bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bimolecular Homolytic Substitution (SH2) at a Transition Metal
Authors: Zhang Ying , Li Kai‐Dian , Huang Huan‐Ming 
Published: August 2024

AbstractTransition metal‐catalyzed cross‐coupling reactions have become a powerful and widely used synthetic approach for the construction of both carbon‐carbon and carbon‐heteroatom bonds. These reactions have revolutionized synthetic chemistry by enabling the efficient formation of complex molecular architectures. Among the various methods available, the bimolecular homolytic substitution (SH2) reaction has emerged as an attractive and versatile method for the formation of C(sp3)−C(sp3) and C(sp3)‐heteroatom bonds. In recent years, significant progress has been made in the development of radical SH2 reactions, particularly those involving different transition metal complexes such as cobalt, nickel, and iron. These advancements have expanded the scope of SH2 reactions, allowing for greater diversity in substrate compatibility and reaction conditions. In this review, we aim to highlight the latest breakthroughs and mechanistic insights into radical SH2 reactions, focusing on the role of transition metal catalysts in facilitating these transformations. We will discuss the various types of transition metal complexes that have been employed, the mechanistic pathways involved, and the potential applications of these reactions in the synthesis of complex organic molecules.
Copper‐Catalyzed Aromatization‐Driven Ring‐Opening Amination and Oxygenation of Spiro Dihydroquinazolinones
Authors: Li Wenke , Miao Hong‐Jie , Zhang Jin‐Hua , Duan Xin‐Hua , Guo Li‐Na 
Published: August 2024

AbstractMild and inexpensive copper‐catalyzed aromatization‐driven ring‐opening amination and oxygenation of spiro dihydroquinazolinones are presented, respectively. These protocols provide facile and atom‐economical access to the aminated and the carbonyl‐containing quinazolin‐4(3H)‐ones in good yields with good functional group compatibility, which are difficult to obtain by conventional methods. Remarkably, a telescoped procedure involving the condensation and the ring‐opening/functionalization for simple cycloalkanone was found to be accessible. Mechanistic studies suggest a radical pathway for this transformation.
Integrating autoencoder with Koopman operator to design a linear data‐driven model predictive controller
Authors: Wang Xiaonian , Ayachi Sheel , Corbett Brandon , Mhaskar Prashant 
Published: August 2024

AbstractNon‐linear model predictive control (NMPC) is increasingly seen as a promising tool to tackle the problem of handling process nonlinearity and achieve optimal operation. One roadblock to NMPC implementation, however, is the lack of a good model, whether a first‐principles‐based or a non‐linear data‐driven‐based model such as artificial neural networks (ANN). This manuscript proposes a data‐driven modelling approach that integrates an autoencoder‐like network and dynamic mode decomposition (DMD) methods to result in a non‐linear modelling technique where the non‐linearity in the model stems from the modelling of the measured variables. The proposed method results in a semi‐linear state‐space model where the mapping between the model state and outputs are non‐linear (via the autoencoder‐like network) while the model dynamics are linear. In the subsequent model predictive controller (MPC) implementation, the autoencoder translates setpoints and outputs to the states of a state space model. The proposed approach is illustrated using a continuously stirred tank reactor simulation example. For comparison, a linear MPC and non‐linear MPC based on a traditional neural network (NN) model, a classic Koopman operator‐based MPC, and (to benchmark) a perfect model‐based NMPC are implemented and tested on several setpoint tracking tasks. The proposed MPC design outperforms the other data driven MPCs, and has similar performance as the first‐principles‐based NMPC while requiring less computational time and without requiring first principles knowledge.
Perioperative skin color in patients undergoing transcatheter aortic valve implantation
Authors: Toya Wakana , Akizuki Yuki , Ohno Yohei , Kutsuzawa Tomoko 
Published: August 2024

AbstractPatients who undergo transcatheter aortic valve implantation (TAVI) may become pale during the early postoperative period. To clarify whether facial colors changed during the postoperative period, patients' skin color from before to 72 h after TAVI was measured spectrophotometrically. Factors associated with skin color were also investigated. Forehead skin color and vital signs were measured before TAVI and at 6, 18, and 72 h after TAVI in 11 patients scheduled for TAVI. Blood examinations were performed before and 18 and 72 h after TAVI. Skin color was assessed using a spectrophotometer and expressed as L* (lightness), a* (red/green), and b* (yellow/blue) according to the CIE1976L*a*b* color space. Skin lightness L* values increased at 6 and 18 h after TAVI and returned at 72 h after TAVI and a* values decreased at 6 h after TAVI. The b* values did not change perioperatively during TAVI. No associations were observed between the changes in skin color and changes in BP or laboratory data. The findings that the skin color became whitish and less reddish in the early postoperative period resembled that occurring during an acute inflammatory response. Observation of skin color is important to detect the possibility of postoperative complications.
Effect of Terminal Hydroxy Groups on the Structural Properties of Acyl Thioureas
Authors: Nossa González Diana L. , Gómez Castaño Jovanny A. , Echeverria Gustavo A. , Piro Oscar E. , Saeed Aamer , Erben Mauricio F. 
Published: August 2024

AbstractThe 1‐acyl thiourea family [R1C(O)NHC(S)NR2R3] exhibits the flexibility to incorporate a wide variety of substituents into their structure. The structural attributes of these compounds are intricately tied to the type and extent of substitution. In the case of 3‐mono‐substituted thioureas (R2=H), the conformational behavior is predominantly shaped by the presence of an intramolecular N−H ⋅ ⋅ ⋅ O=C hydrogen bond. This study delves into the structural consequences stemming from the inclusion of substituents possessing hydrogen‐donor capabilities within four novel 1‐acyl‐3‐mono‐substituted thiourea derivatives. A comprehensive suite of analytical techniques, encompassing FTIR, Raman spectroscopy, multinuclear (1H and 13C) NMR spectroscopy, single‐crystal X‐ray diffraction, and supported by computational methods, notably NBO (Natural Bond Orbital) population analysis, Hirshfeld analysis, and QTAIM (Quantum Theory of Atoms in Molecules), was harnessed to scrutinize and characterize these compounds. In the crystalline state, these compounds exhibit an intricate interplay of intermolecular interactions, prominently featuring an expansive network of hydrogen bonds between the hydroxy (−OH) groups and the carbonyl and thiocarbonyl bonds within the 1‐acyl thiourea fragment. Notably, the topological analysis underscores significant distinctions in the properties of the acyl thiourea fragment and the intramolecular >C=O ⋅ ⋅ ⋅ H−N bond when transitioning from the isolated molecule to the crystalline environment.
Enantioselective Discrimination via Wireless Chemiresistive Devices
Authors: Niamlaem Malinee , Grecchi Sara , Malacarne Filippo , Salinas Gerardo , Arnaboldi Serena 
Published: August 2024

AbstractDeveloping chemiresistive devices for the wireless detection of complex analytes has gained considerable interest. In particular, the enantioselective recognition of chiral molecules is still a challenge. Here, we design a hybrid chemiresistive device for the wireless enantioselective discrimination of chiral analytes by combining the enantiorecognition capabilities of an inherently chiral oligomer, that is, oligo‐(3,3’‐dibenzothiophene) (BT2T4) and the insulating/conducting transition of polypyrrole (Ppy). The device is obtained by modifying each extremity of an interdigitated electrode (IDE) with Ppy on the interdigitated area and oligo‐BT2T4 on the connection pads. Due to the asymmetric electroactivity triggered by bipolar electrochemistry, the wireless enantioselective discrimination of both enantiomers of tryptophan and DOPA was achieved. A difference in the onset resistance values was obtained for both enantiomers due to a favorable or unfavorable diastereomeric interaction between the inherently chiral oligomer and the antipode of the chiral molecule. Interestingly, such a device showed a wide quantification range, from μM to mM levels. This work opens up new alternatives to designing advanced wireless devices in enantiorecognition.
Environment‐Benign Colloidal Quantum Dots‐Modified Dual Photoelectrodes for Self‐Biased Photoelectrochemical Water Splitting
Authors: Xia Li , Li Xin , Yang Yang , Tong Xin 
Published: August 2024

AbstractPhotoelectrochemical (PEC) water splitting based on colloidal quantum dots (QDs) presents a promising approach for utilizing solar energy to produce green hydrogen energy. Previous research has been mainly focused on the single‐photoelectrode QDs‐PEC device operated under external bias, while the investigation of dual‐photoelectrode configuration for self‐biased QDs‐PEC system is still lacking. In this work, two types of eco‐friendly Cu‐AISe/ZnSe:Cu (CZAC) and Mn‐AIS/ZnS@Cu (MAZC) QDs were used to respectively sensitize the semiconductor n‐type TiO2 and p‐type Cu2O photoelectrodes, which acted as the photoanode and photocathode to build a heavy metal‐free QDs‐based bias‐free solar water splitting cell, yielding a maximum photocurrent density of 0.47 mA cm−2 and a solar‐to‐hydrogen (STH) efficiency of 0.4 % under 1 sun AM 1.5G illumination (100 mW cm−2). Moreover, approximate 692 nmol of H2 and 355 nmol of O2 with molar ratio of ~2 : 1 was detected after two hours of continuous light illumination, demonstrating the effective overall water splitting. This work indicates a significant advancement towards the realization of a cost‐effective, efficient and “green” QDs‐based artificial solar‐to‐fuel conversion system.
Assessing Avoidant/Restrictive Food Intake Disorder (ARFID) Symptoms Using the Nine Item ARFID Screen in >9000 Swedish Adults With and Without Eating Disorders
Authors: Presseller Emily K. , Cooper Gabrielle E. , Thornton Laura M. , Birgegård Andreas , Abbaspour Afrouz , Bulik Cynthia M. , Forsén Mantilla Emma , Dinkler Lisa 
Published: August 2024

ABSTRACTObjectiveThe Nine Item ARFID Scale (NIAS) is a widely used measure assessing symptoms of avoidant/restrictive food intake disorder (ARFID). Previous studies suggest that individuals with eating disorders driven by shape/weight concerns also have elevated scores on the NIAS. To further describe NIAS scores among individuals with diverse current and previous eating disorders, we characterized NIAS scores in a large sample of individuals with eating disorders and evaluated overlap in symptoms measured by the NIAS and the Eating Disorder Examination‐Questionnaire (EDE‐Q) version 6.0.MethodOur sample comprised 9148 participants from the Eating Disorders Genetics Initiative Sweden (EDGI‐SE), who completed surveys including NIAS and EDE‐Q. NIAS scores were calculated and compared by eating disorder diagnostic group using descriptive statistics and linear models.ResultsParticipants with current anorexia nervosa demonstrated the highest mean NIAS scores and had the greatest proportion (57.0%) of individuals scoring above a clinical cutoff on at least one of the NIAS subscales. Individuals with bulimia nervosa, binge‐eating disorder, and other specified feeding or eating disorder also demonstrated elevated NIAS scores compared to individuals with no lifetime history of an eating disorder (ps < 0.05). All subscales of the NIAS showed small to moderate correlations with all subscales of the EDE‐Q (rs = 0.26–0.40).DiscussionOur results substantiate that individuals with eating disorders other than ARFID demonstrate elevated scores on the NIAS, suggesting that this tool is inadequate on its own for differentiating ARFID from shape/weight‐motivated eating disorders. Further research is needed to inform clinical interventions addressing the co‐occurrence of ARFID‐related drivers and shape/weight‐related motivation for dietary restriction.
Exploring the association between patient‐drawn pain diagrams and psychological and physical health variables: A large‐scale study of patients with low back pain
Authors: Harsted Steen , Chang Natalie H. S. , Nim Casper , Young James J. , McNaughton David T. , O'Neill Søren 
Published: August 2024

AbstractBackgroundDespite the use of Patient‐Drawn Pain Drawings (PDPDs) in clinical settings, their validity as indicators of psychological distress remains debated. We aimed to assess the association between PDPD areas and physical health and psychological variables.MethodsThis study analysed digitally‐drawn PDPDs from 15,345 chronic low back pain (LBP) patients at a Danish outpatient hospital unit. We employed a novel quantitative approach to calculate four log‐transformed geometric pain areas for each PDPD. We assessed six psychological constructs and seven physical health variables. Associations were modelled using multivariable linear regression.ResultsIncreasing leg pain intensity (estimates from 0.12 to 0.25), disability (estimates from 0.3 to 0.14), and pain duration (estimates from 0.10 to 0.33) had the strongest associations with increasing pain areas. Conversely, increasing fear of movement (estimates from −0.02 to −0.05) and catastrophizing (estimates from −0.02 to −0.03) were associated with slight reductions in pain areas. Anxiety and depression had the weakest and most uncertain relationships to pain area size.ConclusionsIncreasing levels of leg pain intensity, pain duration, and pain‐related disability were consistently associated with larger geometric pain areas in PDPDs. Conversely, the associations between the psychological constructs and the geometric pain areas exhibited varying directions and were notably weaker. Clinicians are encouraged to focus on the association of PDPDs with physical symptoms rather than psychological conditions during clinical assessments.Significance StatementThis large‐scale study demonstrates that extensive pain areas in pain drawings drawn by LBP patients do not signify psychological distress. Our findings reveal that these pain representations are more closely linked to increased pain intensity, pain duration, and disability rather than being independently associated with psychological factors. Clinicians are encouraged to focus on the association of extensive pain areas with physical symptoms rather than psychological distress during clinical assessments.
Correlates of chronic pain onset and recovery in the CoLaus cohort
Authors: Dirupo Giada , Rossel Jean‐Benoît , Fournier Nicolas , D'Andrea Audrey , Vollenweider Peter , Decosterd Isabelle , Suter Marc René , Berna Chantal 
Published: August 2024

AbstractBackgroundOnly few previous cohort studies examined simultaneously predictors of chronic pain (CP) onset and recovery. Furthermore, these studies used various sociodemographic and pain‐related characteristics, without standardized measures of sleep and depression. The present study aimed at expanding and strengthening these findings in a large Swiss population.MethodsWe analysed data from a longitudinal cohort (n = 4602) collected at two time points separated by 5 years in Lausanne, Switzerland. We studied through two independent multivariable logistic regression models, the predictors of CP onset and recovery, including socio‐demographic data as well as standardized measures of sleep and mood.ResultsChronic pain was reported by 43.1% and 44.4% of participants, with 11.6% at the second follow‐up reporting moderate or intense pain. Neuropathic pain, regardless of intensity, had a more negative impact on quality of life. An inferential model (n = 1331) identified the male sex as predictive for recovering from CP. Older age, being overweight or obese (compared to normal weight), higher depression scores and pain medication intake were predictive for sustained pain at the second follow‐up. A second model (n = 1886) identified being overweight or obese (compared to normal weight), low quality of sleep and being a former smoker (compared to a non‐smoker) as predictive for developing CP, while the male sex was lowering the risk.ConclusionsWhile sex and weight are associated with both recovery and new CP onset, separate variables also need to be considered in these processes, underlining specific factors to be addressed, depending on the context, whether preventive or therapeutic.Significance StatementMultivariable models in a Swiss cohort (N = 4602) associate male sex, not taking pain medication, normal weight, lower depression scores and younger age with recovery from chronic pain, while females, obese or overweight, having worse sleep and former smokers are associated with onset of new chronic pain. These common and separate factors need to be considered in treatment and prevention efforts.
Suitable engineering demand parameters for acceleration‐sensitive nonstructural components
Authors: Banihashemi MirAmir , Wiebe Lydell , Filiatrault André 
Published: August 2024

AbstractEarly earthquake design codes used peak ground accelerations (PGAs) as intensity measures (IMs) to characterize the demands of ground motions on structures, but have since shifted towards using spectral accelerations because they provide a better indication of demand. The design of acceleration‐sensitive nonstructural components has followed a similar approach, with modern codes being based on an estimate of the spectral acceleration at the period of the nonstructural component. However, most fragility curves for loss assessment of acceleration‐sensitive nonstructural components, including the existing FEMA P58 library, continue to be based on peak floor accelerations (PFAs). Similar to PGAs as an IM for buildings, a limitation of PFA as an engineering demand parameter (EDP) for nonstructural components is its lack of dependence on the period of those components. In this study, fifteen alternative EDPs suggested in the literature are evaluated as potential candidates for developing seismic damage fragility curves. Acceleration‐sensitive nonstructural components are simulated by single‐degree‐of‐freedom (SDOF) components with elastic perfectly plastic behavior, with a period range of 0.01 to 1 s, and varying strength levels. Nonlinear response history analyses are conducted for the SDOFs, using floor motions obtained from both the first floor and the roof of buildings designed with four distinct seismic force‐resisting systems. Ductility demands for each SDOF are taken as an indicator of damage and are predicted using a linear regression model developed for each specific EDP. The suitability of candidate EDPs is evaluated based on their efficiency and relative sufficiency. Furthermore, a comparison is made between the expected annual loss calculated using fragility curves derived from the selected EDPs to quantify how the EDP used for a fragility curve can affect the seismic loss assessment. The results reveal that the PFA is a suitable EDP only for nonstructural components with very short periods (i.e., less than 0.1 s). Moreover, although the spectral acceleration at the period of the SDOF nonstructural component is a suitable EDP for components that are nearly elastic and are located on the roof of buildings, the peaks that develop in the floor spectra can grossly overstate the demands on nonstructural components that experience significant nonlinearity in their response. In such situations, an average of the spectral accelerations in a range of periods near the period of the SDOF nonstructural component is more appropriate.
Detailed detection and extraction of estuarine tidal channels with multispectral and full‐polarised SAR remote sensing
Authors: Li Peng , Li Shu , Li Zhenhong , Liang Cunren , Wang Houjie 
Published: August 2024

AbstractEstuarine tidal channels are active geomorphic units in tidal flats. However, accurate information on the spatiotemporal changes in tidal channel systems remains scarce. The width of the tidal channels may vary from several kilometres to tens of centimetres. Monitoring tidal channel evolution is complicated because of periodic tidal scouring, anthropogenic activities and sea level rise. In this study, we propose a synergetic classification method to detect and extract morphological information of estuarine tidal channels with a spatial resolution of up to 3 m by fusing PlanetScope multispectral data with C‐band GaoFen‐3 fully polarised Synthetic Aperture Radar (SAR) data and machine learning algorithms. Considering the Yellow River Estuary as an example, the spectral features, vegetation and water index, polarisation and texture features derived from the multispectral and SAR images were selected as input data for classifiers according to feature importance ranking. Comparison to the maximum likelihood, and support vector machine classifiers, the synergetic classification with random forest showed the best performance, with an overall accuracy of 99.6%. Based on these results, the total number of tidal channels in the Yellow River Estuary reached 872, with a total length of 348.8 km. The spatiotemporal changes in the central axis over the last 4 years (2019–2022) suggest that the evolution of tidal channels was mainly controlled by ocean dynamics and anthropogenic activities. This method provides a cost‐effective alternative to accurately map tidal channel systems in global estuarine and coastal zones and helps to quantitatively describe their morphological evolution, stability and drivers.
An extreme wave event in Timanfaya National Park: Possible first geological evidence of the 1755 Lisbon tsunami in Lanzarote, Canary Islands
Authors: Galindo Inés , Romero Carmen , Martín‐González Esther , Sánchez Nieves , Vegas Juana , Lario Javier 
Published: August 2024

AbstractThe identification of extreme wave events' deposits is of the main importance in the contexts of global warming and coastal geohazards. Specifically, improving the knowledge of this phenomenon is extremely relevant for high populated volcanic oceanic islands. In this paper, we analyse two extreme wave event deposits located on a coastal platform formed by lavas from the 1730–1736 Timanfaya eruption in Lanzarote Island (Spain). The first one consists of a boulder ridge parallel to the coast of approximately 750 m in length and 7 m asl in elevation. These are accumulations of non‐cemented large boulders and sands that extend about 150 m inland from the intertidal zone. The boulders are of basaltic composition, heterometric, sub‐rounded to angular, and they reach sizes up to 3 m of major axis. They are imbricated both inland and seaward, indicating a strong inundation and backwash. The second deposit is a small outcrop of boulders of equal composition and sizes up to 1 m of major axis, reaching an elevation up to 6 m asl, and has been correlated with the former deposit. Here, the boulders were also deposited on the Timanfaya lavas and later covered by lava flows extruded during the 1824 eruption. Therefore, both deposits could be related with a chronologically well‐contrasted event, between 1736 and 1824. The origin of these deposits could be interpreted as an extreme storm or a tsunami. There are no historical records of extreme storms in the Canary Islands for this period, but there is documentary evidence of the tsunamis of 1761 and 1755. Moreover, for the latter, there is documentation that indicates its impact on coastal infrastructures in the Canary Islands, including the western slope of Lanzarote, and therefore, we propose these deposits as the first sedimentary evidence of the 1755 tsunami in the Canary Islands.