bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fast and Tunable Phosphorescence from Organic Ionic Crystals
Authors: Partanen Iida , Al‐Saedy Omar , Eskelinen Toni , Karttunen Antti J. , Saarinen Jarkko J. , Mrózek Ondrej , Steffen Andreas , Belyaev Andrey , Chou Pi‐Tai , Koshevoy Igor O. 
Published: May 2023

AbstractCrystalline diphosphonium iodides [MeR2P‐spacer‐R2Me]I with phenylene (1, 2), naphthalene (3, 4), biphenyl (5) and anthracene (6) as aromatic spacers, are photoemissive under ambient conditions. The emission colors (λem values from 550 to 880 nm) and intensities (Φem reaching 0.75) are defined by the composition and substitution geometry of the central conjugated chromophore motif, and the anion‐π interactions. Time‐resolved and variable‐temperature luminescence studies suggest phosphorescence for all the titled compounds, which demonstrate observed lifetimes of 0.46–92.23 μs at 297 K. Radiative rate constants kr as high as 2.8×105 s−1 deduced for salts 1–3 were assigned to strong spin‐orbit coupling enhanced by an external heavy atom effect arising from the anion‐π charge‐transfer character of the triplet excited state. These rates of anomalously fast metal‐free phosphorescence are comparable to those of transition metal complexes and organic luminophores that utilize triplet excitons via a thermally activated delayed fluorescence mechanism, making such ionic luminophores a new paradigm for the design of photofunctional and responsive molecular materials.
Going Beyond Silver in Ethylene Epoxidation with First‐Principles Catalyst Screening
Authors: Huš Matej , Grilc Miha , Teržan Janvit , Gyergyek Sašo , Likozar Blaž , Hellman Anders 
Published: May 2023

AbstractEthylene epoxidation is industrially and commercially one of the most important selective oxidations. Silver catalysts have been state‐of‐the‐art for decades, their efficiency steadily improving with empirical discoveries of dopants and co‐catalysts. Herein, we perform a computational screening of the metals in the periodic table, identify prospective superior catalysts and experimentally demonstrate that Ag/CuPb, Ag/CuCd and Ag/CuTl outperform the pure‐Ag catalysts, while they still confer an easily scalable synthesis protocol. Furthermore, we show that to harness the potential of computationally‐led discovery of catalysts fully, it is essential to include the relevant in situ conditions e.g., surface oxidation, parasitic side reactions and ethylene epoxide decomposition, as neglecting such effects leads to erroneous predictions. We combine ab initio calculations, scaling relations, and rigorous reactor microkinetic modelling, which goes beyond conventional simplified steady‐state or rate‐determining modelling on immutable catalyst surfaces. The modelling insights have enabled us to both synthesise novel catalysts and theoretically understand experimental findings, thus, bridging the gap between first‐principles simulations and industrial applications. We show that the computational catalyst design can be easily extended to include larger reaction networks and other effects, such as surface oxidations. The feasibility was confirmed by experimental agreement.
Chromium‐Doped Nickel Oxide and Nickel Nitride Mediate Selective Electrocatalytic Oxidation of Sterol Intermediates Coupled with H2 Evolution
Authors: Li Suiqin , Wang Shibin , He Jiahui , Li Kai , Xu Yinjie , Wang Mengxin , Zhao Shuying , Wang Yuhang , Li Xiaonian , Zhong Xing , Wang Jianguo 
Published: May 2023

AbstractReplacing the oxygen evolution reaction (OER) with the thermodynamically favorable electrooxidation of organics is considered a promising approach for the simultaneous production of hydrogen (H2) and high‐value chemicals. However, exploring and optimizing efficient electrocatalysts remains a challenge for large‐scale production of value‐added steroid carbonyl and H2. Herein, Cr‐NiO/GF and Cr‐Ni3N/GF (GF: graphite felt) electrocatalysts were designed as anode and cathode for the production of steroid carbonyls and H2, respectively. The cooperative Cr‐NiO and ACT (4‐acetamido‐2,2,6,6‐tetramethyl‐1‐piperidine‐N‐oxyl) electrocatalyst can be extended to the electrooxidation of a series of steroid alcohols to the corresponding aldehydes. Additionally, Cr‐Ni3N displays superior electrocatalytic activity for hydrogen evolution reaction (HER), with a low overpotential of 35 mV to deliver 10 mA cm−2. Furthermore, the system coupled with anodic electrooxidation of sterol and cathodic HER exhibited excellent performance with high space‐time yield of 48.85 kg m−3 h−1 for steroid carbonyl and 1.82 L h−1 for H2 generation in a two‐layer stacked flow cell. Density Functional Theory (DFT) calculations indicated that Cr doping effectively stabilizes ACTH on the NiO surface, and ACTH molecule could be captured via the ketonic oxygen interaction with Cr, resulting in excellent electrocatalytic activity. This work develops a novel approach to the rational design of efficient electrocatalysts for the simultaneous production of H2 and large‐scale value‐added pharmaceutical carbonyl intermediates.
Fine‐Tuning Substrate–Catalyst Halogen–Halogen Interactions for Boosting Enantioselectivity in Halogen‐Bonding Catalysis
Authors: Keuper Alica C. , Fengler Kevin , Ostler Florian , Danelzik Tobias , Piekarski Dariusz G. , García Mancheño Olga 
Published: May 2023

AbstractA new approach towards highly enantioselective halogen‐bonding catalysis has been developed. To circumvent the intrinsic issues of the nature of the halogen‐bond (XB) and the resultant unresolved limitations in asymmetric catalysis, fine‐tuned halogen–halogen interactions between the substrate and XB‐donor were designed to preorganize the substrate in the catalyst's cavity and boost enantiocontrol. The present strategy exploits both the electron cloud (Lewis base site) and the sigma (σ)‐hole site of the halogen substituent of the substrates to form a tight catalyst–substrate–counteranion chiral complex, thus enabling a controlled induction of high levels of chirality transfer. Remarkable enantioselectivities of up to 95 : 5 e.r. (90 % ee) have been achieved in a model dearomatization reaction of halogen‐substituted (iso)quinolines with tetrakis‐iodotriazole multidentate anion‐binding catalysts.
Enhancement of electrospun UHMWPE fiber performance through post‐processing treatment
Authors: Nayak Prajesh , Ghosh Anup K. , Bhatnagar Naresh 
Published: May 2023

AbstractIn this study, the mechanical performance of electrospun ultra‐high molecular weight polyethylene (UHMWPE) fiber was successfully improved by post‐processing treatment. It is performed by stretching the electrospun UHMWPE mat under constant load at temperatures ranging from 90 to 150°C. The temperature is varied in order to achieve the highest possible draw ratio. The prepared fibers were characterized for their morphological and thermal properties. Moreover, the induced fiber morphology and their performance due to the effect of high‐temperature stretching were evaluated using different characterization techniques such as scanning electron microscopy, wide‐angle X‐ray diffraction, and tensile testing analysis. In addition, the characteristics of prepared yarns were also compared with a commercial grade of Spectra® fibers. This analysis shows that the post‐processing of the mat resulted in the production of axially elongated microfibrillar yarn. Maximum tensile strength of 11.14 ± 3.65 GPa was attained at a stretching temperature of 130°C. However, further raising the temperature causes a decline in performance, demonstrating that the stretching temperature dramatically influences the properties of the fiber.
Clinical characteristics and outcomes of patients with mental illnesses who attempted suicide by drug overdose: A retrospective analysis of 109 cases
Authors: Chen Naiyun , Li Shaoli , Huang Shu , Lai Jianbo , Lv Duo 
Published: May 2023

AbstractObjectiveIndividuals with mental illnesses are exposed to an increased risk of suicide. In this study, we aimed to investigate the clinical characteristics and outcome of psychiatric patients who attempted suicide by drug overdose and required emergency care.MethodsA retrospective study was carried out in the Department of Emergency, the First Affiliated Hospital, Zhejiang University School of Medicine. Electronic medical records of psychiatric patients who were hospitalized due to suicide attempts from March 2019 to February 2022, with a discharge diagnosis of drug overdose were reviewed. Suicide‐related data of patients were collected, including suicide month, time from suicide to admission, type of drugs, the number of tablets taken, as well as demographic and clinical profiles (e.g., gender, age, marital status, profession, physical comorbidities, and diagnosis of mental illness).ResultsIn the results, half of the patients were young people, female patients accounted for a higher proportion (72.5%), and the incidence of suicide was higher in winter than other seasons. Among the 109 psychiatric patients, 60 patients (55.0%) had a history of major depressive disorder, and 86 patients (78.9%) committed suicide with various psychotropic drugs, among which anxiolytics were the most commonly used drugs. Thirty‐seven patients (33.9%) experienced severe physical complications caused by drug overdose, with lung infections being the most common. The clinical outcome of most patients was favorable following emergent treatment, while 2 patients (1.8%) older than 80 failed to survive.ConclusionA better understanding of psychiatric patients referred to emergency care due to suicide by drug overdose helps to improve the clinical management and prognosis of patients.
Controlling Swing Rates in Macrocyclic Molecular Mortise Hinges
Authors: Menke Alexander J. , Mellberg Joseph M. , Pan Hongjun , Reibenspies Joseph H. , Janesko Benjamin G. , Simanek Eric E. 
Published: May 2023

AbstractHinge motion is observed in macrocyclic, mortise‐type molecular hinges using variable temperature NMR spectroscopy. The data is consistent with dynamic hinging from a folded‐to‐extended‐to‐folded enantiomeric state. Crystallographic and solution structures of the folded states are reported. Chemical shift predictions derived from crystallographic data corroborate fully revolute hinge motion. The rate of hinging is affected by steric congestion at the hinge axis. A macrocycle containing glycine, 1, hinges faster than one comprising aminoisobutyric acid, 2. The free energies of activation, ΔG≠, for 1 and 2 were determined to be 13.3±0.3 kcal/mol and 16.3±0.3 kcal/mol, respectively. This barrier is largely independent of solvent across those surveyed (CD3OD, CD3CN, DMSO‐d6, pyridine‐d5, D2O). Experiment and computation predict energy barriers that are consistent with disruption of an intramolecular network of hydrogen bonds. DFT calculations reveal a pathway for hinge motion.
Diverse Reactions of α‐Diimine‐Ligated MgI−MgI‐Bonded Compound with Carbodiimides
Authors: Yang Li , Qu Yao , Wang Juju , Xu Wenhua , Zhao Yanxia , Yang Xiao‐Juan 
Published: May 2023

AbstractThe α‐diimine‐ligated dimagnesium(I) compound [K(thf)3]2[LMg−MgL] (1, L=[(2,6‐iPr2C6H3)NC(Me)]22−) displays diverse reactivities toward carbodiimides (RN=C=NR) with different R substituents. In the reaction of 1 with Me3SiNCNSiMe3, one of the easily leaving trimethylsilyl groups is lost to yield the Me3SiNCN− moiety that either bridges two MgII centers (2) or terminally coordinated (3). In contrast, with the similarly bulky tBuNCNtBu, the carbodiimide inserts into Mg−Mg bond with accompanying C−H activation of a ligand or solvent (products 4 and 5). In the case of dicyclohexyl or diisopropyl carbodiimide, reductive C−C coupling of two RNCNR molecules occurs to form the [C2(NR)4]2− diamido moiety, which bridges two Mg centers, giving complexes [{K(dme)2}2LMg(μ‐{C2(NR)4})MgL] (6, R=Cy; 7, R=iPr) and [L⋅−Mg(μ‐{C2(NR)4})MgL⋅−] (8). Most interestingly, upon treating 1 with Me3SiC≡CSiMe3, the acetylide complex [K(dme)][LMg(C≡CSiMe3)(dme)] (9) was prepared, which undergoes a rare “double insertion” with CyNCNCy to afford [K(solv)][K(dme)2LMg(NCy)2C−C≡C−C(NCy)2MgL] (10) containing an acetylenediide‐coupled bis(amidinate) ligand that bridges two Mg atoms.
Supramolecular Chirogenesis in a Sterically Hindered Porphyrin: A Critical Theoretical Analysis**
Authors: Osadchuk Irina , Luts Hanna‐Eliisa , Norvaiša Karolis , Borovkov Victor , Senge Mathias O. 
Published: May 2023

AbstractThe determination of molecular stereochemistry and absolute configuration is an important part of modern chemistry, pharmacology, and biology. Electronic circular dichroism (ECD) spectroscopy is a widely used tool for chirality assignment, especially with porphyrin macrocycles employed as reporter chromophores. However, the mechanisms of induced ECD in porphyrin complexes are yet to be comprehensively rationalized. In this work, the ECD spectra of a sterically hindered hexa‐cationic porphyrin with two camphorsulfonic acids in dichloromethane and chloroform were experimentally measured and computationally analyzed. The influence of geometric factors such as the position of chiral guest molecules, distortion of the porphyrin macrocycle, and orientation of aromatic and non‐aromatic peripheral substituents on the ECD spectra was theoretically studied. Various potential pitfalls, such as a lack of significant conformations and accidental agreement of experimental and simulated spectra, are considered and discussed.
A person‐centered data analytic approach to dopaminergic polygenic moderation of child maltreatment exposure
Authors: Handley Elizabeth D. , Russotti Justin , Ross Andrew J. , Toth Sheree L. , Cicchetti Dante 
Published: May 2023

AbstractThe present study illustrates the utility of latent class analysis, a person‐centered data analytic approach, as an innovative method for identifying naturally occurring patterns of polygenic risk, specifically within the dopaminergic system. Moreover, this study tests whether latent classes of polygenic variation moderate the effect of child maltreatment exposure on internalizing symptoms among African ancestry youth. African ancestry youth were selected for this study because youth of color are overrepresented in the child welfare system and because African ancestry individuals are significantly underrepresented in genomics research. Results identified three latent classes of dopaminergic gene variation. Class 1 was marked predominately by homozygous minor alleles, Class 2 was characterized by homozygous major and heterozygous presentations, and Class 3 was marked by heterozygous alleles on the DAT‐1 single‐nucleotide polymorphisms (SNPs) and a combination of homozygous major and minor alleles on the other SNPs. Results indicated that a greater number of maltreatment subtypes experienced were associated with higher internalizing symptoms only for children with the latent polygenic Class 2 pattern. This latent class was distinctly characterized by more homozygous major or heterozygous allelic presentations along all three DAT‐1 SNPs. This significant latent polygenic class by environment interaction was replicated in an independent replication sample. Together, findings suggest that African ancestry children with a pattern of dopaminergic variation characterized by this specific combination of polygenic variation are more vulnerable to developing internalizing symptoms following maltreatment exposure, relative to their peers with other dopamine‐related polygenic patterns.
Addressing multi‐site functional MRI heterogeneity through dual‐expert collaborative learning for brain disease identification
Authors: Fang Yuqi , Potter Guy G. , Wu Di , Zhu Hongtu , Liu Mingxia 
Published: May 2023

AbstractSeveral studies employ multi‐site rs‐fMRI data for major depressive disorder (MDD) identification, with a specific site as the to‐be‐analyzed target domain and other site(s) as the source domain. But they usually suffer from significant inter‐site heterogeneity caused by the use of different scanners and/or scanning protocols and fail to build generalizable models that can well adapt to multiple target domains. In this article, we propose a dual‐expert fMRI harmonization (DFH) framework for automated MDD diagnosis. Our DFH is designed to simultaneously exploit data from a single labeled source domain/site and two unlabeled target domains for mitigating data distribution differences across domains. Specifically, the DFH consists of a domain‐generic student model and two domain‐specific teacher/expert models that are jointly trained to perform knowledge distillation through a deep collaborative learning module. A student model with strong generalizability is finally derived, which can be well adapted to unseen target domains and analysis of other brain diseases. To the best of our knowledge, this is among the first attempts to investigate multi‐target fMRI harmonization for MDD diagnosis. Comprehensive experiments on 836 subjects with rs‐fMRI data from 3 different sites show the superiority of our method. The discriminative brain functional connectivities identified by our method could be regarded as potential biomarkers for fMRI‐related MDD diagnosis.
Human gut microbiome: A primer for the clinician
Authors: Kedia Saurabh , Ahuja Vineet 
Published: May 2023

AbstractThe human host gets tremendously influenced by a genetically and phenotypically distinct and heterogeneous constellation of microbial species—the human microbiome—the gut being one of the most densely populated and characterized site for these organisms. Microbiome science has advanced rapidly, technically with respect to the analytical methods and biologically with respect to its mechanistic influence in health and disease states. A clinician conducting a microbiome study should be aware of the nuances related to microbiome research, especially with respect to the technical and biological factors that can influence the interpretation of research outcomes. Hence, this review is an attempt to detail these aspects of the human gut microbiome, with emphasis on its determinants in a healthy state.
A real‐world evaluation of the implementation of NLP technology in abstract screening of a systematic review
Authors: Perlman‐Arrow Sara , Loo Noel , Bobrovitz Niklas , Yan Tingting , Arora Rahul K. 
Published: May 2023

AbstractThe laborious and time‐consuming nature of systematic review production hinders the dissemination of up‐to‐date evidence synthesis. Well‐performing natural language processing (NLP) tools for systematic reviews have been developed, showing promise to improve efficiency. However, the feasibility and value of these technologies have not been comprehensively demonstrated in a real‐world review. We developed an NLP‐assisted abstract screening tool that provides text inclusion recommendations, keyword highlights, and visual context cues. We evaluated this tool in a living systematic review on SARS‐CoV‐2 seroprevalence, conducting a quality improvement assessment of screening with and without the tool. We evaluated changes to abstract screening speed, screening accuracy, characteristics of included texts, and user satisfaction. The tool improved efficiency, reducing screening time per abstract by 45.9% and decreasing inter‐reviewer conflict rates. The tool conserved precision of article inclusion (positive predictive value; 0.92 with tool vs. 0.88 without) and recall (sensitivity; 0.90 vs. 0.81). The summary statistics of included studies were similar with and without the tool. Users were satisfied with the tool (mean satisfaction score of 4.2/5). We evaluated an abstract screening process where one human reviewer was replaced with the tool's votes, finding that this maintained recall (0.92 one‐person, one‐tool vs. 0.90 two tool‐assisted humans) and precision (0.91 vs. 0.92) while reducing screening time by 70%. Implementing an NLP tool in this living systematic review improved efficiency, maintained accuracy, and was well‐received by researchers, demonstrating the real‐world effectiveness of NLP in expediting evidence synthesis.
Dietary exposure and risk assessment of polychlorinated biphenyls to artisanal fishermen and fish vendors: A case study of Dar es Salaam
Authors: Mwaijibe Gabriel Jacob Gabriel , Kilima Beatrice Mgaya 
Published: May 2023

AbstractBackgroundFish is one of the main sources of food and income in Tanzania, with 25% of the population depending on fishing activities as a source of food, income, and employment. But fish consumers are vulnerable to exposure to toxic pollutants including PCBs due to the lipophilic nature of the pollutants which accumulate in fish.ResultsThe estimated mean NDL PCBs concentration level was 0.84 ng/g w/w and the mean fish consumption rate among fishermen was 0.4 kg/day. Mean exposure of the fishermen and fish vendors to total PCBs ranged between 9.62 and 36.12 ng/kg bw/day depending on the estimation scenario (lower bound/upper bound) for both normal and higher fish consumers. The general population exposure to total PCBs was 0.4 and 0.8 ng/kg bw/day in lower‐bound and upper‐bound estimation scenarios respectively. The estimated lifetime carcinogenic and non‐carcinogenic hazard indices from intake of estimated total PCBs by fishermen and fish vendors exceeded the recommended tolerable daily intake, TDI, raising serious concerns for adverse health effects to fishermen and fish vendors. However, for the general population, there was no concern for any potential health effects as the estimated hazard indices were far below the recommended levels for intake of total PCBs.ConclusionThe exposure levels of fishermen and fish vendors to PCBs via consumption of Rastrelliger kanagutra (Indian mackerel) in Dar es Salaam are high enough to course serious health concerns, especially for high fish consumers and efforts should be taken to encourage diversification of fish species intake.
Preclinical Models of Laryngeal Papillomavirus Infection: A Scoping Review
Authors: King Renee E. , Bilger Andrea , Rademacher Josef , Lambert Paul F. , Thibeault Susan L. 
Published: May 2023

ObjectiveLaryngeal human papillomavirus (HPV) infection causes recurrent respiratory papillomatosis (RRP) and accounts for up to 25% of laryngeal cancers. Lack of satisfactory preclinical models is one reason that treatments for these diseases are limited. We sought to assess the literature describing preclinical models of laryngeal papillomavirus infection.Data SourcesPubMed, Web of Science, and Scopus were searched from the inception of database through October 2022.Review MethodsStudies searched were screened by two investigators. Eligible studies were peer‐reviewed, published in English, presented original data, and described attempted models of laryngeal papillomavirus infection. Data examined included type of papillomavirus, infection model, and results including success rate, disease phenotype, and viral retention.ResultsAfter screening 440 citations and 138 full‐text studies, 77 studies published between 1923 and 2022 were included. Models used low‐risk HPV or RRP (n = 51 studies), high‐risk HPV or laryngeal cancer (n = 16), both low‐ and high‐risk HPV (n = 1), and animal papillomaviruses (n = 9). For RRP, 2D and 3D cell culture models and xenografts retained disease phenotypes and HPV DNA in the short term. Two laryngeal cancer cell lines were consistently HPV‐positive in multiple studies. Animal laryngeal infections with animal papillomaviruses resulted in disease and long‐term retention of viral DNA.ConclusionsLaryngeal papillomavirus infection models have been researched for 100 years and primarily involve low‐risk HPV. Most models lose viral DNA after a short duration. Future work is needed to model persistent and recurrent diseases, consistent with RRP and HPV‐positive laryngeal cancer.Level of EvidenceNA Laryngoscope, 133:3256–3268, 2023