bluuebunny/crossref_metadata_2025_split huggingface dataset:
Carbene-catalyzed atroposelective synthesis of axially chiral styrenes
Authors: Yan Jia-Lei , Maiti Rakesh , Ren Shi-Chao , Tian Weiyi , Li Tingting , Xu Jun , Mondal Bivas , Jin Zhichao , Chi Yonggui Robin 
Published: January 2022

AbstractAxially chiral styrenes bearing a chiral axis between a sterically non-congested acyclic alkene and an aryl ring are difficult to prepare due to low rotational barrier of the axis. Disclosed here is an N-heterocyclic carbene (NHC) catalytic asymmetric solution to this problem. Our reaction involves ynals, sulfinic acids, and phenols as the substrates with an NHC as the catalyst. Key steps involve selective 1,4-addition of sulfinic anion to acetylenic acylazolium intermediate and sequential E-selective protonation to set up the chiral axis. Our reaction affords axially chiral styrenes bearing a chiral axis as the product with up to > 99:1 e.r., > 20:1 E/Z selectivity, and excellent yields. The sulfone and carboxylic ester moieties in our styrene products are common moieties in bioactive molecules and asymmetric catalysis.
Streamlined single-cell proteomics by an integrated microfluidic chip and data-independent acquisition mass spectrometry
Authors: Gebreyesus Sofani Tafesse , Siyal Asad Ali , Kitata Reta Birhanu , Chen Eric Sheng-Wen , Enkhbayar Bayarmaa , Angata Takashi , Lin Kuo-I , Chen Yu-Ju , Tu Hsiung-Lin 
Published: January 2022

AbstractSingle-cell proteomics can reveal cellular phenotypic heterogeneity and cell-specific functional networks underlying biological processes. Here, we present a streamlined workflow combining microfluidic chips for all-in-one proteomic sample preparation and data-independent acquisition (DIA) mass spectrometry (MS) for proteomic analysis down to the single-cell level. The proteomics chips enable multiplexed and automated cell isolation/counting/imaging and sample processing in a single device. Combining chip-based sample handling with DIA-MS using project-specific mass spectral libraries, we profile on average ~1,500 protein groups across 20 single mammalian cells. Applying the chip-DIA workflow to profile the proteomes of adherent and non-adherent malignant cells, we cover a dynamic range of 5 orders of magnitude with good reproducibility and <16% missing values between runs. Taken together, the chip-DIA workflow offers all-in-one cell characterization, analytical sensitivity and robustness, and the option to add additional functionalities in the future, thus providing a basis for advanced single-cell proteomics applications.
Storms drive outgassing of CO2 in the subpolar Southern Ocean
Authors: Nicholson Sarah-Anne , Whitt Daniel B. , Fer Ilker , du Plessis Marcel D. , Lebéhot Alice D. , Swart Sebastiaan , Sutton Adrienne J. , Monteiro Pedro M. S. 
Published: January 2022

AbstractThe subpolar Southern Ocean is a critical region where CO2 outgassing influences the global mean air-sea CO2 flux (FCO2). However, the processes controlling the outgassing remain elusive. We show, using a multi-glider dataset combining FCO2 and ocean turbulence, that the air-sea gradient of CO2 (∆pCO2) is modulated by synoptic storm-driven ocean variability (20 µatm, 1–10 days) through two processes. Ekman transport explains 60% of the variability, and entrainment drives strong episodic CO2 outgassing events of 2–4 mol m−2 yr−1. Extrapolation across the subpolar Southern Ocean using a process model shows how ocean fronts spatially modulate synoptic variability in ∆pCO2 (6 µatm2 average) and how spatial variations in stratification influence synoptic entrainment of deeper carbon into the mixed layer (3.5 mol m−2 yr−1 average). These results not only constrain aliased-driven uncertainties in FCO2 but also the effects of synoptic variability on slower seasonal or longer ocean physics-carbon dynamics.
Dynamic transcriptome and chromatin architecture in granulosa cells during chicken folliculogenesis
Authors: Li Diyan , Ning Chunyou , Zhang Jiaman , Wang Yujie , Tang Qianzi , Kui Hua , Wang Tao , He Mengnan , Jin Long , Li Jing , Lin Yu , Zeng Bo , Yin Huadong , Zhao Xiaoling , Zhang Yao , Xu Huailiang , Zhu Qing , Li Mingzhou 
Published: January 2022

AbstractFolliculogenesis is a complex biological process involving a central oocyte and its surrounding somatic cells. Three-dimensional chromatin architecture is an important transcription regulator; however, little is known about its dynamics and role in transcriptional regulation of granulosa cells during chicken folliculogenesis. We investigate the transcriptomic dynamics of chicken granulosa cells over ten follicular stages and assess the chromatin architecture dynamics and how it influences gene expression in granulosa cells at three key stages: the prehierarchical small white follicles, the first largest preovulatory follicles, and the postovulatory follicles. Our results demonstrate the consistency between the global reprogramming of chromatin architecture and the transcriptomic divergence during folliculogenesis, providing ample evidence for compartmentalization rearrangement, variable organization of topologically associating domains, and rewiring of the long-range interaction between promoter and enhancers. These results provide key insights into avian reproductive biology and provide a foundational dataset for the future in-depth functional characterization of granulosa cells.
Coherent phase transfer for real-world twin-field quantum key distribution
Authors: Clivati Cecilia , Meda Alice , Donadello Simone , Virzì Salvatore , Genovese Marco , Levi Filippo , Mura Alberto , Pittaluga Mirko , Yuan Zhiliang , Shields Andrew J. , Lucamarini Marco , Degiovanni Ivo Pietro , Calonico Davide 
Published: January 2022

AbstractQuantum mechanics allows distribution of intrinsically secure encryption keys by optical means. Twin-field quantum key distribution is one of the most promising techniques for its implementation on long-distance fiber networks, but requires stabilizing the optical length of the communication channels between parties. In proof-of-principle experiments based on spooled fibers, this was achieved by interleaving the quantum communication with periodical stabilization frames. In this approach, longer duty cycles for the key streaming come at the cost of a looser control of channel length, and a successful key-transfer using this technique in real world remains a significant challenge. Using interferometry techniques derived from frequency metrology, we develop a solution for the simultaneous key streaming and channel length control, and demonstrate it on a 206 km field-deployed fiber with 65 dB loss. Our technique reduces the quantum-bit-error-rate contributed by channel length variations to <1%, representing an effective solution for real-world quantum communications.
Intracellular bound chlorophyll residues identify 1 Gyr-old fossils as eukaryotic algae
Authors: Sforna Marie Catherine , Loron Corentin C. , Demoulin Catherine F. , François Camille , Cornet Yohan , Lara Yannick J. , Grolimund Daniel , Ferreira Sanchez Dario , Medjoubi Kadda , Somogyi Andrea , Addad Ahmed , Fadel Alexandre , Compère Philippe , Baudet Daniel , Brocks Jochen J. , Javaux Emmanuelle J. 
Published: January 2022

AbstractThe acquisition of photosynthesis is a fundamental step in the evolution of eukaryotes. However, few phototrophic organisms are unambiguously recognized in the Precambrian record. The in situ detection of metabolic byproducts in individual microfossils is the key for the direct identification of their metabolisms. Here, we report a new integrative methodology using synchrotron-based X-ray fluorescence and absorption. We evidence bound nickel-geoporphyrins moieties in low-grade metamorphic rocks, preserved in situ within cells of a ~1 Gyr-old multicellular eukaryote,Arctacellularia tetragonala. We identify these moieties as chlorophyll derivatives, indicating thatA. tetragonalawas a phototrophic eukaryote, one of the first unambiguous algae. This new approach, applicable to overmature rocks, creates a strong new proxy to understand the evolution of phototrophy and diversification of early ecosystems.
Catalytic atroposelective synthesis of axially chiral benzonitriles via chirality control during bond dissociation and CN group formation
Authors: Lv Ya , Luo Guoyong , Liu Qian , Jin Zhichao , Zhang Xinglong , Chi Yonggui Robin 
Published: January 2022

AbstractThe applications of axially chiral benzonitriles and their derivatives remain mostly unexplored due to their synthetic difficulties. Here we disclose an unusual strategy for atroposelective access to benzonitriles via formation of the nitrile unit on biaryl scaffolds pre-installed with stereogenic axes in racemic forms. Our method starts with racemic 2-arylbenzaldehydes and sulfonamides as the substrates and N-heterocyclic carbenes as the organocatalysts to afford axially chiral benzonitriles in good to excellent yields and enantioselectivities. DFT calculations suggest that the loss of p-toluenesulfinate group is both the rate-determining and stereo-determining step. The axial chirality is controlled during the bond dissociation and CN group formation. The reaction features a dynamic kinetic resolution process modulated by both covalent and non-covalent catalytic interactions. The axially chiral benzonitriles from our method can be easily converted to a large set of functional molecules that show promising catalytic activities for chemical syntheses and anti-bacterial activities for plant protections.
On the importance of the electric double layer structure in aqueous electrocatalysis
Authors: Shin Seung-Jae , Kim Dong Hyun , Bae Geunsu , Ringe Stefan , Choi Hansol , Lim Hyung-Kyu , Choi Chang Hyuck , Kim Hyungjun 
Published: January 2022

AbstractTo design electrochemical interfaces for efficient electric-chemical energy interconversion, it is critical to reveal the electric double layer (EDL) structure and relate it with electrochemical activity; nonetheless, this has been a long-standing challenge. Of particular, no molecular-level theories have fully explained the characteristic two peaks arising in the potential-dependence of the EDL capacitance, which is sensitively dependent on the EDL structure. We herein demonstrate that our first-principles-based molecular simulation reproduces the experimental capacitance peaks. The origin of two peaks emerging at anodic and cathodic potentials is unveiled to be an electrosorption of ions and a structural phase transition, respectively. We further find a cation complexation gradually modifies the EDL structure and the field strength, which linearly scales the carbon dioxide reduction activity. This study deciphers the complex structural response of the EDL and highlights its catalytic importance, which bridges the mechanistic gap between the EDL structure and electrocatalysis.
Guest-host doped strategy for constructing ultralong-lifetime near-infrared organic phosphorescence materials for bioimaging
Authors: Xiao Fuming , Gao Heqi , Lei Yunxiang , Dai Wenbo , Liu Miaochang , Zheng Xiaoyan , Cai Zhengxu , Huang Xiaobo , Wu Huayue , Ding Dan 
Published: January 2022

AbstractOrganic near-infrared room temperature phosphorescence materials have unparalleled advantages in bioimaging due to their excellent penetrability. However, limited by the energy gap law, the near-infrared phosphorescence materials (>650 nm) are very rare, moreover, the phosphorescence lifetimes of these materials are very short. In this work, we have obtained organic room temperature phosphorescence materials with long wavelengths (600/657–681/732 nm) and long lifetimes (102–324 ms) for the first time through the guest-host doped strategy. The guest molecule has sufficient conjugation to reduce the lowest triplet energy level and the host assists the guest in exciton transfer and inhibits the non-radiative transition of guest excitons. These materials exhibit good tissue penetration in bioimaging. Thanks to the characteristic of long lifetime and long wavelength emissive phosphorescence materials, the tumor imaging in living mice with a signal to background ratio value as high as 43 is successfully realized. This work provides a practical solution for the construction of organic phosphorescence materials with both long wavelengths and long lifetimes.
Two-dimensional Stiefel-Whitney insulators in liganded Xenes
Authors: Pan Mingxiang , Li Dexin , Fan Jiahao , Huang Huaqing 
Published: January 2022

AbstractTwo-dimensional (2D) Stiefel-Whitney insulator (SWI), which is characterized by the second Stiefel-Whitney class, is a class of topological phases with zero Berry curvature. As an intriguing topological state, it has been well studied in theory but seldom realized in realistic materials. Here we propose that a large class of liganded Xenes, i.e., hydrogenated and halogenated 2D group-IV honeycomb lattices, are 2D SWIs. The nontrivial topology of liganded Xenes is identified by the bulk topological invariant and the existence of protected corner states. Moreover, the large and tunable bandgap (up to 3.5 eV) of liganded Xenes will facilitate the experimental characterization of the 2D SWI phase. Our findings not only provide abundant realistic material candidates that are experimentally feasible but also draw more fundamental research interest towards the topological physics associated with Stiefel-Whitney class in the absence of Berry curvature.
Effectiveness of individualized inhaler technique training on low adherence (LowAd) in ambulatory patients with COPD and asthma
Authors: Sánchez-Nieto Juan Miguel , Bernabeu-Mora Roberto , Fernández-Muñoz Irene , Carrillo-Alcaraz Andrés , Alcántara-Fructuoso Juan , Fernández-Alvarez Javier , Vera-Olmos Juan Carlos , Martínez-Ferre María José , Olea Mercedes Garci-Varela , Valenciano Maria José Córcoles , Martínez Diego Salmerón 
Published: January 2022

AbstractTo analyze whether there is improvement in adherence to inhaled treatment in patients with COPD and asthma after an educational intervention based on the teach-to-goal method. This is a prospective, non-randomized, single-group study, with intervention and before-after evaluation. The study population included 120 patients (67 females and 53 males) diagnosed with asthma (70.8%) and COPD (29.1%). The level of adherence (low and optimal) and the noncompliance behavior pattern (erratic, deliberate and unwitting) were determined by the Test of the adherence to Inhalers (TAI). This questionnaire allows you to determine the level of adherence and the types of noncompliance. Low Adherence (LowAd) was defined as a score less than 49 points. All patients received individualized educational inhaler technique intervention (IEITI). Before the IEITI, 67.5% of the patients had LowAd. Following IEITI, on week 24, LowAd was 55% (p = 0.024). Each patient can present one or more types of noncompliance. The most frequent type was forgetting to use the inhaler (erratic), 65.8%. The other types were deliberate: 43.3%, and unwitting: 57.5%. All of them had decreased on the final visit: 51.7% (p = 0.009), 25.8% (p = 0.002), 39.2% (p = 0.002). There were no significant differences in adherence between asthma and COPD patients at the start of the study. The only predicting factor of LowAd was the female gender. An individualized educational intervention, in ambulatory patients with COPD and asthma, in real-world clinical practice conditions, improves adherence to the inhaled treatment.
COVID-19 patient accounts of illness severity, treatments and lasting symptoms
Authors: Thomason Moriah E. , Werchan Denise , Hendrix Cassandra L. 
Published: January 2022

AbstractFirst-person accounts of COVID-19 illness and treatment can complement and enrich data derived from electronic medical or public health records. With patient-reported data, it is uniquely possible to ascertain in-depth contextual information as well as behavioral and emotional responses to illness. The Novel Coronavirus Illness Patient Report (NCIPR) dataset includes complete survey responses from 1,584 confirmed COVID-19 patients ages 18 to 98. NCIPR survey questions address symptoms, medical complications, home and hospital treatments, lasting effects, anxiety about illness, employment impacts, quarantine behaviors, vaccine-related behaviors and effects, and illness of other family/household members. Additional questions address financial security, perceived discrimination, pandemic impacts (relationship, social, stress, sleep), health history, and coping strategies. Detailed patient reports of illness, environment, and psychosocial impact, proximal to timing of infection and considerate of demographic variation, is meaningful for understanding pandemic-related public health from the perspective of those that contracted the disease.
A longitudinal neuroimaging dataset on language processing in children ages 5, 7, and 9 years old
Authors: Wang Jin , Lytle Marisa N. , Weiss Yael , Yamasaki Brianna L. , Booth James R. 
Published: January 2022

AbstractThis dataset examines language development with a longitudinal design and includes diffusion- and T1-weighted structural magnetic resonance imaging (MRI), task-based functional MRI (fMRI), and a battery of psycho-educational assessments and parental questionnaires. We collected data from 5.5-6.5-year-old children (ses-5) and followed them up when they were 7-8 years old (ses-7) and then again at 8.5-10 years old (ses-9). To increase the sample size at the older time points, another cohort of 7-8-year-old children (ses-7) were recruited and followed up when they were 8.5–10 years old (ses-9). In total, 322 children who completed at least one structural and functional scan were included. Children performed four fMRI tasks consisting of two word-level tasks examining phonological and semantic processing and two sentence-level tasks investigating semantic and syntactic processing. The MRI data is valuable for examining changes over time in interactive specialization due to the use of multiple imaging modalities and tasks in this longitudinal design. In addition, the extensive psycho-educational assessments and questionnaires provide opportunities to explore brain-behavior and brain-environment associations.
Phytolith evidence for the pastoral origins of multi-cropping in Mesopotamia (ancient Iraq)
Authors: Laugier Elise Jakoby , Casana Jesse , Cabanes Dan 
Published: January 2022

AbstractMulti-cropping was vital for provisioning large population centers across ancient Eurasia. In Southwest Asia, multi-cropping, in which grain, fodder, or forage could be reliably cultivated during dry summer months, only became possible with the translocation of summer grains, like millet, from Africa and East Asia. Despite some textual sources suggesting millet cultivation as early as the third millennium BCE, the absence of robust archaeobotanical evidence for millet in semi-arid Mesopotamia (ancient Iraq) has led most archaeologists to conclude that millet was only grown in the region after the mid-first millennium BCE introduction of massive, state-sponsored irrigation systems. Here, we present the earliest micro-botanical evidence of the summer grain broomcorn millet (Panicum miliaceum) in Mesopotamia, identified using phytoliths in dung-rich sediments from Khani Masi, a mid-second millennium BCE site located in northern Iraq. Taphonomic factors associated with the region’s agro-pastoral systems have likely made millet challenging to recognize using conventional macrobotanical analyses, and millet may therefore have been more widespread and cultivated much earlier in Mesopotamia than is currently recognized. The evidence for pastoral-related multi-cropping in Bronze Age Mesopotamia provides an antecedent to first millennium BCE agricultural intensification and ties Mesopotamia into our rapidly evolving understanding of early Eurasian food globalization.
Developing and assessing a new web-based tapping test for measuring distal movement in Parkinson’s disease: a Distal Finger Tapping test
Authors: Akram Noreen , Li Haoxuan , Ben-Joseph Aaron , Budu Caroline , Gallagher David A. , Bestwick Jonathan P. , Schrag Anette , Noyce Alastair J. , Simonet Cristina 
Published: January 2022

AbstractDisability in Parkinson’s disease (PD) is measured by standardised scales including the MDS-UPDRS, which are subject to high inter and intra-rater variability and fail to capture subtle motor impairment. The BRadykinesia Akinesia INcoordination (BRAIN) test is a validated keyboard tapping test, evaluating proximal upper-limb motor impairment. Here, a new Distal Finger Tapping (DFT) test was developed to assess distal upper-limb function. Kinetic parameters of the test include kinesia score (KS20, key taps over 20 s), akinesia time (AT20, mean dwell-time on each key) and incoordination score (IS20, variance of travelling time between key taps). To develop and evaluate a new keyboard-tapping test for objective and remote distal motor function in PD patients. The DFT and BRAIN tests were assessed in 55 PD patients and 65 controls. Test scores were compared between groups and correlated with the MDS-UPDRS-III finger tapping sub-scores. Nine additional PD patients were recruited for monitoring motor fluctuations. All three parameters discriminated effectively between PD patients and controls, with KS20 performing best, yielding 79% sensitivity for 85% specificity; area under the receiver operating characteristic curve (AUC) = 0.90. A combination of DFT and BRAIN tests improved discrimination (AUC = 0.95). Among three parameters, KS20 showed a moderate correlation with the MDS-UPDRS finger-tapping sub-score (Pearson’s r = − 0.40, p = 0.002). Further, the DFT test detected subtle changes in motor fluctuation states which were not reflected clearly by the MDS-UPDRS-III finger tapping sub-scores. The DFT test is an online tool for assessing distal movements in PD, with future scope for longitudinal monitoring of motor complications.
Wireless power transfer system with enhanced efficiency by using frequency reconfigurable metamaterial
Authors: Shan Dongyong , Wang Haiyue , Cao Ke , Zhang Junhua 
Published: January 2022

AbstractThe wireless power transfer (WPT) system has been widely used in various fields such as household appliances, electric vehicle charging and sensor applications. A frequency reconfigurable magnetic resonant coupling wireless power transfer (MRCWPT) system with dynamically enhanced efficiency by using the frequency reconfigurable metamaterial is proposed in this paper. The reconfigurability is achieved by adjusting the capacitance value of the adjustable capacitor connected in the coil of the system. Finite element simulation results have shown that the frequency reconfigurable electromagnetic metamaterial can manipulate the direction of the electromagnetic field of the system due to its abnormal effective permeability. The ultra-thin frequency reconfigurable metamaterial is designed at different working frequencies of 14.1 MHz, 15 MHz, 16.2 MHz, 17.5 MHz, 19.3 MHz, 21.7 MHz and 25 MHz to enhance the magnetic field and power transfer efficiency (PTE) of the system. Frequency reconfigurable mechanism of the system with the frequency reconfigurable metamaterial is derived by the equivalent circuit theory. Finally, further measurement which verifies the simulation by reasonable agreement is carried out. PTE of the system by adding the metamaterial are 59%, 73%, 67%, 66%, 65%, 60% and 58% at different working frequencies. PTE of the system with and without the metamaterial is 72% and 49% at the distance of 120 mm and the frequency of 15 MHz, respectively.