bluuebunny/crossref_metadata_2025 huggingface dataset:
Spatiotemporally Controlled T‐Cell Combination Therapy for Solid Tumor
Authors: Hao Meixi , Zhou Ying , Chen Sijia , Jin Yu , Li Xiuqi , Xue Lingjing , Shen Mingxuan , Li Weishuo , Zhang Can
Published: April 2024

Due to multidimensional complexity of solid tumor, development of rational T‐cell combinations and corresponding formulations is still challenging. Herein, a triple combination of T cells are developed with Indoleamine 2,3‐dioxygenase inhibitors (IDOi) and Cyclin‐dependent kinase 4/6 inhibitors (CDK4/6i). To maximize synergism, a spatiotemporally controlled T‐cell engineering technology to formulate triple drugs into one cell therapeutic, is established. Specifically, a sequentially responsive core‐shell nanoparticle (SRN) encapsulating IDOi and CDK4/6i is anchored onto T cells. The yielded SRN‐T cells migrated into solid tumor, and achieved a 1st release of IDOi in acidic tumor microenvironment (TME). Released IDOi restored tryptophan supply in TME, which activated effector T cells and inhibited Tregs. Meanwhile, 1st released core is internalized by tumor cells and degraded by glutathione (GSH), to realize a 2nd release of CDK4/6i, which induced up‐regulated expression of C‐X‐C motif chemokine ligand 10 (CXCL10) and C‐C motif chemokine ligand 5 (CCL5), and thus significantly increased tumor infiltration of T cells. Together, with an enhanced recruitment and activation, T cells significantly suppressed tumor growth, and prolonged survival of tumor‐bearing mice. This study demonstrated rationality and superiority of a tri‐drug combination mediated by spatiotemporally controlled cell‐engineering technology, which provides a new treatment regimen for solid tumor.
A simple “spraying” fluorescence‐guided surgery by AIE probes for liver tumor resection through configuration‐induced cross‐identification
Authors: Chen Didi , Xiao Tian , Wang Liangjie , Chen Sijie , Kam Chuen , Zeng Guoping , Peng Li , Zhang Jinxiang , Li Min , Dong Yuping
Published: April 2024

Surgical resection is the preferred option for hepatocellular carcinoma (HCC), but surgical navigation technology using indocyanine green still has some drawbacks such as non‐specific imaging, thus it is very important to develop new fluorescence imaging technology. All‐cis hexaphenyl‐1,3‐butadiene derivative (ZZ‐HPB‐NC) with aggregation‐induced emission (AIE) feature has been reported to be quickly turned‐on fluorescent response in the intraoperative frozen‐section slides of HCC. However, the probe did not respond to normal liver tissue around HCC. In order to enhance the diagnostic rate and elucidate the response mechanism, all‐trans configuration EE‐HPB‐NC, was furtherly synthesized. Within two minutes, non‐cancer tissues could be fluorescently labeled by EE‐HPB‐NC by spraying, showing the same effect with ZZ‐HPB‐NC to HCC. The results indicated that the configuration‐induced cross‐identification fluorescence imaging strategy was achieved through the combination of ZZ‐ and EE‐HPB‐NC. Then the mechanism of HPB‐NC localization in HCC lesions was explored, and the binding of HPB‐NC with specific proteins in cells resulted in the AIE effect to label HCC cells. On this basis, the accuracy of specific fluorescence imaging for HCC was further verified on the mouse hepatic neoplasm models, indicating that it has clinical application potential for surgical fluorescence real‐time navigation.
Adsorption weakening mechanism and regulation strategy of aluminum‐based lithium adsorbents in carbonate‐style brines
Authors: Chen Jun , Jin Jiaqi , Yu Jianguo , Lin Sen
Published: April 2024

An efficient adsorption‐strengthening regulation was developed for aluminum‐based lithium adsorbents (Li/Al‐LDHs) in carbonate‐type salt lakes based on reasons for adsorption performance degradation. It was confirmed by adsorption–desorption experiments and density functional theory (DFT) that CO32− in brines preferentially entered Li/Al‐LDH interlayers with a tighter binding energy to the laminates, resulting in the decreasing sharply cyclic re‐adsorption capacity. Intercalated CO32− was effectively removed by high concentration of Cl− to enhance Li+ re‐adsorption, and X‐ray absorption spectroscopy (XAS) demonstrated that this process had no impact on the host laminate integrity. On this basis, an innovative strategy of incorporating interlayer anion regulation into lithium extraction process was proposed and employed for the continuous extraction of Li+ from carbonate‐type brines, bringing about a completely restored re‐adsorption capacity with cyclic stability, and the lithium extraction capacity per unit time could be exceeded by about double compared with the conventional process, assuring the efficiency of lithium extraction from carbonate‐type brines by Li/Al‐LDHs.
Water‐Promoted Metal‐Free Aerobic Oxidative Annulation for the Multicomponent Synthesis of Acridine‐1,8‐Diones Derivatives and Their Photophysical Studies
Authors: Reicha  , Puhazhendhi Arulmozhi , Sivalingam Soumya , Yamajala Rajesh B. R. D.
Published: April 2024

Among the optimistic areas of research, is the creation of novel C−C, C−N, and C−O bonds by replacing toxic and waste‐generating chemicals with alcohols as more sustainable and greener reagents. The co‐existence of molecular oxygen and TBHP was admired by its capacity to oxidize and cyclize to form biologically active acridine‐1,8‐dione derivatives from alcohol, aniline and dimedone without any metal catalyst. The decomposition of TBHP and aeration of molecular oxygen on the surface of water was the key factor for effective catalytic outcome. The current method exhibits tolerance for diverse substrates to afford acridine‐1,8‐dione derivatives (18 compounds) with high yield (up to 95 %). Additionally, the photophysical properties of the acridine‐1,8‐dione derivatives were also studied, and found that few of the acridine‐1,8‐dione derivatives have shown appreciable Aggregation Induced Emission Enhancement (AIEE) behaviour.
Efficacy of antithrombin administration for patients with sepsis: A systematic review, meta‐analysis, and meta‐regression
Authors: Tsuchida Takumi , Makino Yuto , Wada Takeshi , Ushio Noritaka , Totoki Takaaki , Fujie Naoki , Yasuo Shunsuke , Matsuoka Tadashi , Koami Hiroyuki , Yamakawa Kazuma , Iba Toshiaki
Published: April 2024

Aims

There have been inconsistent reports regarding the effect of antithrombin on sepsis; furthermore, there are limited reports on how dosage affects therapeutic efficacy. Thus, we aimed to perform a systematic review and meta‐analysis of the use of antithrombin for sepsis and a meta‐regression analysis of antithrombin dosage.

Methods

We included randomized controlled trials (RCTs) and observational studies of adult patients with sepsis who received antithrombin. Outcomes included all‐cause mortality and serious bleeding complications. Statistical analyses and data synthesis were performed using a random‐effects model; further, meta‐regression and funnel plots were used to explore heterogeneity and biases.

Results

Seven RCTs and six observational studies were included. Most patients in the RCTs and observational studies had severe sepsis and septic‐disseminated intravascular coagulation (DIC), respectively. A meta‐analysis using RCTs showed no significant differences in mortality between the antithrombin and control groups. However, the meta‐analysis of observational studies indicated a trend of decreasing mortality rates with antithrombin administration (odds ratio [OR], 0.79; 95% confidence interval [CI], 0.68–0.92; p = 0.002). Bleeding complications were significantly higher in the antithrombin group than in the control group in both study types (OR, 1.90; 95% CI, 1.52–2.37; p < 0.01). The meta‐regression analysis showed no correlation between antithrombin dosage and mortality.

Conclusion

A meta‐analysis of RCTs confirmed no survival benefit of antithrombin, whereas that of observational studies, which mostly focused on septic DIC, showed a significant beneficial effect on improving outcomes. Indications of antithrombin should be considered based on its beneficial and harmful effects.
Photogeneration of Chlorine Radical from a Self‐Assembled Fluorous 4CzIPN•Chloride Complex: Application in C−H Bond Functionalization
Authors: Carré Victor , Godard Pascale , Méreau Raphaël , Jacquot de Rouville Henri‐Pierre , Jonusauskas Gediminas , McClenaghan Nathan , Tassaing Thierry , Vincent Jean‐Marc
Published: April 2024

The chlorine radical is a strong HAT (Hydrogen Atom Transfer) agent that is very useful for the functionalization of C(sp3)−H bonds. Albeit highly attractive, its generation from the poorly oxidizable chloride ion mediated by an excited photoredox catalyst is a difficult task. We now report that 8Rf8‐4CzIPN, an electron‐deficient fluorous derivative of the benchmark 4CzIPN photoredox catalyst belonging to the donor‐acceptor carbazole‐cyanoarene family, is not only a better photooxidant than 4CzIPN, but also becomes an excellent host for the chloride ion. Combining these two properties ultimately makes the self‐assembled 8Rf8‐4CzIPN•Cl− dual catalyst highly reactive in redox‐neutral Giese‐type C(sp3)−H bond alkylation reactions promoted by the chlorine radical. Additionally, because of its fluorous character, the efficient separation/recovery of 8Rf8‐4CzIPN could be envisioned.
An MBene Modulating the Buried SnO2/Perovskite Interface in Perovskite Solar Cells
Authors: Zhang Yuning , Yu Bo , Sun Yapeng , Zhang Jiankai , Su Zhan , Yu Huangzhong
Published: April 2024

The interface of perovskite solar cells (PSCs) plays an important role in transferring and collecting charges. Interface defects are important factors affecting the efficiency and stability of PSCs. Here, the buried interface between SnO2 and the perovskite layer is bridged by two‐dimensional (2D) MBene, which improves charge transfer. MBene can deposit additional electrons on the surface of SnO2, passivate its surface defects and facilitate the charge collection. Moreover, the dipole moment formed at the interface increases the electron transfer ability in the PSCs. MBene also regulates the growth of perovskite crystals, improves the quality of perovskite films, and reduces its grain boundary defects. As a result, PSCs based on FA0.2MA0.8PbI3 and (FAPbI3)0.95(MAPbBr3)0.05 get the enhanced efficiencies of 22.34 % and 24.32 % with negligible hysteresis. Furthermore, the optimized device exhibits better stability. This work opens up the application of MBene materials in PSCs, reveals a deeper understanding of the mechanism behind using 2D materials as an interface modification layer, and shows opportunities for using MBene as potential material in photoelectric devices.
Organometallic Chirality Sensing via “Click”‐Like η6‐Arene Coordination with an Achiral Cp*Ru(II) Piano Stool Complex
Authors: Nelson Eryn , Bertke Jeffery A. , Thanzeel F. Yushra , Wolf Christian
Published: April 2024

Piano stool complexes have been studied over many years and found widespread applications in organic synthesis, catalysis, materials and drug development. We now report the first examples of quantitative chiroptical molecular recognition of chiral compounds through click‐like η6‐arene coordination with readily available half sandwich complexes. This conceptually new approach to chirality sensing is based on irreversible acetonitrile displacement of [Cp*Ru(CH3CN)3]PF6 by an aromatic target molecule, a process that is fast and complete within a few minutes at room temperature. The metal coordination coincides with characteristic circular dichroism inductions that can be easily correlated to the absolute configuration and enantiomeric ratio of the bound molecule. A relay assay that decouples the determination of the enantiomeric composition and of the total sample amount by a practical CD/UV measurement protocol was developed and successfully tested. The introduction of piano stool complexes to the chiroptical sensing realm is mechanistically unique and extends the scope of currently known methods with small‐molecule probes that require the presence of amino, alcohol, carboxylate or other privileged functional groups for binding of the target compound. A broad application range including pharmaceutically relevant multifunctional molecules and the use in chromatography‐free asymmetric reaction analysis are also demonstrated.
Supramolecular Entanglement in a Hydrogen‐Bonded Organic Framework Enables Flexible‐Robust Porosity for Highly Efficient Purification of Natural Gas
Authors: Jiang Chenghao , Wang Jia‐Xin , Liu Di , Wu Enyu , Gu Xiao‐Wen , Zhang Xu , Li Bin , Chen Banglin , Qian Guodong
Published: April 2024

The development of porous materials with flexible‐robust characteristics shows some unique advantages to target high performance for gas separation, but remains a daunting challenge to achieve so far. Herein, we report a carboxyl‐based hydrogen‐bonded organic framework (ZJU‐HOF‐8a) with flexible‐robust porosity for efficient purification of natural gas. ZJU‐HOF‐8a features a four‐fold interpenetrated structure with dia topology, wherein abundant supramolecular entanglements are formed between the adjacent subnetworks through weak intermolecular hydrogen bonds. This structural configuration could not only stabilize the whole framework to establish the permanent porosity, but also enable the framework to show some flexibility due to its weak intermolecular interactions (so‐called flexible‐robust framework). The flexible‐robust porosity of ZJU‐HOF‐8a was exclusively confirmed by gas sorption isotherms and single‐crystal X‐ray diffraction studies, showing that the flexible pore pockets can be opened by C3H8 and n‐C4H10 molecules rather by C2H6 and CH4. This leads to notably higher C3H8 and n‐C4H10 uptakes with enhanced selectivities than C2H6 over CH4 under ambient conditions, affording one of the highest n‐C4H10/CH4 selectivities. The gas‐loaded single‐crystal structures coupled with theoretical simulations reveal that the loading of n‐C4H10 can induce an obvious framework expansion along with pore pocket opening to improve n‐C4H10 uptake and selectivity, while not for C2H6 adsorption. This work suggests an effective strategy of designing flexible‐robust HOFs for improving gas separation properties.
Cu‐supported amine‐functionalized Fe3O4 magnetically recoverable nanocatalyst for A3 coupling reactions
Authors: Banda Prashanth Goud , Kurup Gayathri Bindu , Pooja  , Mounika Bhukya , Pawar Ravinder , Mucherla Raghasudha
Published: April 2024

In this study, a Cu‐supported amine‐functionalized Fe3O4 nanocatalyst (Fe3O4‐NH2‐Cu) has been synthesized for A3 (amine, aldehyde, and alkyne) coupling reactions. The synthesized nanocatalyst was characterized by PXRD, FT‐IR, FESEM‐EDX, XPS, and VSM analysis. The catalytic action of the synthesized Fe3O4‐NH2‐Cu nanocatalyst was evaluated for A3 coupling reactions, with an excellent product yield of 97% in propargylamine synthesis and 98% in indolizines synthesis, respectively. The substrate scope of the catalyst was validated for various amines, substituted aryl aldehydes, and phenyl acetylene. The uniqueness of the synthesized nanocatalyst is effective performance of the catalyst under solvent‐free conditions and less reaction time for the aforementioned application. With the aid of an external magnet, the catalyst can be easily recovered from the reaction mixture and reused at least for five times without significant loss in catalytic activity, and its structural stability was confirmed by XRD, FT‐IR, and FESEM‐EDX analysis of the recovered catalyst. Overall, it is a green approach to synthesize simple Fe3O4‐NH2‐Cu catalytic system with magnetic recoverability, reusability, and recyclability for A3 coupling reactions under solvent‐free conditions with broad substrate scope. The proposed plausible mechanism is supported by DFT studies.
Harnessing the potential of oilcane waste mud for recovering biobased waxes
Authors: Banerjee Shivali , Eilts Kristen K. , Singh Vijay
Published: April 2024

Oilcane is an engineered sugarcane with the ability to hyper‐accumulate vegetative lipids. It is processed to obtain juice and bagasse as a potential substrate for the production of biofuels and biochemicals. The juice comprises solid particles that are separated as waste mud before the fermentation of the juice. In this study, the oilcane waste mud (OWM) generated from 1000 liters of oilcane juice was quantified and evaluated as a potential resource for recovering biobased waxes. Hexane and ethyl acetate were evaluated as two different solvents for extracting waxes from OWM followed by its purification using acetone. The extracted biobased wax samples were characterized for their chemical and thermal profiles which were then compared with commercial natural waxes. Detailed mass balance shows that 53.6 ± 2.6 kg (dry basis) of solid OWM gets generated upon processing 1000 L (~1068 kg) of oilcane juice. Hexane and ethyl acetate led to a crude wax yield of 25.6 ± 0.2% and 16.6 ± 0.4% (wt/wt, dry basis) respectively from OWM at the end of 8 h. The relative purification of the wax samples was reported in the range of 58%–65% (wt/wt). The purified OWM wax has a melting point of 74.7°C. The waste mud was valorized as a source of biobased waxes with characteristic chemical and thermal profiles comparable to commercial natural waxes (carnauba and beeswax). Considering the decline in the supply of petroleum wax in the future coupled with the switch to “greener” alternative products by consumers, OWM could be a valuable source of natural wax in the industrial sector reducing the dependence on petroleum waxes. Eventually, recovering biobased wax as a co‐product from OWM would bring in an additional stream of revenue leading to the development of a zero‐waste biorefinery based on bioenergy crops.
Diamondoid Ni(II) Coordination Polymer as an Electrocatalyst for Hydrogen and Oxygen Evolution Reactions and Overall Water Splitting
Authors: Naaz Sanobar , Chatterjee Taposi , Roy Saswati , Dutta Basudeb , Wabaidur Saikh Mohammad , Siddiqui Masoom Raza , Wahid Malik , Mafiz Alam Seikh , Hedayetullah Mir Mohammad
Published: April 2024

We have successfully synthesized a new Ni(II)‐based coordination polymer (CP) [Ni2(cis‐1,4‐chdc)2(4,4′‐bpy)3(H2O)2] (1); (cis‐1,4‐ H2chdc=cis‐1,4‐cyclohexanedicarboxylic acid and 4,4′‐bpy=4,4′‐bipyridine) employing slow diffusion method in a single pot technique. The connectivity of Ni(II) ions and bridging cis‐1,4‐chdc ligand gives rise to a three‐dimensional (3D) framework with 2‐fold interpenetrated diamondoid topology. Interestingly, the synthesized CP acts as efficient catalyst for electrocatalytic water splitting. The water oxidation activity of compound 1 exhibits Tafel slope equivalent to 361.48 mV.dec−1 for hydrogen evolution reaction (HER) and 353.53 mV.dec−1 for oxygen evolution reaction (OER) in an alkaline medium while almost similar values of Tafel slope for HER and OER equivalent to 287.33 mV.dec−1 and 289.93 mV.dec−1 respectively in acidic medium. Thus, the compound 1 has excellent efficacy in catalyzing HER and OER in acidic as well as alkaline medium, which is ascribed to its distinctive 3D architecture.
A repeated cross‐sectional study of daily activities of autistic adults
Authors: Bury Simon M. , Hedley Darren , Uljarević Mirko , Stokes Mark A. , Begeer Sander
Published: April 2024

It is crucial to arrive at a comprehensive understanding of the types of daily activities autistic adults typically engage in. However, previous research has almost exclusively focused on vocational or education activities. Further, it remains unclear how and whether specific daily activities participation rates change proportionally over time, vary by gender, or compare to nationally representative data. Utilizing eight annual data waves from the Netherlands Autism Register (NAR) this study aims to bridge this gap. Participants were 2449 autistic adults who indicated their participation in 18 daily activities. Results suggest that autistic adults engaged most frequently in vocational activities (e.g., paid employment, study) and participation rates were stable over time. Participation rates in non‐vocational activities (e.g., hobbies, homemaking) fluctuated proportionally over time, with reports of no structured daytime activities reducing over time. Labor force participation amongst NAR participants was significantly lower than Dutch population data for the same time periods. Unemployment rates fluctuated, and were significantly higher than population data, but not for all time points. Females compared to males were overrepresented in unpaid daily activities (e.g., study, volunteer, housemaker) and work incapacitation, and underrepresented in paid employment. Employment differences in gender corresponded to national data. These findings characterize more clearly the daily activities of autistic adults, and highlights areas where support may have greater impact (e.g., females in employment).
Post‐mortem rapid aneuploidy testing for holoprosencephaly
Authors: Gergely Lajos , Repiská Vanda , Böhmer Daniel , Korbeľ Miroslav , Václavová Zuzana , McCullough Liam , Melišová Katarína , Priščáková Petra
Published: April 2024

Background

Abortion and fetal death are common in fetuses with holoprosencephaly, so genetic examinations often have to be made in a post‐mortem setting. The efficiency of the conventional karyotyping using cultured fibroblasts in these situations is limited due to frequent culture failure. In the current study, archived cases of holoprosencephaly, where post‐mortem genetic evaluation was requested and sufficient frozen material was available, were reevaluated using the quantitative fluorescence polymerase chain reaction (QF‐PCR) technique.

Methods

Testing for aneuploidies of chromosomes 13, 15, 16, 18, 21, 22, X, and Y with the QF‐PCR technique was carried out on DNA isolated from archived frozen chorionic villi in seven cases of holoprosencephaly.

Results

QF‐PCR was successful in all seven cases. Two cases of trisomy 13, two cases of triploidy, and one case of trisomy 18 was found meaning a 71% diagnostic yield. The success rate of QF‐PCR (100%, 7/7) was superior compared to conventional karyotyping (43%, 3/7).

Conclusions

Rapid aneuploidy testing using the QF‐PCR technique is a simple, reliable, time‐ and cost‐effective method sufficient to conclude the etiologic investigation in the majority of holoprosencephaly cases post‐mortem.
Towards sustainability: Digital capability, sustainable business model innovation, and corporate environmental responsibility of high‐performing enterprises in an emerging market
Authors: Luo Xingwu , Qian Wei , Liu Min , Yu Xiaodan , Liu Yang
Published: April 2024

High‐performing enterprises committing to Corporate Environmental Responsibility (CER) is a prevalent phenomenon in emerging markets. However, the theoretical underpinnings of this phenomenon remain underdeveloped. Drawing on the behavior theory of the firm and a panel data of Chinese listed companies covering the period 2010–2020, we build a moderated mediation framework to explain the CER commitment of high‐performing enterprises, and we further examine the mediating role of sustainable business model innovation and the moderating role of digital capability. We find that (1) enterprises' performance aspiration surplus leads to an increasing commitment to CER, (2) high‐performing enterprises can foster CER through executing sustainable business model innovation, and (3) the direct and indirect (via sustainable business model innovation) effects of performance aspiration surplus on CER are favorably moderated by digital capability. This paper contributes to the literature of CER and provides strategic insights for high‐performing enterprises to undertake sustainable business model innovation.
Phytochemical Composition, Antioxidant and Antimicrobial Activity of Three Monarda Species: M. bradburiana L. C. Beck, M. × media Willd., and M. punctata L.
Authors: Gontar Łukasz , Geszprych Anna , Drutowska Andżelika , Osińska Ewa
Published: April 2024

Plants of the genus Monarda receive growing interest as the sources of herbal raw materials with wide range of potential applications in food, cosmetics, and phytopharmaceutical industry. This study aimed to evaluate the differences in chemical characteristics and biological activity among different organs of plants representing three underinvestigated species of this genus: Monarda bradburiana L. C. Beck, Monarda × media Willd., and Monarda punctata L. The content of phenolic compounds and the antioxidant activity of leaves, stems, and inflorescences were determined. Essential oil (EO) content, composition, and antimicrobial activity were also examined. M. punctata leaves and inflorescences had the highest EO content (4.43 % and 5.59 %, respectively), with carvacrol as a dominant constituent. Leaf EO was also rich in thymoquinone (17.48 %). In EOs of M. bradburiana and M. × media, thymol dominated. EOs inhibited the growth of all tested strains of microorganisms at a concentration of 0.625 μL×mL−1. The studied plant organs were rich in phenolic compounds, especially rosmarinic acid. M. bradburiana inflorescences were distinguished by high linarin content. Differences in flavonoid distribution seem to have special chemotaxonomic importance. Further research is needed to facilitate standardisation of the investigated plant organs as potential new herbal raw materials.
A Triply Linked Copper(III) Dicarbacorrole Dimer
Authors: Jiao Ruijuan , Liu Ningchao , Zong Zhaohui , Ke Xian‐Sheng
Published: April 2024

A triply linked dicarbacorrole dimer (7) was synthesized from a new meso‐meso singly linked dicarbacorrole dimer precursor (6) via an oxidative fusion reaction by 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone (DDQ) in the presence of trifluoromethanesulfonic acid (TfOH). Single crystal X‐ray structure of 7 adopts a flat conformation with a length as ca. 15.946 Å and a width as 6.903 Å, which can be regarded as a short carbaporphyrinoid tape. Two coordinated Cu ions keeps the +3 oxidation state in 7, as confirmed by NMR spectroscopy, single crystal X‐ray diffraction and X‐ray photoelectron spectroscopy (XPS). This is in sharp contrast to the Osuka's triply linked tetrapyrrolic corrole dimers, where the inner 3NH form is not stable and thus can only act as a divalent ligand. Due to the non‐aromatic nature of dicarbacorrole macrocycle, the largely decreased HOMO‐LUMO gap and red‐shifted absorption of 7 are best ascribed to the strong electronic interaction between two dipyrromethene‐type chromophores. To our knowledge, this is the first fully fused carbaporphyrinoid dimer with β‐β, meso‐meso, β‐β triply linkages prepared to date.
Kolonnen‐Fouling: Präventivmaßnahmen finden mit der Standardapparatur
Authors: Winterbauer Hansjürgen
Published: April 2024

Unerwünschte Belagbildung auf wärme‐ und/oder stoffübertragenden Oberflächen (Fouling) führt auch in Kolonnen zu Problemen beim Betrieb. Durch erhöhten Energiebedarf und Betriebsstörungen trägt Kolonnen‐Fouling damit auch zur Klimaerwärmung bei. Die im Rahmen des BMWK geförderten Verbundvorhabens SAMARA neu entwickelte Standardapparatur zur Untersuchung von Kolonnen‐Fouling ermöglicht es, Prozesse zur Entstehung und Vermeidung von Fouling in Kolonnen aufzuklären und zielgerichtete Gegenmaßnahmen zu ergreifen.
Co/Fe Dual Catalysis for Sequential Hydrosilylation–Isomerization: Access to Trisubstituted (E)‐Alkenyl Silanes from Terminal Alkynes
Authors: Guo Zhihao , Liu Guixia , Huang Zheng
Published: April 2024

Comprehensive Summary

By rational modification of electronic and steric properties of pincer ligands, a Co/Fe dual catalyst system is developed for one‐pot sequential Markovnikov alkyne hydrosilylation and stereoselective alkene isomerization. The protocol provides an atom‐economical and efficient approach to trisubstituted (E)‐alkenyl silanes from widely accessible terminal alkynes with high regio‐ and stereoselectivities under mild conditions. The utility of this reaction was demonstrated by gram‐scale synthesis and derivatization of bioactive molecules. The radical clock and trapping experiments indicated that radical pathway might be operative in the alkene isomerization step.
Gas‐Phase Preparation of the 14π Hückel Polycyclic Aromatic Anthracene and Phenanthrene Isomers (C14H10) via the Propargyl Addition–BenzAnnulation (PABA) Mechanism
Authors: Wang Chang Yang , Zhao Long , Kaiser Ralf I.
Published: April 2024

Polycyclic aromatic hydrocarbons (PAHs) imply the missing link between resonantly stabilized free radicals and carbonaceous nanoparticles, commonly referred to as soot particles in combustion systems and interstellar grains in deep space. Whereas gas phase formation pathways to the simplest PAH – naphthalene (C10H8) – are beginning to emerge, reaction pathways leading to the synthesis of the 14π Hückel aromatic PAHs anthracene and phenanthrene (C14H10) are still incomplete. Here, by utilizing a chemical microreactor in conjunction with vacuum ultraviolet (VUV) photoionization (PI) of the products followed by detection of the ions in a reflectron time‐of‐flight mass spectrometer (ReTOF‐MS), the reaction between the 1′‐ and 2′‐methylnaphthyl radicals (C11H9⋅) with the propargyl radical (C3H3⋅) accesses anthracene (C14H10) and phenanthrene (C14H10) via the Propargyl Addition–BenzAnnulation (PABA) mechanism in conjunction with a hydrogen assisted isomerization. The preferential formation of the thermodynamically less stable anthracene isomer compared to phenanthrene suggests a kinetic, rather than a thermodynamics control of the reaction.
Ultrafast Spectroelectrochemistry of the Catechol/o‐Quinone Redox Couple in Aqueous Buffer Solution
Authors: Goia Sofia , Richings Gareth W. , Turner Matthew A. P. , Woolley Jack M. , Tully Joshua J. , Cobb Samuel J. , Burriss Adam , Robinson Ben R. , Macpherson Julie V. , Stavros Vasilios G.
Published: April 2024

Eumelanin is a natural pigment found in many organisms that provides photoprotection from harmful UV radiation. As a redox‐active biopolymer, the structure of eumelanin is thought to contain different redox states of quinone, including catechol subunits. To further explore the excited state properties of eumelanin, we have investigated the catechol/o‐quinone redox couple by spectroelectrochemical means, in a pH 7.4 aqueous buffered solution, and using a boron doped diamond mesh electrode. At pH 7.4, the two proton, two electron oxidation of catechol is promoted, which facilitates continuous formation of the unstable o‐quinone product in solution. Ultrafast transient absorption (femtosecond to nanosecond) measurements of o‐quinone species involve initial formation of an excited singlet state followed by triplet state formation within 24 ps. In contrast, catechol in aqueous buffer leads to formation of the semiquinone radical Δt>500 ps. Our results demonstrate the rich photochemistry of the catechol/o‐quinone redox couple and provides further insight into the excited state processes of these key building blocks of eumelanin.
Day‐to‐day organizational life and environmental protection: Evidence from Chinese chemical firms
Authors: Yu Irina Y. , Tso Scarlet H. , Chen Shihua , Du Peng
Published: April 2024

Focusing on the issue of environmental protection, we conducted an empirical study testing the relationship between day‐to‐day organizational life and organizational behavior in a culture influenced by Confucianism. We first reviewed the major characteristics of organizational life in this cultural context, based on which we proposed a model focusing on the relationship between organizational life and firms' performance in environmental protection. We then conducted an empirical study using data from Chinese firms. Our findings suggested that in a developing society such as China, the more a firm's organizational life stresses the value of “being a noble man,” the value of zhongyong, the family–state concept, and the higher the firm's dependency on resources from the government, the greater the likelihood that the firm will perform well in environmental protection. However, surprisingly, yin/yang balance in organizational life did not seem to improve firms' environmental performance. We conclude this paper with a discussion of the implications of our findings and make suggestions for future research.
Isotopic evidence for seasonal water sources in tree xylem and forest soils
Authors: Floriancic Marius G. , Allen Scott T. , Kirchner James W.
Published: April 2024

Forest trees greatly influence both the routing of water downward into the subsurface and the re‐routing of water upward through water uptake and transpiration. To reveal how the subsurface soil water pools used by trees change across seasons, we analysed 2 years of stable isotope ratios of precipitation, soil water from different depths (using both bulk sampling and suction‐cup lysimeters), and xylem in a mixed beech and spruce forest. Precipitation as well as mobile and bulk soil waters all showed a distinct seasonal signature; the seasonal amplitude decreased with depth, and mobile soil waters fluctuated less than bulk soil waters. Xylem water signatures in both tree species were similar to the bulk soil water signatures and rather different from the mobile soil water signatures. The beech and spruce trees had different isotope ratios, suggesting the use of different water sources, and these differences were larger under dry antecedent conditions than wet antecedent conditions. Despite these differences, both species predominantly transpired waters with a winter‐precipitation isotopic signature throughout the summer, including during wet conditions when more recent precipitation was available. Over most of the sampling dates, the fraction of recent precipitation (i.e. from the preceding 30 days) in xylem water was low, despite both species typically demonstrating the use of both shallow and deeper soil waters. These results provide evidence that the soil water storages used by these trees are largely filled in winter and bypassed by recent precipitation, implying long residence times.
The resistance of Georgia coastal marshes to hurricanes
Authors: Smith Rachel S. , Pennings Steven C. , Alber Merryl , Craft Christopher , Byers James E.
Published: April 2024

Ecosystems vary broadly in their responses to disturbance, ranging from highly impacted to resilient or resistant. We conducted a large‐scale analysis of hurricane disturbance effects on coastal marshes by examining 20 years of data from 10 sites covering 100,000 ha at the Georgia Coastal Ecosystems Long‐Term Ecological Research site distributed across gradients of salinity and proximity to the ocean. We analyzed the impacts of Hurricanes Matthew (in 2016) and Irma (in 2017) on marsh biota (plants, crabs, and snails) and physical attributes (erosion, wrack deposition, and sedimentation). We compared these variables prior to the storms (2000–2015) to years with storms (2016, 2017) to those after the storms (2018–2020). Hurricanes generated storm surges that increased water depth and salinity of oligotrophic areas for up to 48 h. Biological variables in the marsh showed few effects of the hurricanes. The only physical variable affected was creek bank slumping; however, slumping had already increased a year before the hurricanes, suggesting that slumping could have a different cause. Thus, our study uncovered only minor, ephemeral impacts on Georgia coastal marshes, highlighting their resistance to hurricane disturbance of the lower magnitude that typically confronts this region of coastline.
Prediction of cardiac worsening through to cardiogenic shock in patients with acute heart failure
Authors: Beer Benedikt N. , Kellner Caroline , Sundermeyer Jonas , Besch Lisa , Dettling Angela , Kirchhof Paulus , Blankenberg Stefan , Magnussen Christina , Schrage Benedikt
Published: April 2024

Aims

Acute heart failure (AHF) can result in worsening of heart failure (WHF), cardiogenic shock (CS), or death. Risk factors for these adverse outcomes are not well characterized. This study aimed to identify predictors for WHF or new‐onset CS in patients hospitalized for AHF.

Methods and results

Prospective cohort study enrolling consecutive patients with AHF admitted to a large tertiary care centre with follow‐up until death or discharge. WHF was defined by the RELAX‐AHF‐2 criteria. CS was defined as SCAI stages B–E. Potential predictors were assessed by fitting logistic regression models adjusted for age and sex. N = 233 patients were enrolled, median age was 78 years, and 80 were women (35.9%). Ischaemic cardiomyopathy was present in 82 patients (40.8%). Overall, 96 (44.2%) developed WHF and 18 (9.7%) CS. In‐hospital death (8/223, 3.6%) was related to both events (WHF: OR 6.64, 95% CI 1.21–36.55, P = 0.03; CS: OR 38.27, 95% CI 6.32–231.81, P < 0.001). Chronic kidney disease (OR 2.20, 95% CI 1.25–3.93, P = 0.007), logarithmized serum creatinine (OR 2.90, 95% CI 1.51–5.82, P = 0.002), cystatin c (OR 1.86, 95% CI 1.27–2.77, P = 0.002), tricuspid valve regurgitation (OR 2.08, 95% CI 1.11–3.94, P = 0.023) and logarithmized pro‐adrenomedullin (OR 3.01, 95% CI 1.75–5.38, P < 0.001) were significant predictors of WHF. Chronic kidney disease (OR 3.17, 95% CI 1.16–9.58, P = 0.03), cystatin c (OR 1.88, 95% CI 1.00–3.53, P = 0.045), logarithmized pro‐adrenomedullin (OR 2.90, 95% CI 1.19–7.19, P = 0.019), and tricuspid valve regurgitation (OR 10.44, 95% CI 2.61–70.00, P = 0.003) were significantly with new‐onset CS.

Conclusions

Half of patients admitted with AHF experience WHF or new‐onset CS. Chronic kidney disease, tricuspid valve regurgitation, and elevated pro‐adrenomedullin concentrations predict these events. They could potentially serve as early warning signs for further deterioration in AHF patients.
NORSE seasonality may vary geographically in adults
Authors: Bolle Andrea Enerstad , Gaist Thomas , Kuljis Anna Maria Eleonora , Blaabjerg Morten , Beier Christoph Patrick
Published: April 2024

The mechanisms causing new onset refractory status epilepticus (NORSE) are often unknown. Recently, a seasonal variation with NORSE peaking during the summer was described in a mixed cohort of adults and children why we here studied the seasonal variation in a Danish status epilepticus (SE) cohort. This retrospective cohort study comprised SE patients aged ≥18 diagnosed and treated 2008–2017 at the Odense University Hospital. Clinical characteristics and seasonality of patients fulfilling the diagnostic criteria for NORSE were compared with patients with refractory SE (RSE) due to other reasons and with the seasonal variation of autoantibodies associated with autoimmune encephalitis in the Danish autoimmune encephalitis register. In this cohort, 26 patients met NORSE criteria. As compared to RSE patients not fulfilling NORSE criteria (n = 152), NORSE patients were more likely to have symptoms of systemic inflammation (C‐reactive protein concentrations ≥10 mg/L or fever ≥38°C) at admission; nine fulfilled the criteria for febrile infection related epilepsy syndrome (FIRES). In contrast to the even seasonal distribution of patients with RSE not fulfilling the NORSE criteria, admissions due to NORSE peaked during the winter (46.1%, p = 0.04 as compared to non‐NORSE RSE); six out of nine FIRES episodes occurred in the winter season. The seasonal variation was not explained by a seasonal variation of the detection rates of autoantibodies associated with autoimmune encephalitis (incl. NMDAR, LGI1, CASPR2, GABAR, GFAP) in a Danish nationwide register (n = 259). In conclusion, we confirm the seasonality of NORSE in a Danish cohort, however, with a peak during winter suggesting a geographical variation not solely explained by autoimmune encephalitis associated with known autoantibodies.

Plain Language Summary

The study investigated the seasonal patterns of new‐onset refractory status epilepticus (NORSE), i.e. severe seizures that occur without an obvious cause and require very intensive treatment. In contrast to the previously observed peak frequency in summer, this Danish study found that NORSE cases peak in winter. Furthermore, the seasonal variation in NORSE cases was not found to be associated with autoimmune encephalitis caused by known autoantibodies. Together with the high rate of patients showing symptoms of systemic inflammation compared to other status epilepticus patients, the data suggest a link between misdirected immune system responses and NORSE. The study can therefore help in the further search for the currently unknown causes of NORSE.
Acid‐etching induced metal cation competitive lattice occupancy of perovskite quantum dots for efficient pure‐blue QLEDs
Authors: Zhu Hanwen , Tong Guoqing , Li Junchun , Tao Xuyong , Shen Yang , Sheng Yuanyuan , Shi Lin , Xie Fengming , Tang Jianxin , Jiang Yang
Published: April 2024

Low efficiency and spectral instability caused by the surface defects have been considerable issues for the mixed‐halogen blue emitting perovskite quantum dots light‐emitting diodes (PeQLEDs). Here, an in situ surface passivation to perovskite quantum dots (PeQDs) is realized by introducing the metal cations competitive lattice occupancy assisted with acid‐etching, in which the long‐chain, insulating and weakly bond surface ligands are removed by addition of octanoic acid (OTAC). Meanwhile, the dissolved A‐site cations (Na+) compete with the protonated oleyl amine and are subsequently anchored to the surface vacancies. The preadded lead bromide, acting as inorganic ligands, demonstrates strong bonding to the uncoordinated surface ions. The as‐synthesized PeQDs show the boosted photoluminescence quantum yield (PLQY) and superior stability with longer lifetime. As a result, the PeQLEDs (470 nm) based on the OTAC‐Na PeQDs exhibit an external quantum efficiency of 8.42% in the mixed halogen PeQDs (CsPb(BrxCl1−x)3). Moreover, the device exhibits superior spectra stability with negligible shift. Our competition mechanism in combination with in situ passivation strategy paves a new way for improving the performance of blue PeQLEDs.
Treatment strategies for pelvic organ prolapse and postoperative outcomes in older women with long‐term care needs: A population‐based retrospective cohort study
Authors: Wada Yoshimitsu , Takei Yuji , Sasabuchi Yusuke , Matsui Hiroki , Yasunaga Hideo , Kohro Takahide , Fujiwara Hiroyuki , Yamana Hayato
Published: April 2024

Objective

The study aimed to investigate treatment options for older women with pelvic organ prolapse (POP) and postoperative outcomes based on their long‐term care (LTC) status.

Methods

We used the medical and LTC insurance claims databases of Tochigi Prefecture in Japan, covering 2014 to 2019. We included women 65 years and older with POP and evaluated their care status and treatment, excluding women with an observation period <6 months. Among women with a postsurgical interval ≥6 months, we compared care level changes and deaths within 6 months and complications within 1 month postoperatively between those with and without LTC using Fisher exact test.

Results

We identified 3406 eligible women. Of the 447 women with LTC and 2959 women without LTC, 16 (3.6%) and 415 (14.0%), respectively, underwent surgery. Among 393 women with a postsurgical interval ≥6 months, 19 (4.8%) required LTC at surgery. Two of the 19 women with LTC (10.5%) and eight of 374 women without LTC (2.1%) experienced worsening care–needs level. No deaths were recorded. Urinary tract infection (UTI) was significantly more frequent in women with LTC than in women without LTC (36.8% vs 8.6%). Other complications were rare in both groups.

Conclusion

The proportion of patients who underwent surgery for POP was lower in women with LTC than in women without LTC. Postoperative UTI was common and 11% had a worsening care–needs level postoperatively, whereas other complications were infrequent. Further detailed studies would contribute to providing optimal treatment to enhance patients' quality of life.
Constructing density forecasts from quantile regressions: Multimodality in macrofinancial dynamics
Authors: Mitchell James , Poon Aubrey , Zhu Dan
Published: April 2024

Quantile regression methods are increasingly used to forecast tail risks and uncertainties in macroeconomic outcomes. This paper reconsiders how to construct predictive densities from quantile regressions. We compare a popular two‐step approach that fits a specific parametric density to the quantile forecasts with a nonparametric alternative that lets the “data speak.” Simulation evidence and an application revisiting GDP growth uncertainties in the United States demonstrate the flexibility of the nonparametric approach when constructing density forecasts from both frequentist and Bayesian quantile regressions. They identify its ability to unmask deviations from symmetrical and unimodal densities. The dominant macroeconomic narrative becomes one of the evolution, over the business cycle, of multimodalities rather than asymmetries in the predictive distribution of GDP growth when conditioned on financial conditions.
Quality of financial reporting in the Indian insurance industry: Does corporate governance matter?
Authors: Goyal Barkha , Gulati Rachita
Published: April 2024

This study explores the relationship between financial reporting quality and insurer governance, with the hypothesis that robust governance procedures exert better control over managers’ opportunistic behavior. The analysis is based on a dataset of insurer firms from 2014 to 2021. The econometric results obtained using the two‐step system GMM technique reveal that the overarching influence of corporate governance on enhancing financial reporting quality is evident, with board and risk governance matters the most. Among individual governance attributes, the optimal board size, a higher proportion of independent directors, audit and risk committees’ size, and risk committee independence play a significant role in governing discretionary accruals. The efficacy of governance mechanisms considerably differs across life and non‐life insurers, shedding light on the nuanced dynamics within the Indian insurance market. The results lend empirical support to resource dependency and agency theories within the Indian insurance sector. The implications suggest potential avenues for amending or redesigning governance norms with specificities of insurers and the ultimate goal of fostering an environment conducive to enhancing the reporting quality of Indian insurance firms.
Does social capital matter to stock price crash risk? Evidence from the US listed firms
Authors: Sun Liang , Yu Huaibing
Published: April 2024

Using a dataset comprised of US publicly traded firms from 2002 to 2018, this paper reveals a significantly negative relationship between social capital and stock price crash risk. Firms located in regions with higher levels of social capital tend to have lower stock price crash risk. This result holds after addressing potential endogeneity. The negative association is more prominent for firms located in rural areas, with greater R&D expenditure, with higher default risk, and during the time periods of non‐financial crisis, respectively. The results of this study are robust to alternative measurements of stock price crash risk, index interpolation, index aggregation, and additional controls.