bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fine Tuning of Donor‐Acceptor Structures in Fused‐Carbazole Containing Thermally Activated Delayed Fluorescence Materials towards High‐Efficiency OLEDs
Authors: Yuan Wenbo , Hu Weiyang , Wang Jian , Zhu Mengyuan , Shi Changsheng , Sun Ning , Tao Youtian 
Published: March 2023

Comprehensive SummaryConjugated fused‐ring structures have attracted extensive attention due to their high molecular rigidity to restrain excited‐state relaxation and non‐radiative decay, and further to enhance the luminance efficiency for emissive materials. Herein, we develop a series of donor‐acceptor type thermally activated delayed fluorescence (TADF) emitters by introducing fused‐ring 5H‐benzofuro[3,2‐c]carbazole (32BFCz) as electron donating unit. Through optimizing the numbers and structure of donor and acceptor moieties, three compounds named 32BFCzA, mCF3BFCzOXD and dCF3BFCzOXD are designed, which are composed by mono‐32BFCz/trifluoromethylpicolinonitrile, penta‐BFCz/3‐(trifluoromethyl)phenyl)‐1,3,4‐oxadiazol‐2‐yl)benzene and penta‐32BFCz/3,5‐bis(trifluoromethyl)phenyl)‐1,3,4‐oxadiazol‐2‐yl)benzene as donor/acceptor groups, respectively. They all exhibited green emission with peak value ranging from 532 to 540 nm. Through rationally tuning the donor/acceptor properties to reduce the distance between positive and negative charges, the ground state dipole moments decline from 8.93, 6.18 to 5.30 Debye, which further induced sequentially reduced singlet‐triplet energy splits (ΔESTs), increased photoluminescence quantum yields (PLQYs), enhanced reverse intersystem crossing rate (kRISCs) and diminished delayed fluorescence lifetime from 32BFCzA, mCF3BFCzOXD to dCF3BFCzOXD. Therefore, gradually increased external quantum efficiency (EQE) is accordingly achieved when employing them as emitters for TADF OLEDs. dCF3BFCzOXD with the mostly optimized donor/acceptor structures demonstrates the highest efficiency with maximum EQE to 21.4%. Our work provides guidelines on the design of high‐efficiency D‐A type TADF materials.
Clinical characteristics, treatment, and survival of 30 patients with gastrointestinal natural killer/T‐cell lymphoma
Authors: Liu Jia‐Xin , Liu Xin , Yang Yong , Liu Wei‐Ping , Wang Ying , He Xia , Zhang Li‐Ling , Qu Bao‐Lin , Qian Li‐Ting , Hou Xiao‐Rong , Qiao Xue‐Ying , Wang Hua , Li Gao‐Feng , Zhu Yuan , Cao Jian‐Zhong , Wu Jun‐Xin , Wu Tao , Zhu Su‐Yu , Shi Mei , Zhang Hui‐Lai , Su Hang , Zhang Yu‐Jing , Zhu Jun , Qi Shu‐Nan , Li Ye‐Xiong , Song Yu‐Qin 
Published: March 2023

AbstractBackgroundThe gastrointestinal (GI) tract is the second most frequent extranasal involvement site for ENKTL. This study aimed to explore the clinicopathological features, treatment models, survival outcomes, and prognosis of gastrointestinal ENKTL (GI‐ENKTL).MethodsThe clinical data of GI‐ENKTL patients were extracted from the China Lymphoma Collaborative Group (CLCG) database and were analyzed retrospectively.ResultsA total of 30 patients were enrolled, with a male/female ratio of 4:1 and a median age of 42 years. Twenty‐nine patients received chemotherapy, of whom 15 patients received asparaginase‐based (ASP‐based) regimens. Moreover, seven received surgery and three received radiotherapy. The overall response an d complete remission rates were 50.0% and 30.0% for the whole cohort, 50.0% and 37.5% for patients treated with ASP‐based regimens, and 50.0% and 25.0% for those treated with non‐ASP‐based regimens, respectively. The median follow‐up was 12.9 months and the 1‐year overall survival rate was 40.0% for the whole cohort. For those patients in an early stage, ASP‐based regimens resulted in a superior 1‐year progression‐free survival rate compared to non‐ASP‐based regimens (100.0% vs. 36.0%, p = .07). However, ASP‐based regimens did not improve survival in patients at an advanced stage.ConclusionGI‐ENKTL still has a poor prognosis, even in the era of modern asparaginase‐based treatment strategies.
Effects of Edge Functionalization of Nanographenes with Small Aromatic Systems
Authors: Takahashi Shusaku , Sekiya Ryo , Haino Takeharu 
Published: March 2023

AbstractRegulation of the physical properties of nanographenes (NGs) by edge functionalization is an active research area. We conducted a computational study of the effects of edge functionalization on the physical properties of NGs. The computed NGs were models of experimentally obtained NGs and composed of a C174 carbon framework with one to four 3,5‐dimethylnaphthalene units on the edge. The effects were assessed structurally, magnetically, and electronically by the least square planarity index, harmonic oscillator model of aromaticity, nucleus‐independent chemical shift, and HOMO–LUMO (H–L) gaps. Density functional theory calculations indicate that although the structures of the model NGs are not very sensitive to edge functionalization, but the magnetic and electronic properties are. The installed substituents narrowed the H−L gap and induced a redshift of the photoluminescence (PL) band by the π conjugation between NG and the substituent. These results are consistent with the extension of the absorption band and the redshift of the PL bands of the experimentally modified NGs. Furthermore, the calculations confirmed the contribution of the charge transfer character to the absorption spectra.
Association between Life's Essential 8 score and risk of premature mortality in people with and without type 2 diabetes: A prospective cohort study
Authors: Sun Ying , Yu Yuefeng , Zhang Kun , Yu Bowei , Yu Yuetian , Wang Yuying , Wang Bin , Tan Xiao , Wang Yu , Lu Yingli , Wang Ningjian 
Published: March 2023

AbstractAimsTo evaluate the association of cardiovascular health (CVH), measured by Life's Essential 8 score, with the risk of premature mortality and to determine the patterns of CVH‐related differences in life expectancy among people with and without type 2 diabetes (T2D).Materials and MethodsThis prospective study included 309,789 participants (age 56.6 ± 8.1 years; 46% men) enroled in the UK Biobank. The Life's Essential 8 composite measure consists of four health behaviours (diet, physical activity, nicotine exposure, and sleep) and four health factors (BMI, non‐HDL cholesterol, blood glucose, and blood pressure), and the maximum CVH score was 100 points. CVH was categorised into low, moderate, and high groups. Premature death was defined as death before the age of 75. Cox proportional hazard ratios (HRs) with 95% confidence intervals (CIs) were calculated, and life expectancy was estimated.ResultsDuring a median follow‐up of 12.7 years, 13,683 cases of premature death were documented. Compared to participants with low CVH, the multivariable HRs (95% CIs) of premature death were 0.59 (0.56–0.62) and 0.42 (0.39–0.45) for the moderate and high CVH groups, respectively. This association was stronger in participants with T2D compared with those without T2D. At the age of 50 years, compared to low CVH groups, high CVH was associated with a gain of 9.79 (9.70–9.87) and 5.58 (5.48–5.67) additional life years for men with and without T2D, respectively. The corresponding life gain for women with and without T2D was 24.21 (24.13–24.27) and 10.18 (10.10–10.27), respectively.ConclusionsMaintaining an ideal Life's Essential 8 score may provide more benefits for people with T2D than for those without T2D, including a lower risk of premature death and an increased lifespan.
Water availability and seasonality shape elemental stoichiometry across space and time
Authors: Atkinson Carla L. , Shogren Arial J. , Smith Chelsea R. , Golladay Stephen W. 
Published: March 2023

AbstractThe interaction of climate change and increasing anthropogenic water withdrawals is anticipated to alter surface water availability and the transport of carbon (C), nitrogen (N), and phosphorus (P) in river networks. But how changes to river flow will alter the balance, or stoichiometry, of these fluxes is unknown. The Lower Flint River Basin (LFRB) is part of an interstate watershed relied upon by several million people for diverse ecosystem services, including seasonal crop irrigation, municipal drinking water access, and public recreation. Recently, increased water demand compounded with intensified droughts have caused historically perennial streams in the LFRB to cease flowing, increasing ecosystem vulnerability. Our objectives were to quantify how riverine dissolved C:N:P varies spatially and seasonally and determine how monthly stoichiometric fluxes varied with overall water availability in a major tributary of LFRB. We used a long‐term record (21–29 years) of solute water chemistry (dissolved organic carbon, nitrate/nitrite, ammonia, and soluble reactive phosphorus) paired with long‐term stream discharge data across six sites within a single LFRB watershed. We found spatial and seasonal differences in soluble nutrient concentrations and stoichiometry attributable to groundwater connections, the presence of a major floodplain wetland, and flow conditions. Further, we showed that water availability, as indicated by the Palmer Drought Severity Index (PDSI), strongly predicted stoichiometry with generally lower C:N and C:P and higher N:P fluxes during periods of low water availability (PDSI < −4). These patterns suggest there may be long‐term and significant changes to stream ecosystem function as water availability is being dramatically altered by human demand with consequential impacts on solute transport, in‐stream processing, and stoichiometric ratios.
Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity
Authors: Peyrot Analia Mercedes , Zelaya María Priscila , Alborés Pablo , Fagalde Florencia 
Published: March 2023

AbstractIn this work, we report the synthesis and physicochemical characterization of new chloro and aqua mononuclear Ru (II) complexes of formula [Ru(LLL)(dpp)Cl]PF6and [Ru(LLL)(dpp)OH2](PF6)2(LLL=tpy =2,2’ : 6’,2’’‐terpyridine; tptz=2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine and dpp=2,3‐bis(2‐pyridil)pyrazine). For the complex [Ru(tptz)(dpp)Cl]PF6, the complete structure was determined by X‐ray diffraction. Catalytic studies of aqua‐complexes revealed that they are active for the water oxidation reaction at pH 1 using cerium ammonium nitrate (CAN) as a sacrificial oxidant. Also, we were able to establish the reaction mechanism and rate constants of each stage of the catalytic cycle, turnover frequencies (TOFs), and turnover numberes (TONs). The experimental TON values for the aqua complexes were very close to the theoretical value of 7.5, indicating a high degree of recovery. DFT and TD‐DFT calculations of electronic states for all complexes were consistent with experimental results and allowed the complete assignment of their UV‐Visible bands and redox states.
Syntheses, Structures, and Electronic Properties of Mono‐ and Bimetallic Thiolato Complexes Containing Unusual Coordination Modes of Thiolato Ligands
Authors: Bairagi Subhash , Pradhan Alaka Nanda , Cordier Marie , Roisnel Thierry , Ghosh Sundargopal 
Published: March 2023

AbstractSynthesis, bonding and chemistry of mono‐ and bimetallic complexes supported by chelating thiolato ligands have been established. Treatment of [Cp*VCl2]3(1) with [LiBH4 ⋅ THF] followed by the addition of ethane‐1,2‐dithiol led to the formation of an EPR active bimetallic vanadium thiolato complex [(Cp*V){μ‐(SCH2CH2S)‐κ2S,S′)2{V(SCH2CH2S‐SH)}] (2). In complex2, two ethane‐1,2‐dithiolato ligands are symmetrically coordinated to two vanadium atoms throughμ‐S atoms. Interestingly, when similar reactions were carried out with heavier group 5 metal precursors, such as [Cp*NbCl4] (3 a), it afforded monometallic thiolato complex [Cp*Nb(SCH2CH2S)(SCH2CH2S−CH2S)] (4 a). On the other hand, the Ta‐analogue [Cp*TaCl4] (3 b) yielded thiolato species [Cp*Ta(SCH2CH2S)(SCH2CH2S−CH2S)] (4 b) and [Cp*Ta(SCH2CH2S) (SCH2CH2S−S)] (5). In complexes4 aand4 b, one ethane‐1,2‐dithiolato and one trithiolato ligand are coordinated to Nb and Ta centers, respectively. Whereas, in complex5, one ethane‐1,2‐dithiolato and one 2‐disulfanylethanethiolato is coordinated to the Ta center. Moreover, the photolytic reaction of5with [Mo(CO)5 ⋅ THF] yielded heterobimetallic thiolato complex [(Cp*Ta){μ‐(SCH2CH2S)‐κ2S,S′}{μ‐(SCH2CH2S−CH2(CH3)S)κ2S′′ : κ1S‐′′′′ : κ1S′′′′′}{Mo(CO)3}] (6). All the complexes have been characterized by multinuclear NMR spectroscopy and single crystal X‐ray diffraction studies. Further, computational analyses were performed to provide an insight into the bonding of these complexes.
Highly Fluorescent 2‐Aminopurine Derivatives: Synthesis, Photo‐physical Characterization, and Preliminary Cytotoxicity Evaluation
Authors: Gonçalves Jorge M. , Gonçalves João N. D. , Pêra Ana S. , Senhorães Nádia R. , Rodrigues Ana Rita O. , Oliveira Rui , Coutinho Paulo J. G. , Castanheira Elisabete M. S. , Dias Alice M. 
Published: March 2023

AbstractNew fluorescent nucleobase analogues (FBAs) are emerging as extraordinarily useful tools for DNA labelling technologies. The highly fluorescent adenine analogue 2‐aminopurine (2AP) is still the most used within the few hundreds of newly FBAs synthesized, but its excitation in the UV region demands for high energy sources endangering living cells. New and highly fluorescent 2AP derivatives, 2‐amino‐6‐cyanopurines, were obtained using simpler but efficient synthesis method. All the new compounds exhibit advantageous photophysical properties over 2AP, showing absorption and emission bands ranging the visible region (blue‐green region), high fluorescence quantum yields and Stokes’ shifts, especially in non‐protic organic solvents. Density Functional Theory calculations (DFT) of electronic and vibrational structure were performed, allowing to predict absorption and emission spectra. In addition, these 2‐amino‐6‐cyanopurines exhibit little to no toxicity in assays using yeast cells.
Tolerability and pharmacokinetics of intravenous allopregnanolone with and without midazolam pretreatment in two healthy dogs
Authors: Bruun Donald A. , Ma Betty , Chen Yi‐Je , Wu Chun‐Yi , Aleman Monica , Zolkowska Dorota , Smiley‐Jewell Suzette M. , Rogawski Michael A. , Lein Pamela J. 
Published: March 2023

AbstractThe neurosteroid allopregnanolone (ALLO) is under investigation as a treatment for benzodiazepine‐refractory status epilepticus (SE). Here, we assess the cardiopulmonary safety of intravenous ALLO by itself and after a clinically recommended dose of midazolam (MDZ) in two healthy adult beagles. Each dog received ALLO (1 mg/kg, IV), and after a washout period of 2 weeks, each dog was dosed with MDZ (0.2 mg/kg, IV) followed 10 minutes later by ALLO. Behavioral state, vital signs, arterial blood gases, blood chemistries, and plasma ALLO concentrations were monitored for up to 6 hours after dosing. The dogs appeared sleepy but were fully responsive after both treatments. No depression of mean arterial pressure or respiratory rate was noted. Blood gas measurements failed to show evidence of drug‐induced acute respiratory acidosis. Estimated maximum plasma ALLO concentrations were in the range of 1500 to 3000 ng/ml. The results indicate that intravenous ALLO can be used safely to treat benzodiazepine‐refractory SE, even when administered shortly after a benzodiazepine.
Validation of Nickel Bioavailability Models for Algae, Invertebrates, and Fish in Chinese Surface Waters
Authors: He Jia , Wang Cheng , Schlekat Christian E. , Wu Fengchang , Middleton Elizabeth , Garman Emily , Peters Adam 
Published: March 2023

Abstract
Nickel (Ni) is used primarily in the production of alloys like stainless steel and is increasingly being used in the production of batteries for the electric vehicle market. Exposure of Ni to ecosystems is of concern because Ni can be toxic to aquatic organisms. The influence of water chemistry constituents (e.g., hardness, pH, dissolved organic carbon) on the toxicity of Ni has prompted the development and use of bioavailability models, such as biotic ligand models (BLMs), which have been demonstrated to accurately predict Ni toxicity in broadly different ecosystems, including Europe, North America, and Australia. China, a leading producer of Ni, is considering bioavailability-based approaches for regulating Ni emissions. Adoption of bioavailability-based approaches in China requires information to demonstrate the validity of bioavailability models for the local water chemistry conditions. The present study investigates the toxicity of Ni to three standard test species (Daphnia magna, Pseudokirchneriella subcapitata, and Danio rerio) in field-collected natural waters that are broadly representative of the range of water chemistries and bioavailabilities encountered in Chinese lakes and rivers. All experimental data are within a factor of 3 of the BLM predicted values for all tests with all species. For D. magna, six of seven waters were predicted within a factor of 2 of the experimental result. Comparison of experimental data against BLM predictions shows that the existing Ni bioavailability models are able to explain the differences in toxicity that result from water chemistry conditions in China. Validation of bioavailability models to water chemistries and bioavailability ranges within China provides technical support for the derivation of site-specific Ni water quality criteria in China. Environ Toxicol Chem 2023;42:1257–1265. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Ecological Harm and Economic Damages of Chemical Contamination to Linked Aquatic-Terrestrial Food Webs: A Study-Design Tool for Practitioners
Authors: Kraus Johanna M. , Skrabis Kristin , Ciparis Serena , Isanhart John , Kenney Aleshia , Hinck Jo Ellen 
Published: March 2023

Abstract
Contamination of aquatic ecosystems can have cascading effects on terrestrial consumers by altering the availability and quality of aquatic insect prey. Comprehensive assessment of these indirect food-web effects of contaminants on natural resources and their associated services necessitates using both ecological and economic tools. In the present study we present an aquatic-terrestrial assessment tool (AT2), including ecological and economic decision trees, to aid practitioners and researchers in designing contaminant effect studies for linked aquatic-terrestrial insect-based food webs. The tool is tailored to address the development of legal claims by the US Department of the Interior's Natural Resource Damage Assessment and Restoration Program, which aims to restore natural resources injured by oil spills and hazardous substance releases into the environment. Such cases require establishing, through scientific inquiry, the existence of natural resource injury as well as the determination of the monetary or in-kind project-based damages required to restore this injury. However, this tool is also useful to researchers interested in questions involving the effects of contaminants on linked aquatic-terrestrial food webs. Stylized cases exemplify how application of AT2 can help practitioners and researchers design studies when the contaminants present at a site are likely to lead to injury of terrestrial aerial insectivores through loss of aquatic insect prey and/or dietary contaminant exposure. Designing such studies with ecological endpoints and economic modeling inputs in mind will increase the relevance and cost-effectiveness of studies, which can in turn improve the outcomes of cases and studies involving the ecological effects of contaminants on food webs. Environ Toxicol Chem 2023;42:2029–2039. Published 2023. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Facile Bond Activation of Small Molecules by an Acyclic Imino(silyl)silylene
Authors: Zhu Huaiyuan , Hanusch Franziska , Inoue Shigeyoshi 
Published: March 2023

AbstractThe activation of small molecules by silylenes bearing unique electronic properties has been well established in the past few decades. Here, we disclose the reactivity study of acyclic imino(silyl)silylene 1 with an N‐heterocyclic imine ligand (NHI) towards various small molecules. Silylene 1 undergoes facile activation of gaseous molecules like dihydrogen, ethylene, and carbon dioxide. While the cycloaddition of carbonyl compounds to 1 was shown as a straightforward synthetic approach of oxasilacycles, reaction with silane as well as borane led to the corresponding E−H (E=Si, B) insertion products. Moreover, reaction with heavier chalcogens allow the isolation of neutral three‐coordinate silicon‐heavier chalcogen double bond complexes.
Modified Periodic Acid‐Schiff (PAS) Is an Alternative to Safranin O for Discriminating Bone–Cartilage Interfaces
Authors: Kjosness Kelsey M , Reno Philip L , Serrat Maria A 
Published: March 2023

ABSTRACTCartilage histomorphometry is often performed on decalcified, paraffin‐embedded bone sections, which provide versatility in staining applications from basic morphology to immunohistochemistry. Safranin O is a cationic dye that binds to proteoglycans in cartilage and is routinely used to assess growth plate dynamics and/or fracture repair at bone–cartilage interfaces. When used with a counterstain such as fast green, safranin O can offer exquisite differentiation of cartilage from surrounding bone. However, various decalcification and processing methods can deplete proteoglycans, rendering inconsistent, weak, or absent safranin O staining with indiscriminate bone–cartilage boundaries. We sought to develop an alternative staining methodology that preserves the contrast of bone and cartilage in cases of proteoglycan depletion that can be applied when other cartilage stains are unsuccessful. Here, we describe and validate a modified periodic acid‐Schiff (PAS) protocol that we developed using Weigert's iron hematoxylin and light green stains as an alternative to safranin O for discriminating bone–cartilage interfaces of skeletal tissues. This method provides a practical solution for differentiating bone and cartilage when safranin O staining is not detected after decalcification and paraffin processing. The modified PAS protocol can be useful for studies in which identification of the bone–cartilage interface is essential but may not be preserved with standard staining approaches. © 2023 The Authors. JBMR Plus published by Wiley Periodicals LLC on behalf of American Society for Bone and Mineral Research.