sea urchins are a highly prized worldwide delicacy, and the harvesting of this seafood has increased over the last decades, particularly in South West Atlantic coast, where this organism is harvested mainly for exportation. Sampling was performed in three harvesting sites of the NW Portuguese coast subjected to distinct anthropogenic pressures: Carreço, Praia Norte and Vila Chã, with sea urchins being collected in the north and south areas of each site. Butyltins and pharmaceuticals were not found at measurable levels. Several PAHs, four pyrethroids insecticides, four PCPs and eleven flame retardants were found in roe/gonads of sea urchins, though in general at low levels. Differences among harvesting sites and between areas within each site were found, the lowest levels of contaminants being registered in Carreço. The accumulation of contaminants in sea urchins’ roe/gonads seemed to reflect the low anthropogenic pressure felt in the sampling sites. Nevertheless, taking into account the low accumulated levels of chemicals, results indicate that sea urchins collected in South West Atlantic coast are safe for human consumption.

54 ENVIRONMENTAL SCIENCES↗

Induction and Persistence of Large γH2AX Foci by High Linear Energy Transfer Radiation in DNA-Dependent protein kinase–Deficient Cells

Purpose: To evaluate the cell response to DNA double-strand breaks induced by low and high linear energy transfer (LET) radiations when the catalytic subunit of DNA-dependent protein kinase (DNA-PKcs), an essential protein of the nonhomologous end-joining repair pathway, lacks kinase activity. Methods and Materials: CHO10B2, a Chinese hamster ovary cell line, and its derived radiosensitive mutant cell line, irs-20, lacking DNA-PKcs activity, were evaluated after 0 to 3 Gy of γ-rays, plateau and Bragg peak protons, and lithium beams by clonogenic assay, and as a measurement of double-strand breaks, phosphorylated H2AX (γH2AX) foci number and size were quantified by immunocytofluorescence. Results: Irs-20 exhibited greater radiosensitivity and a higher amount of γH2AX foci than CHO10B2 at 6 hours after irradiation for all types of radiations. Remarkably, CHO10B2 and irs-20 maintained their difference in radiosensitivity after high-LET radiation. Six hours after low-LET radiations, irs-20 did not reach basal levels of γH2AX at high doses, whereas CHO10B2 recovered basal levels for all doses. After high-LET radiation, only CHO10B2 exhibited a reduction in γH2AX foci, but it never reached basal levels. Persistent foci in irs-20 confirmed a repair deficiency. Interestingly, after 30 minutes of high-LET radiation both cell lines exhibited large foci (size >0.9 μm{sup 2}) related to the damage nature, whereas at 6 hours irs-20 showed a higher amount of large foci than CHO10B2, with a 7-fold increase at 3 Gy, that could also be associated to radiosensitivity. Conclusions: We demonstrated, for the first time, an association between deficient DNA-PKcs activity and not only high levels of H2AX phosphorylation but also persistence and size increase of γH2AX foci after high-LET irradiation.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Prostate-Specific Antigen Persistence After Radical Prostatectomy as a Predictive Factor of Clinical Relapse-Free Survival and Overall Survival: 10-Year Data of the ARO 96-02 Trial

Objective: The ARO 96-02 trial primarily compared wait-and-see (WS, arm A) with adjuvant radiation therapy (ART, arm B) in prostate cancer patients who achieved an undetectable prostate-specific antigen (PSA) after radical prostatectomy (RP). Here, we report the outcome with up to 12 years of follow-up of patients who retained a post-RP detectable PSA and received salvage radiation therapy (SRT, arm C). Methods and Materials: For the study, 388 patients with pT3-4pN0 prostate cancer with positive or negative surgical margins were recruited. After RP, 307 men achieved an undetectable PSA (arms A + B). In 78 patients the PSA remained above thresholds (median 0.6, range 0.05-5.6 ng/mL). Of the latter, 74 consented to receive 66 Gy to the prostate bed, and SRT was applied at a median of 86 days after RP. Clinical relapse-free survival, metastasis-free survival, and overall survival were determined by the Kaplan-Meier method. Results: Patients with persisting PSA after RP had higher preoperative PSA values, higher tumor stages, higher Gleason scores, and more positive surgical margins than did patients in arms A + B. For the 74 patients, the 10-year clinical relapse-free survival rate was 63%. Forty-three men had hormone therapy; 12 experienced distant metastases; 23 patients died. Compared with men who did achieve an undetectable PSA, the arm-C patients fared significantly worse, with a 10-year metastasis-free survival of 67% versus 83% and overall survival of 68% versus 84%, respectively. In Cox regression analysis, Gleason score ≥8 (hazard ratio [HR] 2.8), pT ≥ 3c (HR 2.4), and extraprostatic extension ≥2 mm (HR 3.6) were unfavorable risk factors of progression. Conclusions: A persisting PSA after prostatectomy seems to be an important prognosticator of clinical progression for pT3 tumors. It correlates with a higher rate of distant metastases and with worse overall survival. A larger prospective study is required to determine which patient subgroups will benefit most from which treatment option.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Inhibition of Bcl-2/xl With ABT-263 Selectively Kills Senescent Type II Pneumocytes and Reverses Persistent Pulmonary Fibrosis Induced by Ionizing Radiation in Mice

Purpose: Ionizing radiation (IR)–induced pulmonary fibrosis (PF) is an irreversible and severe late effect of thoracic radiation therapy. The goal of this study was to determine whether clearance of senescent cells with ABT-263, a senolytic drug that can selectively kill senescent cells, can reverse PF. Methods and Materials: C57BL/6J mice were exposed to a single dose of 17 Gy on the right side of the thorax. Sixteen weeks after IR, they were treated with 2 cycles of vehicle or ABT-263 (50 mg/kg per day for 5 days per cycle) by gavage. The effects of ABT-263 on IR-induced increases in senescent cells; elevation in the expression of selective inflammatory cytokines, matrix metalloproteinases, and tissue inhibitors of matrix metalloproteinases; and the severity of the tissue injury and fibrosis in the irradiated lungs were evaluated 3 weeks after the last treatment, in comparison with the changes observed in the irradiated lungs before treatment or after vehicle treatment. Results: At 16 weeks after exposure of C57BL/6 mice to a single dose of 17 Gy, thoracic irradiation resulted in persistent PF associated with a significant increase in senescent cells. Treatment of the irradiated mice with ABT-263 after persistent PF had developed reduced senescent cells and reversed the disease. Conclusions: To our knowledge, this is the first study to demonstrate that PF can be reversed by a senolytic drug such as ABT-263 after it becomes a progressive disease. Therefore, ABT-263 has the potential to be developed as a new treatment for PF.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Long-persistent luminescence in near-ultraviolet from silicon nanowires

Graphical abstract: Silicon-rich nanowires with persistent near-ultraviolet luminescence were fabricated with thermal evaporation of silicon monoxide (SiO) powder at 1350 K. They contain quantum-confined elemental silicon structures of the order of nm dimension, and are capped by silicon oxide. The samples exhibit orderly color distribution along the direction of the carrier gas flow. When excited with the 280 nm light, the samples emit broad photoluminescence band from 330 to 470 nm with a long afterglow of more than 10 s, and the color shifts from near-ultraviolet to blue and green gradually. Display Omitted Highlights: ► We synthesized Si-rich nanowire from thermal evaporation of silicon monoxide. ► The Si-rich nanowires exhibit orderly color distribution along the direction of the gas flow. ► The Si-rich nanowires emit broad photoluminescence band from 330 to 470 nm under UV irradiation for >10 s. ► The color shifts from near-ultraviolet to blue and green gradually. -- Abstract: Silicon-rich nanowires with persistent near-ultraviolet luminescence were fabricated with thermal evaporation of silicon monoxide (SiO) powder at 1350 K. They contain quantum-confined elemental silicon structures of the order of nm dimension, and are capped by silicon oxide. The samples exhibit orderly color distribution along the direction of the carrier gas flow. When excited with the 280 nm light, the samples emit broad photoluminescence band from 330 to 470 nm with a long afterglow of more than 10 s, and the color shifts from near-ultraviolet to blue and green gradually. The morphology dependent luminescence might be attributed to the emission from the quantum-confined silicon crystallites of various sizes embedded in the oxide layer, and near surface states in the nanowires.

36 MATERIALS SCIENCE↗

Red persistent luminescence in rare earth-free AlN:Mn 2+ phosphor

Here, we investigated the persistent luminescence (PersL) properties of a rare earth-free Mn 2+ doped AlN (AlN:Mn) red phosphor together with a commercial SrAl 2 O 4 :Eu 2+ , Dy 3+ green persistent phosphor as a reference. Similar to its photoluminescence (PL) spectrum, the PersL spectrum of the AlN:Mn phosphor exhibited a red emission band centered at 600 nm due to the Mn 2+ : 4 T 1 ( 4 G) → 6 A 1 ( 6 S) transition with a relatively narrow full width at half maximum (FWHM) of 43 nm. The luminance of AlN:Mn powders was 0.65 mcd/m 2 at 60 min after ceasing ultraviolet (UV) illumination, and its duration upon 0.32 mcd/m 2 could reach over 110 min. An extremely broad thermoluminescence (TL) glow curve was observed ranging from 100 K to 600 K and peaked at around 310 K, indicating a wide trap distribution in this material.

36 MATERIALS SCIENCE↗

Effects of defined mixtures of persistent organic pollutants (POPs) on multiple cellular responses in the human hepatocarcinoma cell line, HepG2, using high content analysis screening

Persistent organic pollutants (POPs) are toxic substances, highly resistant to environmental degradation, which can bio-accumulate and have long-range atmospheric transport potential. Most studies focus on single compound effects, however as humans are exposed to several POPs simultaneously, investigating exposure effects of real life POP mixtures on human health is necessary. A defined mixture of POPs was used, where the compound concentration reflected its contribution to the levels seen in Scandinavian human serum (total mix). Several sub mixtures representing different classes of POPs were also constructed. The perfluorinated (PFC) mixture contained six perfluorinated compounds, brominated (Br) mixture contained seven brominated compounds, chlorinated (Cl) mixture contained polychlorinated biphenyls and also p,p’-dichlorodiphenyldichloroethylene, hexachlorobenzene, three chlordanes, three hexachlorocyclohexanes and dieldrin. Human hepatocarcinoma (HepG2) cells were used for 2 h and 48 h exposures to the seven mixtures and analysis on a CellInsight™ NXT High Content Screening platform. Multiple cytotoxic endpoints were investigated: cell number, nuclear intensity and area, mitochondrial mass and membrane potential (MMP) and reactive oxygen species (ROS). Both the Br and Cl mixtures induced ROS production but did not lead to apoptosis. The PFC mixture induced ROS production and likely induced cell apoptosis accompanied by the dissipation of MMP. Synergistic effects were evident for ROS induction when cells were exposed to the PFC + Br mixture in comparison to the effects of the individual mixtures. No significant effects were detected in the Br + Cl, PFC + Cl or total mixtures, which contain the same concentrations of chlorinated compounds as the Cl mixture plus additional compounds; highlighting the need for further exploration of POP mixtures in risk assessment. - Highlights: • High content analysis (HCA) is a novel approach for determining toxicity of complex mixtures. • Multiple cytotoxic endpoints were investigated for defined mixtures of persistent organic pollutants (POPs). • POP mixtures are based on levels relevant to human exposure. • POP mixtures can increase ROS induction and impact mitochondrial health, which could result in apoptosis. • HCA can detect pre-lethal and reversible signs of cellular stress.

60 APPLIED LIFE SCIENCES↗

Persistent human Borna disease virus infection modifies the acetylome of human oligodendroglia cells towards higher energy and transporter levels

Background: Borna disease virus (BDV) is a neurotropic RNA virus persistently infecting mammalian hosts including humans. Lysine acetylation (Kac) is a key protein post-translational modification (PTM). The unexpectedly broad regulatory scope of Kac let us to profile the entire acetylome upon BDV infection. Methods: The acetylome was profiled through stable isotope labeling for cell culture (SILAC)-based quantitative proteomics. The quantifiable proteome was annotated using bioinformatics. Results: We identified and quantified 791 Kac sites in 473 Kac proteins in human BDV Hu-H1-infected and non-infected oligodendroglial (OL) cells. Bioinformatic analysis revealed that BDV infection alters the acetylation of metabolic proteins, membrane-associated proteins and transmembrane transporter activity, and affects the acetylation of several lysine acetyltransferases (KAT). Conclusions: Upon BDV persistence the OL acetylome is manipulated towards higher energy and transporter levels necessary for shuttling BDV proteins to and from nuclear replication sites. - Highlights: • We used SILAC-based proteomics to analyze the acetylome of BDV infected OL cells. • We quantified 791Kac sites in 473 proteins. • Bioinformatic analysis revealed altered acetylation of metabolic proteins et al. • BDV manipulates the OL acetylome towards higher energy and transporter levels. • BDV infection is associated with enriched phosphate-associated metabolic processes.

60 APPLIED LIFE SCIENCES↗

Planning for sustained water-electricity resilience over the U.S.: Persistence of current water-electricity operations and long-term transformative plans

The electricity system relies upon the availability and predictability of water to support hydropower operations and cooling of thermoelectric plants, implying that water plays a fundamental role in power operations and that water-related stresses may have a critical effect on the electricity system. Designing for electricity system resilience to changing societal demands and environmental conditions is a complex and urgent endeavor, one that requires robust diagnosis and an articulation of interdependencies among key system components. Here we consider the argument that water may help to navigate that complexity, revealing thresholds for system change and the transformations that may be required for enduring resilience of the electricity sector. To assess this thesis, we apply a framework for understanding resilient systems following Folke et al., that is extended in this special issue, by which resilience comprises three capabilities: system persistence, adaptability, and transformation. We apply this resilience diagnosis approach to the bulk electricity system of the contiguous United States, with particular attention to water-driven stressors. We provide a qualitative narrative that discusses the spectrum of resilience capabilities (persistence, adaptability, and transformability) of the water-electricity system in the United States over three scales of inter-dependencies: individual power plant, urban and grid scales.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Shape-persistent phthalocyanine cages

Phthalocyanine (Pc), an electro-redox active moiety, has many attractive properties stemming from its large aromatic system and ability to act as a catalyst in electrochemical reactions, such as the CO 2 reduction reaction (CO 2 RR). However, due to the synthetic challenge related to geometric requirements and poor solubility (strong aggregation), discrete shape-persistent cages consisting of site-isolated, readily accessible Pc moieties have not been available. Here, we report the synthesis of Zn- and Ni-metallated Pc-based molecular cages via one-step dynamic spiroborate linkage formation in high yields. The ZnPc cage structure is unambiguously elucidated at the atomic level by single-crystal X-ray diffraction. Moreover, owing to the site-isolated redox-active metal centers, readily accessible intrinsic cavity, and shape-persistent backbone, the Ni-metallated Pc (NiPc) cage exhibits high catalytic efficiency, selectivity, and stability, superior to the non-caged control molecules in electrocatalytic CO 2 RR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interaction of Soil pH and Mineralogy Controls Soil Organic Matter Persistence through Changes in the Composition and Amount of Microbial Necromass

Microbial necromass–mineral associations are key to long-term soil organic matter (SOM) persistence. However, how soil pH and mineralogy interact to regulate SOM stability remains poorly understood. Here, we used artificial soils to test how three clay minerals (bentonite, kaolinite, and goethite), adjusted to four pH levels (5–8), affect microbial activity (respiration), microbial physiology (carbon use efficiency, CUE), microbial-derived residue material (necromass), and the formation and stability of mineral-associated organic matter (MAOM). Artificial soils were inoculated with a rhizosphere-derived microbial community cultured under the same pH conditions and on two representative simulated exudate types (organic acids and carbohydrates) and incubated for 6 weeks. In two complementary experiments, we added necromass from known microbial taxa to the same minerals across pH levels to isolate the role of necromass chemistry and loading. We found that soil pH shaped MAOM chemistry by altering microbial activity and necromass composition. In interaction with mineral type, pH also controlled MAOM thermal stability. Higher necromass loading weakened mineral-organic bonding, reducing MAOM stability, consistent with zonal mineral–organic interaction models. Our results demonstrate that microbial activity, rather than carbon use efficiency, better predicts MAOM formation and that pH-dependent necromass composition and loading govern MAOM persistence. These findings advance mechanistic understanding of SOM stabilization and have implications for predicting soil carbon dynamics under shifting environmental conditions.

carbon use efficiency↗

Uranyl Peroxide Nanocluster (U 60 ) Persistence and Sorption in the Presence of Hematite

The presence of uranium-based nanomaterials in environmental systems may significantly impact our current understanding of the fate and transport of U(VI). Sorption of the uranyl peroxide nanocluster [(UO 2 )(O 2 )(OH)] 60 60– (U 60 ) to hematite (α-Fe 2 O 3 ) was studied using batch sorption experiments with varying U 60 , hematite, and alkali electrolyte (i.e., NaCl, KCl, and CsCl) concentrations. Data from electrospray ionization mass spectrometry and centrifugal microfiltration revealed that U 60 persisted in the presence of hematite and the background electrolyte for at least 120 days. K + ions were removed from solution with uranium whereas Li + ions remained in solution, indicating that the U 60 cluster behaved like an anion and that the Li + ions did not play a significant role in the sorption mechanism. Analysis of the reacted mineral surface using X-ray photoelectron and Raman spectroscopies confirmed the presence of U(VI) and uranyl species with bridged peroxo groups associated with the mineral surface. These results indicate that uranyl peroxide nanoclusters may persist in the aqueous phase under environmentally relevant conditions for reasonably long periods of time, as compared to that of the uranyl cation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

More Frequent and Persistent Heatwaves Due To Increased Temperature Skewness Projected by a High‐Resolution Earth System Model

Abstract Heatwaves are strongly associated with temperature distributions, but the mechanisms by which distributions are influenced by climate change remains unclear. Comparing simulations from a high‐spatial resolution Community Earth System Model (CESM‐HR) with those from low‐resolution models, we identify substantial improvements by CESM‐HR in reproducing observed Northern Hemisphere summer temperature skewness, as well as the frequency, intensity, persistence, and total heatwave days. Temperature skewness is strongly linked to land‐atmosphere interactions and atmospheric circulation. Under global warming projections, some regions exhibit enhanced temperature skewness, along with more frequent and persistent heatwaves of greater intensity. We find that in energy‐limited regimes, such as India, negative skewness in latent heat flux facilitates large positive skewness in sensible heat flux, which modulates near‐surface air temperatures. Skewness differences of latent and sensible heat fluxes are amplified under global warming, increasing the temperature skewness. We find that this contrasting flux mechanism is active in several heatwave‐prone regions.

Gao, Yang↗

Spin-orbital coupling and slow phonon effects enabled persistent photoluminescence in organic crystal under isomer doping

When periodically packing the intramolecular donor-acceptor structures to form ferroelectric-like lattice identified by second harmonic generation, our CD49 molecular crystal shows long-wavelength persistent photoluminescence peaked at 542 nm with the lifetime of 0.43 s, in addition to the short-wavelength prompt photoluminescence peaked at 363 nm with the lifetime of 0.45 ns. Interestingly, the long-wavelength persistent photoluminescence demonstrates magnetic field effects, showing as crystalline intermolecular charge-transfer excitons with singlet spin characteristics formed within ferroelectric-like lattice based on internal minority/majority carrier-balancing mechanism activated by isomer doping effects towards increasing electron-hole pairing probability. Our photoinduced Raman spectroscopy reveals the unusual slow relaxation of photoexcited lattice vibrations, indicating slow phonon effects occurring in ferroelectric-like lattice. Here, we show that crystalline intermolecular charge-transfer excitons are interacted with ferroelectric-like lattice, leading to exciton-lattice coupling within periodically packed intramolecular donor-acceptor structures to evolve ultralong-lived crystalline light-emitting states through slow phonon effects in ferroelectric light-emitting organic crystal.

36 MATERIALS SCIENCE↗

Calcium promotes persistent soil organic matter by altering microbial transformation of plant litter

Abstract Calcium (Ca) can contribute to soil organic carbon (SOC) persistence by mediating physico-chemical interactions between organic compounds and minerals. Yet, Ca is also crucial for microbial adhesion, potentially affecting colonization of plant and mineral surfaces. The importance of Ca as a mediator of microbe-mineral-organic matter interactions and resulting SOC transformation has been largely overlooked. We incubated 44 Ca labeled soils with 13 C 15 N labeled leaf litter to study how Ca affects microbial transformation of litter and formation of mineral associated organic matter. Here we show that Ca additions promote hyphae-forming bacteria, which often specialize in colonizing surfaces, and increase incorporation of litter into microbial biomass and carbon use efficiency by approximately 45% each. Ca additions reduce cumulative CO 2 production by 4%, while promoting associations between minerals and microbial byproducts of plant litter. These findings expand the role of Ca in SOC persistence from solely a driver of physico-chemical reactions to a mediator of coupled abiotic-biotic cycling of SOC.

54 ENVIRONMENTAL SCIENCES↗