bluuebunny/crossref_metadata_2025_split huggingface dataset:
Unsupervised machine learning model to predict cognitive impairment in subcortical ischemic vascular disease
Authors: Qin Qi , Qu Junda , Yin Yunsi , Liang Ying , Wang Yan , Xie Bingxin , Liu Qingqing , Wang Xuan , Xia Xinyi , Wang Meng , Zhang Xu , Jia Jianping , Xing Yi , Li Chunlin , Tang Yi 
Published: February 2023

AbstractINTRODUCTIONIt is challenging to predict which patients who meet criteria for subcortical ischemic vascular disease (SIVD) will ultimately progress to subcortical vascular cognitive impairment (SVCI).METHODSWe collected clinical information, neuropsychological assessments, T1 imaging, diffusion tensor imaging, and resting‐state functional magnetic resonance imaging from 83 patients with SVCI and 53 age‐matched patients with SIVD without cognitive impairment. We built an unsupervised machine learning model to isolate patients with SVCI. The model was validated using multimodal data from an external cohort comprising 45 patients with SVCI and 32 patients with SIVD without cognitive impairment.RESULTSThe accuracy, sensitivity, and specificity of the unsupervised machine learning model were 86.03%, 79.52%, and 96.23% and 80.52%, 71.11%, and 93.75% for internal and external cohort, respectively.DISCUSSIONWe developed an accurate and accessible clinical tool which requires only data from routine imaging to predict patients at risk of progressing from SIVD to SVCI.HighlightsOur unsupervised machine learning model provides an accurate and accessible clinical tool to predict patients at risk of progressing from subcortical ischemic vascular disease (SIVD) to subcortical vascular cognitive impairment (SVCI) and requires only data from imaging routinely used during the diagnosis of suspected SVCI.The model yields good accuracy, sensitivity, and specificity and is portable to other cohorts and to clinical practice to distinguish patients with SIVD at risk for progressing to SVCI.The model combines assessment of diffusion tensor imaging and functional magnetic resonance imaging measures in patients with SVCI to analyze whether the “disconnection hypothesis” contributes to functional and structural changes and to the clinical presentation of SVCI.
Easy Access to Diverse Multiblock Copolymers with On‐Demand Blocks via Thioester‐Relayed In‐Chain Cascade Copolymerization
Authors: Zhang Ze , Xiong Yu , Yang Peng , Li Yang , Tang Rui , Nie Xuan , Chen Guang , Wang Long‐Hai , Hong Chun‐Yan , You Ye‐Zi 
Published: February 2023

AbstractMultiblock copolymers are envisioned as promising materials with enhanced properties and functionality compared with their diblock/triblock counterparts. However, the current approaches can construct multiblock copolymers with a limited number of blocks but tedious procedures. Here, we report a thioester‐relayed in‐chain cascade copolymerization strategy for the easy preparation of multiblock copolymers with on‐demand blocks, in which thioester groups with on‐demand numbers are built in the polymer backbone by controlled/living polymerizations. These thioester groups further serve as the in‐chain initiating centers to trigger the acyl group transfer ring‐opening polymerization of episulfides independently and concurrently to extend the polymer backbone into multiblock structures. The compositions, number of blocks, and block degree of polymerization can be easily regulated. This strategy can offer easy access to a library of multiblock copolymers with ≈100 blocks in only 2 to 4 steps.
Symmetry‐Induced Singlet‐Triplet Inversions in Non‐Alternant Hydrocarbons**
Authors: Terence Blaskovits J. , Garner Marc H. , Corminboeuf Clémence 
Published: February 2023

AbstractMolecules with inversion of the singlet and triplet excited‐state energies are highly promising for the development of organic light‐emitting diodes (OLEDs). To date, azaphenalenes are the only class of molecules where these inversions have been identified. Here, we screen a curated database of organic crystal structures to identify existing compounds for violations of Hund's rule in the lowest excited states. We identify two further classes with this behavior. The first, a class of zwitterions, has limited relevance to molecular emitters as the singlet‐triplet inversions occur in the third excited singlet state. The second class consists of twoD2h‐symmetry non‐alternant hydrocarbons, a fused azulene dimer and a bicalicene, whose lowest excited singlet states violate Hund's rule. Due to the connectivity of the polycyclic structure, they achieve this symmetry through aromatic stabilization. These hydrocarbons show promise as the next generation of building blocks for OLED emitters.
Highly Selective Photoelectroreduction of Carbon Dioxide to Ethanol over Graphene/Silicon Carbide Composites
Authors: Feng Guanghui , Wang Shibin , Li Shenggang , Ge Ruipeng , Feng Xuefei , Zhang Junwei , Song Yanfang , Dong Xiao , Zhang Jiazhou , Zeng Gaofeng , Zhang Qiang , Ma Guijun , Chuang Yi‐De , Zhang Xixiang , Guo Jinghua , Sun Yuhan , Wei Wei , Chen Wei 
Published: February 2023

AbstractUsing sunlight to produce valuable chemicals and fuels from carbon dioxide (CO2), i.e., artificial photosynthesis (AP) is a promising strategy to achieve solar energy storage and a negative carbon cycle. However, selective synthesis of C2compounds with a high CO2conversion rate remains challenging for current AP technologies. We performed CO2photoelectroreduction over a graphene/silicon carbide (SiC) catalyst under simulated solar irradiation with ethanol (C2H5OH) selectivity of>99 % and a CO2conversion rate of up to 17.1 mmol gcat−1 h−1with sustained performance. Experimental and theoretical investigations indicated an optimal interfacial layer to facilitate the transfer of photogenerated electrons from the SiC substrate to the few‐layer graphene overlayer, which also favored an efficient CO2to C2H5OH conversion pathway.
Synthesis of P‐Stereogenic Phosphine Oxides via Nickel‐Catalyzed Asymmetric Cross‐Coupling of Secondary Phosphine Oxides with Alkenyl and Aryl Bromides
Authors: Wang Chuanyong , Hu Xiaobo , Xu Cheng , Ge Qiangqiang , Yang Qingliang , Xiong Jianqi , Duan Wei‐Liang 
Published: February 2023

AbstractA general and mild nickel‐catalyzed enantioselective C(sp2)−P cross‐coupling for synthesizing P‐stereogenic phosphine oxides has been developed. The asymmetric alkenylation/arylation of racemic secondary phosphine oxides with alkenyl/aryl bromides generated P‐stereogenic phosphine oxides with high yields and enantioselectivities. Various functional groups were tolerated, and the applications of this method were demonstrated through late‐stage functionalization and product transformations.
Direct π‐Activation vs. O‐Activation in Halogen‐Bonding Catalysis
Authors: Robidas Raphaël , Legault Claude Y. 
Published: February 2023

AbstractHalogen bond donors had an increasing impact on catalysis in recent years, and their development is highly active. In particular, numerous iodine‐based halogen bond donors have been developed and used to promote various reactions through coordinating carbonyl groups, a ubiquitous mode of activation in catalysis. We now report computational data which strongly suggests that an alternative activation mode, through direct π‐complexation, is operative for unsaturated carbonyl substrates. Calculations also suggest that solvent polarity could have a clear impact on the preference of the mode of activation, raising the possibility of a mechanistic manifold switch through solvent variation. These findings could profoundly impact the development of the next generation of halogen‐bond donor catalysts.
Single‐Atom‐Mediated Spinel Octahedral Structures for Elevated Performances of Li‐Oxygen Batteries
Authors: Zhang Yu , Zhang Shuting , Ma Junguo , Chen Xin , Nan Caiyun , Chen Chen 
Published: February 2023

AbstractLi‐oxygen batteries have attracted much attention due to its ultra‐high theoretical specific capacity, but the discharge product Li2O2is easy to accumulate, leading to low battery stability. Here, we demonstrate a series of high‐efficiency cathode catalysts of Co3O4loaded with single‐atomic metals (M=Ru, Pd, Pt, Au, Ir). The single‐atomic metal could substitute the central Co atom in the octahedral coordination structure and maintain the structural stability; benefiting from the electron promoter effect, rendering more highly active Co3+exposed, providing rich nucleation sites for Li2O2deposition. And the loaded M atoms could separate the active Co3+centers, thereby regulating the dispersion of Li2O2to obtained a sheet‐like morphology, which could facilitate its decomposition in the subsequent charge cycle. Our work found that the single atoms could effectively modulate the active metal oxide with which it is coordinated, thus collectively boosting the catalytic performance.
Recycling Valuable Metals from Spent Lithium‐Ion Batteries Using Carbothermal Shock Method
Authors: Zhu Xu‐Hui , Li Yan‐Juan , Gong Meng‐Qi , Mo Ran , Luo Si‐Yuan , Yan Xiao , Yang Shun 
Published: February 2023

AbstractPyrometallurgy technique is usually applied as a pretreatment to enhance the leaching efficiencies in the hydrometallurgy process for recovering valuable metals from spent lithium‐ion batteries. However, traditional pyrometallurgy processes are energy and time consuming. Here, we report a carbothermal shock (CTS) method for reducing LiNi0.3Co0.2Mn0.5O2 (NCM325) cathode materials with uniform temperature distribution, high heating and cooling rates, high temperatures, and ultrafast reaction times. Li can be selectively leached through water leaching after CTS process with an efficiency of >90 %. Ni, Co, and Mn are recovered by dilute acid leaching with efficiencies >98 %. The CTS reduction strategy is feasible for various spent cathode materials, including NCM111, NCM523, NCM622, NCM811, LiCoO2, and LiMn2O4. The CTS process, with its low energy consumption and potential scale application, provides an efficient and environmentally friendly way for recovering spent lithium‐ion batteries.
A Highly Stable Organic Luminescent Diradical
Authors: Abdurahman Alim , Wang Jingmin , Zhao Yihan , Li Ping , Shen Li , Peng Qiming 
Published: February 2023

AbstractIt is very challenging to obtain stable room‐temperature luminescent open‐shell singlet diradicals. Herein we report the first stable Müller's hydrocarbon TTM‐PhTTM with luminescent properties. Variable‐temperature electron paramagnetic resonance spectroscopy measurements and theoretical calculations show that TTM‐PhTTM has an open‐shell singlet ground state with a diradical character of 90 %. Because of a small singlet‐triplet energy gap, the open‐shell singlet ground state can be thermally excited to a triplet state. TTM‐PhTTM shows room‐temperature deep‐red emission in various solutions. Unusually high stability of TTM‐PhTTM was also observed owing to effective steric hindrance and spin delocalization. Our results are beneficial to the rational design and discovery of more stable luminescent diradical materials.
Engineered Metallacycle‐Based Supramolecular Photosensitizers for Effective Photodynamic Therapy
Authors: Tu Le , Li Chonglu , Xiong Xiaoxing , Hyeon Kim Ji , Li Qian , Mei Longcan , Li Junrong , Liu Shuang , Seung Kim Jong , Sun Yao 
Published: February 2023

AbstractAlthough metallacycle‐based supramolecular photosensitizers (PSs) have attracted increasing attention in biomedicine, their clinical translation is still hindered by their inherent dark toxicity. Herein, we report what to our knowledge is the first example of a molecular engineering approach to building blocks of metallacycles for constructing a series of supramolecular PSs (RuA–RuD), with the aim of simultaneously reducing dark toxicity and enhancing phototoxicity, and consequently obtaining high phototoxicity indexes (PI). Detailed in vitro investigations demonstrate thatRuA–RuDdisplay high cancer cellular uptake and remarkable antitumor activity even under hypoxic conditions. Notably,RuDexhibited no dark toxicity and displayed the highest PI value (≈406). Theoretical calculations verified thatRuDhas the largest steric hindrance and the lowest singlet‐triplet energy gap (ΔEST, 0.61 eV). Further in vivo studies confirmed thatRuDallows safe and effective phototherapy against A549 tumors.
ESIPT‐Inspired Dual‐Mode Photoswitches with Fast Molecular Isomerization in the Solid State
Authors: Chen Yahui , Lee You Rim , Wang Wenjing , Fang Yu , Lu Sheng , Han Jingjing , Chen Xiaoqiang , Kim Myung Hwa , Yoon Juyoung 
Published: February 2023

AbstractPhotoswitchable materials have attracted considerable attention in various fields. Developing excellent solid‐state dual‐mode photoswitches is an important but challenging task. Herein, we propose a new strategy to construct an excited‐state intramolecular proton transfer (ESIPT) inspired photoswitch (DiAH‐pht) that possesses aggregation‐induced emission (AIE) features and displays a fast molecular isomerization process characterized by dual‐mode behavior in the solid state. Mechanistic studies indicate that introduction of a bulky group can create a folded molecular conformation that provides adequate volume to facilitate photoisomerization and the enhanced ESIPT effect can boost the isomerization process. The feasibility of our strategy was further demonstrated by the activated photoisomerization performance of the Schiff base derivatives. Furthermore,DiAH‐phtshows good performance in the fields of dual‐mode information encryption and high‐density data storage.
Perioperative management of a parturient with VACTERL association for a caesarean section
Authors: Tonks K. E. , Birch S. , Ito Y. , Bhagwat A. 
Published: February 2023

SummaryA parturient with VACTERL association (vertebral defects, anal atresia, cardiac defects, trachea‐oesophageal fistula, renal abnormalities and limb abnormalities) was listed for an elective caesarean section. She had a short neck with reduced cervical extension and flexion. Magnetic resonance imaging of her whole spine was performed which showed failure of cervical spine segmentation and cervical stenosis. Neuraxial blockade could have resulted in unpredictable spread of local anaesthetic due to the low volume of the spinal canal, and could have caused myelopathic changes within the spinal cord due to cerebrospinal fluid pressure changes. A general anaesthetic using a rapid sequence induction was also predicted to be challenging due to her fixed, unstable neck and severe cervical spine stenosis. After a multidisciplinary discussion Including neurosurgeons, we planned for awake tracheal intubation followed by general anaesthesia. However, before the date of her planned delivery, she required an urgent caesarean section due to severe preeclampsia. This was performed under general anaesthesia following uncomplicated awake tracheal intubation.
Pigment epithelium‐derived factor enhances peripheral nerve regeneration through modulating oxidative stress and stem cells
Authors: Onger Mehmet Emin , Altun Gamze , Yildiran Alisan 
Published: February 2023

AbstractPeripheral nerve injury is common and negatively affects an individual's quality of life. Drugs used for peripheral nerve regeneration should aim to eliminate symptoms such as neuropathic pain and have therapeutic effects. In recent studies, pigment epithelium‐derived factor (PEDF) has been considered an essential therapeutic agent because of its potential neuroprotective properties. In this study, we aimed to investigate the efficacy of locally applied PEDF for peripheral nerve regeneration. Twenty‐four Wistar albino male rats were used. The study groups included Injury (n = 12) and Injury+PEDF (n = 12). An injury model was created by applying 50 N pressure to the right sciatic nerves in groups, and 10 μg/kg local PEDF was injected into the Injury+PEDF group. After 28 days of recovery, functional tests and stereological, immunohistochemical, and biochemical analyses were performed. A significant difference was found between the Injury and Injury+PEDF groups in amplitude, whereas no difference was found in latency. The number of myelinated axons and the myelinated axon area increased significantly in the Injury+PEDF group, while no statistically significant difference was found in myelin sheath thickness. Superoxide dismutase, catalase, and glutathione peroxidase activities were increased by PEDF, whereas they were suppressed in mesenchymal stem cells. PEDF exerts functional, quantitative, and antioxidative effects on sciatic nerve injury during neuroregeneration. In addition, when oxidative stress parameters were examined, it was seen that PEDF reduced oxidative stress following sciatic nerve injury.
The sacred stone from the sea. Archaeological and ethnographic perspectives on the ritual value of coral across the Pacific
Authors: Molle Guillaume , Wadrawane Jean‐Marie , Lagarde Louis , Wright Duncan 
Published: February 2023

ABSTRACTThe Pacific Islands offer a variety of marine environments providing peoples in the present and past with abundant coral materials, a “stone from the sea”. Archaeologists have long recognised the importance of coral in ancient contexts, whether as gravel, natural branches, squared blocks or cut‐and‐dress slabs. Coral was also used to manufacture tools such as files or pounders and incorporated in monumental ceremonial architecture as a favoured construction material and foundation offerings. However, Pacific Islanders also employed coral material for other ritual applications that remain overlooked in the literature. In this article, we consider the multiple uses of coral in the archaeological and ethnographic records of three Pacific regions: Central‐East Polynesia (CEP), New Caledonia and the Torres Strait Islands. This includes offering of coral branches, sometimes associated with cairns, paraphernalia and magic stones, also production of coral lime for body ornamentation. Using these case studies, we consider material selection, modes of deposition, archaeological and ethnographic contexts, associations with other features and artefacts, before interrogating the potential significance of these unrealised datasets. By doing so, we shed new light on the ritual value of coral and reflect on the symbolic nature and function of this material.
Approximate controllability of stochastic delay differential systems driven by Poisson jumps with instantaneous and noninstantaneous impulses
Authors: Kumar Surendra , Yadav Shobha 
Published: February 2023

AbstractControl systems in which instantaneous and noninstantaneous impulses occur simultaneously are difficult to handle. In this article, we investigate the solvability and approximate controllability for a new category of stochastic differential equations steered by Poisson jumps with instantaneous and noninstantaneous impulses. Utilizing the theory of fundamental solution, stochastic analysis, the measure of noncompactness, and the fixed‐point approach, we establish the presence of a mild solution for the proposed system. We have also constructed a new set of sufficient constraints that assures approximate controllability of the considered system. Next, we discuss the existence of a solution and approximate controllability for an impulsive deterministic control system in which the nonlinear term contains spatial derivatives. Lastly, two examples are presented to encapsulate the abstract results.
Autism severity and its relationship to disability
Authors: Waizbard‐Bartov Einat , Fein Deborah , Lord Catherine , Amaral David G. 
Published: February 2023

AbstractAutism severity is currently defined and measured based exclusively on the severity levels of the two core symptom domains: social‐communication and restricted or repetitive patterns of behaviors and interests. Autistic individuals, however, are often diagnosed with other medical, developmental, and psychological co‐occurring conditions. These additional challenges such as intellectual disability, limited expressive and/or receptive language, and anxiety disorders, can have a tremendous impact on the day‐to‐day lives of autistic individuals, for both their adaptive functioning as well as their sense of wellbeing. Furthermore, the initial presentation of core symptoms and their likelihood of changing over time are influenced by the presence of such co‐occurring conditions. In order to truly understand how a person's autism impacts their life, both core symptoms as well as other challenges should be considered. This approach was recently taken byThe Lancet Commission on the future of care and clinical research in autism, which proposed the term “profound autism” for a subgroup of individuals presenting with high core symptom severity, co‐occurring intellectual disability, and little or no language, who require extensive long‐term care. Considering other individual factors such as daily living skills, specific support needs and environmental resources would also enhance the evaluation of disability in autistic individuals. As currently employed in the assessment of intellectual disability, a multidimensional approach to autism could provide a more comprehensive system for classification of impairment. At present, however, there is no formal way to designate the combined effect of these different aspects of autism on a person's life. A comprehensive outlook that acknowledges impairments, capabilities, co‐occurring conditions, and environmental factors would be useful for identifying subgroups of individuals as well as for determining individual needs and strengths in clinical assessments.
A classification model for continuous responses: Identifying risk perception groups on health‐related activities
Authors: de Oliveira Eduardo S. B. , Wang Xiaojing , Bazán Jorge L. 
Published: February 2023

AbstractIn the current literature on latent variable models, much effort has been put on the development of dichotomous and polytomous cognitive diagnostic models (CDMs) for assessments. Recently, the possibility of using continuous responses in CDMs has been brought to discussion. But no Bayesian approach has been developed yet for the analysis of CDMs when responses are continuous. Our work is the first Bayesian framework for the continuous deterministic inputs, noisy, and gate (DINA) model. We also propose new interpretations for item parameters in this DINA model, which makes the analysis more interpretable than before. In addition, we have conducted several simulations to evaluate the performance of the continuous DINA model through our Bayesian approach. Then, we have applied the proposed DINA model to a real data example of risk perceptions for individuals over a range of health‐related activities. The application results exemplify the high potential of the use of the proposed continuous DINA model to classify individuals in the study.
Bias‐reduced estimators of conditional odds ratios in matched case‐control studies with unmatched confounding
Authors: Blagus Rok 
Published: February 2023

AbstractWe study bias‐reduced estimators of exponentially transformed parameters in general linear models (GLMs) and show how they can be used to obtain bias‐reduced conditional (or unconditional) odds ratios in matched case‐control studies. Two options are considered and compared: the explicit approach and the implicit approach. The implicit approach is based on the modified score function where bias‐reduced estimates are obtained by using iterative procedures to solve the modified score equations. The explicit approach is shown to be a one‐step approximation of this iterative procedure. To apply these approaches for the conditional analysis of matched case‐control studies, with potentially unmatched confounding and with several exposures, we utilize the relation between the conditional likelihood and the likelihood of the unconditional logit binomial GLM for matched pairs and Cox partial likelihood for matched sets with appropriately setup data. The properties of the estimators are evaluated by using a large Monte Carlo simulation study and an illustration of a real dataset is shown. Researchers reporting the results on the exponentiated scale should use bias‐reduced estimators since otherwise the effects can be under or overestimated, where the magnitude of the bias is especially large in studies with smaller sample sizes.