bluuebunny/crossref_metadata_2025_split huggingface dataset:
Asymmetric Synthesis with Organoselenium Compounds – The Past Twelve Years
Authors: Stadel Jessica T. , Back Thomas G. 
Published: January 2024

AbstractThe discovery and synthetic applications of novel organoselenium compounds and their reactions proceeded rapidly during the past fifty years and such processes are now carried out routinely in many laboratories. At the same time, the growing demand for new enantioselective processes provided new challenges. The convergence of selenium chemistry and asymmetric synthesis led to key developments in the 1970s, although the majority of early work was based on stoichiometric processes. More recently, greater emphasis has been placed on greener catalytic variations, along with the discovery of novel reactions and a deeper understanding of their mechanisms. The present review covers the literature in this field from 2010 to early 2023 and encompasses asymmetric reactions mediated by chiral selenium‐based reagents, auxiliaries, and especially, catalysts. Protocols based on achiral selenium compounds in conjunction with other species of chiral catalysts, as well as reactions that are controlled by chiral substrates, are also included.
Analysis of the Unusual Chemical Bonds and Dipole Moments of AeF− (Ae=Be−Ba): A Lesson in Covalent Bonding
Authors: Qin Lei , Liu Yu‐qian , Liu Ruiqin , Yang Xing , Cui Zhong‐hua , Zhao Lili , Pan Sudip , Fau Stefan , Frenking Gernot 
Published: January 2024

AbstractQuantum chemical calculations of the anions AeF− (Ae=Be−Ba) have been carried out using ab initio methods at the CCSD(T)/def2‐TZVPP level and density functional theory employing BP86 with various basis sets. The detailed bonding analyses using different charge‐ and energy partitioning methods show that the molecules possess three distinctively different dative bonds in the lighter species with Ae=Be, Mg and four dative bonds when Ae=Ca, Sr, Ba. The occupied 2p atomic orbitals (AOs) and to a lesser degree the occupied 2s AO of F− donate electronic charge into the vacant spx(σ) and p(π) orbitals of Be and Mg which leads to a triple bond Ae
F−. The heavier Ae atoms Ca, Sr, Ba use their vacant (n‐1)d AOs as acceptor orbitals which enables them to form a second σ donor bond with F− that leads to quadruply bonded Ae
F− (Ae=Ca−Ba). The presentation of molecular orbitals or charge distribution using only one isodensity value may give misleading information about the overall nature of the orbital or charge distribution. Better insights are given by contour line diagrams. The ELF calculations provide monosynaptic and disynaptic basins of AeF− which nicely agree with the analysis of the occupied molecular orbitals and with the charge density difference maps. A particular feature of the covalent bonds in AeF− concerns the inductive interaction of F− with the soft valence electrons in the (n)s valence orbitals of Ae. The polarization of the (n)s2 electrons induces a (n)spx hybridized lone‐pair orbital at atom Ae, which yields a large dipole moment with the negative end at Ae. The concomitant formation of a vacant (n)spx AO of atom Ae, which overlaps with the occupied 2p(σ) AO of F−, leads to a strong covalent σ bond.
Silver‐Catalyzed Dearomative Skeletal Editing of Indazoles by Donor Carbene Insertion
Authors: Li Linxuan , Chen Hongzhu , Liu Menglin , Zhu Qingwen , Zhang Hongru , de Ruiter Graham , Bi Xihe 
Published: January 2024

AbstractGiven the prevalence of heterocyclic scaffolds in drug‐related molecules, converting these highly modular heterocyclic scaffolds into structural diversified and dearomatized analogs is an ideal strategy for improving their physicochemical and pharmacokinetic properties. Here, we described an efficient method for silver carbene‐mediated dearomative N−N bond cleavage leading to skeletal hopping between indazole and 1,2‐dihydroquinazoline via a highly selective single‐carbon insertion procedure. Using this methodology, a series of dihydroquinazoline analogues with diarylmethylene‐substituted quaternary carbon centers were constructed with excellent yields and good functional group compatibility, which was further illustrated by the late‐stage diversification of important pharmaceutically active ingredients. DFT calculations indicated that the silver catalyst not only induces the formation of the silver carbene, but also activates the diazahexatriene intermediate, which plays a crucial role in the formation of the C−N bond.
Semiparametric estimation for the functional additive hazards model
Authors: Hao Meiling , Liu Kin‐yat , Su Wen , Zhao Xingqiu 
Published: January 2024

AbstractWe propose a new functional additive hazards model to investigate the potential effects of functional and scalar predictors on mortality risks, and develop a penalized least squares estimation method for model parameters based on a pseudoscore estimating equation. A reproducing kernel Hilbert space approach is used to establish the consistency, convergence rate, and joint asymptotic distribution of the resulting estimators for finite‐dimensional and infinite‐dimensional parameters. Our simulation studies demonstrate that the proposed estimation procedure performs well. For illustration, we apply the proposed method to the Medical Information Mart for Intensive Care III dataset.
Patient selection considerations for AADC deficiency gene therapy
Authors: Roubertie Agathe , Anselm Irina , Ben‐Zeev Bruria , Hwu Wuh‐Liang , Kumar Ashutosh , Monteleone Berrin , Muramatsu Shin‐ichi , Leuzzi Vincenzo , Ibáñez Salvador , Stone Scellig , Pearl Phillip L. 
Published: January 2024

AbstractBackgroundAromatic ʟ‐amino acid decarboxylase (AADC) deficiency is a rare, severe neurological disorder caused by pathogenic variants in the dopa decarboxylase (DDC) gene, resulting in a combined deficiency of monoamine neurotransmitters. Clinically, patients present with a range of dysfunctions that impact motor, autonomic, and cognitive development. The constellation of symptoms of AADC deficiency varies among patients, and clinical presentation falls across a wide spectrum. However, most patients with AADC deficiency experience significant impairments when compared with children with normal development, irrespective of genotype, phenotype, or disease severity. Further, AADC deficiency is associated with increased mortality.MethodsIn response to the recent approval of a disease‐modifying gene therapy for AADC deficiency, this review presents considerations for the selection of patients for treatment.ConclusionSuggested clinical criteria to determine whether a patient is a candidate for gene therapy are: (1) genetically and biochemically confirmed AADC deficiency; (2) lack of achievement of gross motor milestones and/or persistence of clinically significant movement disorders; (3) persistent neurocognitive or systemic symptoms secondary to AADC deficiency despite standard medical therapy; and (4) informed parental/guardian decision and consent to treatment.
Retrospective analysis of presymptomatic treatment in Sturge–Weber syndrome
Authors: Valery Chelsea B. , Iannotti Isabelle , Kossoff Eric H. , Zabel Andrew , Cohen Bernard , Ou Yangming , Pinto Anna , Comi Anne M. 
Published: January 2024

AbstractBackgroundNinety percent of infants with Sturge–Weber syndrome (SWS) brain involvement have seizure onset before 2 years of age; early‐onset seizures are associated with worse neurological outcome. Presymptomatic treatment before seizure onset may delay seizure onset and improve outcome, as has been shown in other conditions with a high risk of developing epilepsy, such as tuberous sclerosis complex. The electroencephalogram (EEG) may be a biomarker to predict seizure onset. This retrospective clinical data analysis aims to assess the impact of presymptomatic treatment in SWS.MethodsThis two‐center, Institutional Review Board–approved, retrospective study analyzed records from patients with SWS brain involvement. Clinical data recorded included demographics, age of seizure onset (if present), brain involvement extent (unilateral versus bilateral), port‐wine birthmark (PWB) extent, family history of seizures, presymptomatic treatment if received, Neuroscore, and antiseizure medications. EEG reports prior to seizure onset were analyzed.ResultsNinety‐two patients were included (48 females), and 32 received presymptomatic treatment outside of a formal protocol (five aspirin, 16 aspirin and levetiracetam; nine aspirin and oxcarbazepine, two valproic acid). Presymptomatically treated patients were more likely to be seizure‐free at 2 years (15 of 32, 47% versus 7 of 60, 12%; p < 0.001). A greater percentage of presymptomatically treated patients had bilateral brain involvement (38% treated versus 17% untreated; p = 0.026). Median hemiparesis Neuroscore at 2 years was better in presymptomatically treated patients. In EEG reports prior to seizure onset, the presence of slowing, epileptiform discharges, or EEG‐identified seizures was associated with seizure onset by 2 years (p = 0.001).ConclusionPresymptomatic treatment is a promising approach to children diagnosed with SWS prior to seizure onset. Further study is needed, including prospective drug trials, long‐term neuropsychological outcome, and prospective EEG analysis, to assess this approach and determine biomarkers for presymptomatic treatment.
Tunable Phosphorescence in Metastable CuI Assemblies Prepared by Acid‐Fueled Crystal‐to‐Crystal Conversion
Authors: Fan Jingyi , Gu Zhuoya , Han Xiao , Zhou Xiuwen , Hou Hong‐Wei , Ding Jie 
Published: January 2024

AbstractAcid acts as a “fuel” in driving kinetic self‐assembly, with crystals of the CuII complex ([CuIICl2(BH)2], BH=benzothiadiazole helicene derivative) being successfully converted to crystals of 1 ([H2BH][CuBr3]) and 2 ([H2BH][CuBr3⋅2H2O]). The metastable features of 1 and 2 enable CuI guest release, with transformation into a thermodynamically favorable form 3 (H2BH⋅2Br). Compound 1 exhibits dual phosphorescence at 452 nm (3MC) and 709 nm (3CT) at room temperature. At lower temperatures, the 3CT band disappears and the 3MC band weakens, while a new emission band at 621 nm (3ππ*) is enhanced. In 1, the subtle structural change and significant emission change depending on temperature is reversible. In contrast, 2 exhibits only 3MC emission at room temperature, with less efficient triplet‐triplet energy transfer (TTET) below 250 K, and with residual 3ππ* emission occurring upon returning to room temperature, even after one week.
Multiphase injection locking for multiple rotary pulses in a coupled oscillator lattice loop
Authors: Narahara Koichi 
Published: January 2024

SummaryThis study provides design criteria of multiphase injection locking for an oscillator loop with multiple rotary pulses that can be utilized for an effective frequency multiplier. Coupled oscillator lattice loops can support phase waves. In the case where
pulses rotate in the loop, the oscillatory signal exhibits
times higher frequency than the rotation frequency of a single rotary pulse. Once an external signal succeeds in injection locking the single‐pulse rotation, the loop operates as an efficient
times frequency multiplier. As in a ring oscillator, the progressive multiphase injection locking is best employed, when the loop supports only a single rotary pulse. Because the phase of the external signal becomes different for each pulse, progressive phase assignment does not work well for multiple rotary pulses; therefore, a more efficient scheme of phase assignment is investigated and validated by bifurcation analyses and measurements. The most effective multiphase injection locking is expected for the phase difference between two neighboring oscillators to be set to
(
), when
pulses rotate to the cell address increases (decreases) in an oscillator loop.
Association of latent factors of neuroinflammation with Alzheimer's disease pathology and longitudinal cognitive decline
Authors: Teipel Stefan J. , Dyrba Martin , Kleineidam Luca , Brosseron Frederic , Levin Fedor , Bruno Davide , Buerger Katharina , Cosma Nicoleta , Schneider Luisa‐Sophie , Düzel Emrah , Glanz Wenzel , Fliessbach Klaus , Janowitz Daniel , Kilimann Ingo , Laske Christoph , Munk Matthias H. , Maier Franziska , Peters Oliver , Pomara Nunzio , Perneczky Robert , Rauchmann Boris‐Stephan , Priller Josef , Ramirez Alfredo , Roy Nina , Schneider Anja , Spottke Annika , Spruth Eike J. , Roeske Sandra , Wagner Michael , Wiltfang Jens , Wolfsgruber Steffen , Bartels Claudia , Jessen Frank , Heneka Michael T. ,   for the DELCODE study group and the Alzheimer´s Disease Neuroimaging Initiative
Published: January 2024

AbstractINTRODUCTIONWe investigated the association of inflammatory mechanisms with markers of Alzheimer's disease (AD) pathology and rates of cognitive decline in the AD spectrum.METHODSWe studied 296 cases from the Deutsches Zentrum für Neurodegenerative Erkrankungen Longitudinal Cognitive Impairment and Dementia Study (DELCODE) cohort, and an extension cohort of 276 cases of the Alzheimer's Disease Neuroimaging Initiative study. Using Bayesian confirmatory factor analysis, we constructed latent factors for synaptic integrity, microglia, cerebrovascular endothelial function, cytokine/chemokine, and complement components of the inflammatory response using a set of inflammatory markers in cerebrospinal fluid.RESULTSWe found strong evidence for an association of synaptic integrity, microglia response, and cerebrovascular endothelial function with a latent factor of AD pathology and with rates of cognitive decline. We found evidence against an association of complement and cytokine/chemokine factors with AD pathology and rates of cognitive decline.DISCUSSIONLatent factors provided access to directly unobservable components of the neuroinflammatory response and their association with AD pathology and cognitive decline.
Microstructural alterations in the locus coeruleus‐entorhinal cortex pathway in Alzheimer's disease and frontotemporal dementia
Authors: Quattrini Giulia , Pini Lorenzo , Boscolo Galazzo Ilaria , Jelescu Ileana O. , Jovicich Jorge , Manenti Rosa , Frisoni Giovanni B. , Marizzoni Moira , Pizzini Francesca B. , Pievani Michela 
Published: January 2024

AbstractINTRODUCTIONWe investigated in vivo the microstructural integrity of the pathway connecting the locus coeruleus to the transentorhinal cortex (LC‐TEC) in patients with Alzheimer's disease (AD) and frontotemporal dementia (FTD).METHODSDiffusion‐weighted MRI scans were collected for 21 AD, 20 behavioral variants of FTD (bvFTD), and 20 controls. Fractional anisotropy (FA), mean, axial, and radial diffusivities (MD, AxD, RD) were computed in the LC‐TEC pathway using a normative atlas. Atrophy was assessed using cortical thickness and correlated with microstructural measures.RESULTSWe found (i) higher RD in AD than controls; (ii) higher MD, RD, and AxD, and lower FA in bvFTD than controls and AD; and (iii) a negative association between LC‐TEC MD, RD, and AxD, and entorhinal cortex (EC) thickness in bvFTD (all p < 0.050).DISCUSSIONLC‐TEC microstructural alterations are more pronounced in bvFTD than AD, possibly reflecting neurodegeneration secondary to EC atrophy.Highlights
Microstructural integrity of LC‐TEC pathway is understudied in AD and bvFTD.
LC‐TEC microstructural alterations are present in both AD and bvFTD.
Greater LC‐TEC microstructural alterations in bvFTD than AD.
LC‐TEC microstructural alterations in bvFTD are associated to EC neurodegeneration.
Identification of three unexpected new psychoactive substances at an Australian drug checking service
Authors: Algar Jess L. , Lawes Douglas J. , Carroll Adam J. , Caldicott David , McLeod Malcolm D. 
Published: January 2024

AbstractDrug checking is a harm reduction measure that provides people with the opportunity to confirm the identity and purity of substances before consumption. The CanTEST Health and Drug Checking Service is Australia's first fixed‐site drug checking service, where clients can learn about the contents of the samples they provide while receiving tailored harm reduction and health advice. Three samples were recently presented to the service with the expectation of 4‐fluoromethylphenidate (4F‐MPH) 1, methoxetamine (MXE) 2 and 3‐methylmethcathinone (3‐MMC) 3. The identity of all three samples did not meet these expectations and remained unknown on‐site, as no high confidence identifications were obtained. However, further analysis by nuclear magnetic resonance spectroscopy, high resolution gas chromatography‐electron ionisation‐mass spectrometry and liquid chromatography‐electrospray ionisation‐mass spectrometry at the nearby Australian National University allowed for the structure elucidation of the three samples as 4‐fluoro‐α‐pyrrolidinoisohexanophenone (4F‐α‐PiHP) 4, 1‐(4‐fluorobenzyl)‐4‐methylpiperazine (4F‐MBZP) 5 and N‐propyl‐1,2‐diphenylethylamine (propylphenidine) 6, respectively. Given all three samples were not of the expected identity and have not yet been described as new psychoactive substances in the literature, this study presents a full characterisation of each compound. As exemplified by this rapid identification of three unexpected new psychoactive substances, drug checking can be used as an effective method to monitor the unregulated drug market.
Clinical characteristics of hospitalized male adolescents and young adults with atypical anorexia nervosa
Authors: Nagata Jason M. , Vargas Ruben , Sanders Austin E. , Stuart Elena , Downey Amanda E. , Chaphekar Anita V. , Nguyen Anthony , Ganson Kyle T. , Buckelew Sara M. , Garber Andrea K. 
Published: January 2024

AbstractObjectiveTo describe the clinical characteristics of male adolescents and young adults hospitalized for medical complications of atypical anorexia nervosa (atypical AN) and to compare their clinical characteristics with females with atypical AN and males with anorexia nervosa (AN).MethodA retrospective review of electronic medical records for patients with atypical AN and AN aged 9–25 admitted to the UCSF Eating Disorders Program from May 2012 to August 2020 was conducted.ResultsAmong 21 males with atypical AN (mean age 15.1 ± 2.7, mean %mBMI 102.0 ± 11.8), medical complications evidenced by admission laboratory values included anemia (52.9%), vitamin D insufficiency/deficiency (52.6%), and zinc deficiency (31.6%). Compared with females with atypical AN (n = 69), males with atypical AN had longer length of stay (11.4 vs 8.4 days, p = .004), higher prescribed kcal at discharge (4114 vs 3045 kcal, p < .001), lower heart rate nadir (40.0 vs 45.8, p = .038), higher aspartate transaminase (AST, 37.9 vs 26.2 U/L, p = .032), higher alanine transaminase (ALT, 30.6 vs 18.3 U/L, p = .005), and higher rates of anemia (52.9% vs 19.4%, p = .005), with no differences in vitamin D, zinc, and vital signs. Compared with males with AN (n = 40), males with atypical AN had no significant differences in vital signs or laboratory assessments during the hospitalization.DiscussionAtypical AN in males leads to significant medical comorbidity, and males with atypical AN require longer hospital stays compared to females with atypical AN. Rates of abnormal vital signs and abnormal serum laboratory values during hospital admissions do not differ in males with atypical AN compared to AN.Public SignificanceAdolescent and young adult males with atypical anorexia nervosa experience significant medical complications. Males with atypical anorexia nervosa had longer hospitalizations and higher prescribed nutrition at discharge than females. Medical complications of atypical anorexia nervosa in male adolescents and young adults were generally equal to those of male adolescents and young adults with anorexia nervosa. Clinicians should be aware of unique medical complications of males with atypical anorexia nervosa.
Cyclic Alkyl(amino) Carbene‐Induced Rearrangement of Ga‐Phosphaketene
Authors: Li Bin , Wölper Christoph , Weinert Hanns Micha , Siera Hannah , Haberhauer Gebhard , Schulz Stephan 
Published: January 2024

AbstractReactions of LGa(Cl)P(cAAC) (L=HC[C(Me)N(2,6‐iPr2C6H3)]2, MecAAC (MecAAC=1‐(2,6‐di‐iso‐propylphenyl)‐3,3,5,5‐tetramethyl‐pyrrolidin‐2‐ylidene) with NaPCO and NaN3 gave LGa(PCO)P(MecAAC) (1) and LGa(N3)P(MecAAC) (2), respectively. DFT calculations on the nature of compounds 1 and 2 reveal a phosphaalkene rather than a carbene‐phosphinidene structure. The reaction of 1 with MecAAC resulted in a nucleophilic attack of the electron‐rich P atom on the γ‐C backbone of the β‐diketiminate ligand to give compound 3 as the major product and cyclic 1,2‐diphospha‐1,3‐butadiene LGa(P2OC)MecAAC (4) in minor yield.
TL‐PBot: Twitter bot profile detection using transfer learning based on DNN model
Authors: Bibi Maryam , Hussain Qaisar Zahid , Aslam Naeem , Faheem Muhammad , Akhtar Perveen 
Published: January 2024

AbstractOnline social networks (OSNs) have reduced global boundaries, with Twitter enabling perspective sharing. Bot profile‐propagated false information misuse raises serious concerns. Considering this issue, we present our research on classifying Twitter accounts as “human” or “bot” using deep neural networks and transfer learning. Our proposed approach, TL‐PBot, stands for bot profile detection using transfer learning. The TL‐PBot framework utilizes Twitter account metadata such as follower count. Our TL‐PBot also incorporates text data from the Twitter description field as a feature. Word representation of the text data is achieved using Global Vectors (GloVe), a pre‐trained model. By employing user profile‐based features, we significantly reduce the overhead of feature engineering. The hybrid nature of the model enables it to effectively handle mixed‐type features, including text, binary, and numerical data. We design the network using long‐short‐term memory (LSTM) units. DNN model layers were trained, and the weights of the pre‐trained model layers were frozen to apply the transfer learning, resulting in reduced training time and improved bot profile detection accuracy. The performance of the proposed TL‐PBot is evaluated using publicly available datasets. The proposed approach is trained and tested on the same datasets and further evaluated on the validation datasets that were not used in the training phase, which is also a novelty in our approach. Comparative analysis with state‐of‐the‐art approaches demonstrates that the TL‐PBot approach achieves a higher accuracy of 98.07%, while excelling in precision of 99%, recall of 98%, f measure of 98.32%, and AUC of 0.99. Employing the transfer learning strategy resulted in an accelerated detection rate of 5.04 milliseconds, attesting to the effectiveness of this approach in enhancing computational efficiency.