bluuebunny/crossref_metadata_2025_split huggingface dataset:
Total Synthesis of Mutanobactins A, B from the Human Microbiome: Macrocyclization and Thiazepanone Assembly in a Single Step
Authors: Hansen Moritz E. , Yasmin Samuel O. , Wolfrum Susanne , Carreira Erick M. 
Published: May 2022

AbstractWe report the first total syntheses of tricyclic mutanobactins A and B, lipopeptides incorporating a thiazepanone, isolated from Streptococcus mutans, a member of the human oral microbiome. A rapid, solid‐phase peptide synthesis (SPPS) based route delivers these natural products from a cascade of cyclization reactions. This versatile process was also employed in a streamlined synthesis of mutanobactin D. Additionally, we provide an independent synthesis of a truncated mutanobactin A analog, utilizing a novel thiazepanone amino acid building block.
Superchaotropic Boron Clusters as Membrane Carriers for the Transport of Hydrophilic Cargos
Authors: Hu Xin‐Yue , Guo Dong‐Sheng 
Published: May 2022

AbstractDesign of membrane transporters is important in pharmaceutical drug delivery and bioimaging. Traditionally, the amphiphilic transport mechanism has governed the design of membrane carriers over the last 50 years. Recently, Montenegro, Nau and co‐workers discarded classical amphiphilic models and proposed a new transport principle based on the chaotropic effect. They utilized globular boron clusters as membrane carriers to transport a broad range of hydrophilic cargo. Herein, we highlight this recent pioneering work, which is a landmark for membrane transport.
An Ultrastable 155‐Nuclei Silver Nanocluster Protected by Thiacalix[4]arene and Cyclohexanethiol for Photothermal Conversion
Authors: Wang Zhi , Alkan Fahri , Aikens Christine M. , Kurmoo Mohamedally , Zhang Zhen‐Yi , Song Ke‐Peng , Tung Chen‐Ho , Sun Di 
Published: May 2022

AbstractThiacalix[4]arenes have emerged as a family of macrocyclic ligands to protect metal nanoparticles, but it remains a great challenge to solve the mystery of their structures at the atomic level, especially for those larger than 2 nm. Here, we report the largest known mixed‐valence silver nanocluster [Ag155(CyS)40(TC4A)5Cl2] (Ag155) protected by deprotonated cyclohexanethiol (CySH) and macrocyclic ligand p‐tert‐butylthiacalix[4]arene (H4TC4A). Its single‐crystal structure consists of a metallic core of four concentric shells, Ag13@Ag42@Ag30@Ag70, lined with a organic skin of 40CyS− and 5TC4A4− and 2Cl−. Ag155 manifests an unusual pseudo‐5‐fold symmetry dictated by the intrinsic metal atom packing and the regioselective distribution of mixed protective ligands. This work not only reveals a macrocyclic ligand effect on the formation of a large silver nanocluster, but also provides a new structural archetype for comprehensively perceiving their interface and metal kernel structures.
Synthesis and electrospinning of multiscale‐ordered PLA/LDH@AgGB composite nanofibrous membrane for antibacterial and oil–water separation
Authors: Cheng Xiao‐Qiong , Liu Wei , Zhang Chun , Chen Xiao‐Cheng , Duan Shu‐Qian , Fu Hai 
Published: May 2022

AbstractIn recent years, the problem of oily sewage has seriously affected the ecological environment and human health. Thus, we prepared a novel biodegradable poly (lactic acid) (PLA) membrane with antibacterial property and oil–water separation function via electrospinning method. First, the matter of silver ion glass microbeads (AgGB) loaded with layered double hydroxides (LDHs) and the LDH@AgGB modified with 3‐triethoxysilyl‐1‐Propanamine (APTES) were synthesized. Then, the LDH@AgGB were blended with PLA to prepare PLA/LDH@AgGB composite. And the PLA nanofibrous membranes were electrospun. The results showed that APTES could significantly improve the dispersion and compatibility of LDH@AgGB in PLA matrix. The addition of A‐LDH@AgGB could greatly improve the crystallinity, and control the porosity and pore‐size of PLA membranes. The maximum water contact angle of the PLA membranes could reach to 109.31°, while the oil contact angle of the PLA membranes decreased to 0° resulting in a high oil absorption capacity, and fast oil absorption rate performance. Meanwhile, the PLA membrane had efficient antibacterial property against Escherichia coli. The reported novel LDH@AgGB and its PLA composite membrane provided a method for designing and preparing environmental‐friendly, high‐performance materials with both excellent antibacterial property and oil–water separation.
Clustered restricted mean survival time regression
Authors: Chen Xinyuan , Harhay Michael O. , Li Fan 
Published: May 2022

AbstractFor multicenter randomized trials or multilevel observational studies, the Cox regression model has long been the primary approach to study the effects of covariates on time‐to‐event outcomes. A critical assumption of the Cox model is the proportionality of the hazard functions for modeled covariates, violations of which can result in ambiguous interpretations of the hazard ratio estimates. To address this issue, the restricted mean survival time (RMST), defined as the mean survival time up to a fixed time in a target population, has been recommended as a model‐free target parameter. In this article, we generalize the RMST regression model to clustered data by directly modeling the RMST as a continuous function of restriction times with covariates while properly accounting for within‐cluster correlations to achieve valid inference. The proposed method estimates regression coefficients via weighted generalized estimating equations, coupled with a cluster‐robust sandwich variance estimator to achieve asymptotically valid inference with a sufficient number of clusters. In small‐sample scenarios where a limited number of clusters are available, however, the proposed sandwich variance estimator can exhibit negative bias in capturing the variability of regression coefficient estimates. To overcome this limitation, we further propose and examine bias‐corrected sandwich variance estimators to reduce the negative bias of the cluster‐robust sandwich variance estimator. We study the finite‐sample operating characteristics of proposed methods through simulations and reanalyze two multicenter randomized trials.
Tumor‐associated macrophages regulate the function of cytotoxic T lymphocyte through PD‐1/PD‐L1 pathway in multiple myeloma
Authors: Zhang Jiangbo , Liu Zhaoyun , Cao Panpan , Wang Hao , Liu Hui , Hua Luoming , Xue Hua , Fu Rong 
Published: May 2022

AbstractBackgroundTumor‐associated macrophages (TAMs) are originated from circulating mononuclear cells in peripheral blood. They result from the recruitment of tumor cells and are a vital constituent of the tumor microenvironment. TAMs may be involved in the immunological escape of vicious clonal plasma cells (PC) in the bone marrow (BM) of sufferers with myeloma.MethodsFrom March 2020 to January 2021, 28 healthy controls (HC) and 86 multiple myeloma (MM) (53 newly diagnosed MM [NDMM] and 33 remissions) patients were enrolled as objects of the study. The expression of TAMs in the BM, CSF1 on CD138 + cells, and CSF1R on macrophages were detected by the method of flow cytometry, and the expression of PD‐1 on CD8 + T cells and PD‐L1 on TAMs were also done. Bone marrow mononuclear cells (BMMNCs) were extracted and cultured into TAMs, CD8 + T cells were sorted by magnetic beads and cultured, a coculture system was established and different inhibitors were added. The expression of the perforin and granzyme B was detected by flow cytometry.ResultsThe percentage of TAMs in NDMM group (61.49 ± 2.176%) increased when compared with remission (23.08 ± 1.699%, p < 0.001) and HC group (17.95 ± 1.865%, p < 0.001), and TAMs decreased after adding CSF1R inhibitor. Moreover, the expression of CSF1 on CD138 + cells increased significantly in NDMM group (17.090 ± 0.9156%) than remission (8.214 ± 0.5911% p < 0.001), and HC group (5.257 ± 0.6231%, p < 0.001), and CSF1R on macrophages increased significantly in NDMM group (58.78 ± 2.286%) than remission (20.74 ± 1.376%, p < 0.001) and HC group (17.42 ± 1.081%, p < 0.001). The expression of PD‐1 on CD8 + T cells in NDMM group (32.64 ± 2.982%) increased than remission (20.35 ± 2.335% p < 0.01) and HC group (17.53 ± 1.349%, p < 0.001), and PD‐L1 on TAMs also increased in NDMM group (50.92 ± 2.554%) than remission (20.02 ± 1.893%, p < 0.001) and HC group (13.08 ± 1.289%, p < 0.001). When CD8 + T cells were cocultured with TAMs, the perforin and granzyme B levels decreased significantly. However, the perforin and granzyme B levels were partly restored after adding CSF1R inhibitor and anti‐PD‐L1 antibody.ConclusionOur study shows that TAMs were increased in MM patients which can inhibit the function of cytotoxic T lymphocyte (CTL) through the PD‐1/ PD‐L1 signaling pathway and participate in the occurrence of immune escape of myeloma cells.
On‐purpose Ethylene Production via CO2‐assisted Ethane Oxidative Dehydrogenation: Selectivity Control of Iron Oxide Catalysts
Authors: Theofanidis Stavros A. , Kasun Kalhara Gunasooriya G. T. , Itskou Ioanna , Tasioula Maria , Lemonidou Angeliki A. 
Published: May 2022

AbstractThe potential of on‐purpose ethylene production, in parallel with CO2 conversion to CO, is of great interest. Iron oxide‐based catalysts supported on mixed oxides zNiO−MgO−ZrO2, z=0–10 wt%, are active for the CO2‐assisted oxidative dehydrogenation of ethane at 873 K and 101.3 kPa. Enhanced control of their selectivity towards C−H bond cleavage and not towards C−C bond cleavage can be achieved by adjusting the Ni/Fe ratio. Fine tuning Ni/Fe molar ratio results in stable catalytic performance, with selectivity towards C2H4 >65 % and C2H6 conversion >20 %. Density functional theory (DFT) calculations show a significant enhancement in activity due to decrease in the oxygen‐vacancy formation energy and the increase in hydrogen adsorption energy at the Ni oxide‐Fe oxide interface. The latter interface is the potential active site responsible for the enhanced performance that was experimentally exemplified for the Fe oxide/zNiO−MgO−ZrO2 catalysts vs Fe oxide/MgO−ZrO2.
Experimental Measurement and Quantification of the Local Cell Reaction in Blended Lithium Insertion Electrodes
Authors: Ariyoshi Kingo , Suzuki Rikuya 
Published: May 2022

AbstractBlended electrodes in which two types of active materials are mixed exhibit synergetic effects due to the interplay between different active materials. Although a local cell reaction within the electrode plays an important role in the blended electrodes, its nature is not yet known because of difficulties associated with experimental measurements. In this study, we developed a method for measuring the local cell reaction using a blended electrode containing a mixture of Li[Ni1/2Mn3/2]O4 and Li[Li0.1Al0.1Mn1.8]O4. The rate of the local cell reaction was successfully quantified using the change in the open‐circuit potential after high‐current discharge. The current for the local cell reaction (ILCR) decreased in inverse proportion to the relaxation time after current interruption. ILCR could be formulated using t0, a parameter representing the time at which the local cell reaction started, and α, a coefficient representing the rate of the local cell reaction.
Amorphous and Crystalline Vanadium Orthophosphate and Oxidized Multiwalled Carbon Nanotube Composites as Anode Materials in Sodium‐Ion Batteries
Authors: Basa Anna , Gajko Ewelina , Goclon Jakub , Wilczewska Agnieszka Z. , Winkler Krzysztof 
Published: May 2022

AbstractVanadium orthophosphate and oxidized multiwalled carbon nanotube (ox‐MWCNT) composites were applied as anodic electroactive materials in a sodium‐ion battery. Carbon nanotubes reduce the resistance of anodic materials, prevent drastic volume expansion, and allow easy transport of electrolyte ions, leading to an improvement in the electrochemical performance of electroactive materials. Theoretical modeling of the VPO4 /ox‐CNT interphase indicates the conducting properties of the crystalline c‐VPO4 /ox‐MWCNT composite and the significant contribution of CNTs in the charge transfer process. As anodes in sodium‐ion batteries, crystalline VPO4 (c‐VPO4 ) and amorphous VPO4 (a‐VPO4 ) exhibited initial discharge capacities of 125 mAh g−1 and 110 mAh g−1, respectively. The incorporation of vanadium phosphate into the network of ox‐MWCNTs results in a large increase in the capacity performance of electroactive materials. Discharge capacities of 1642 mAh g−1 and 1680 mAh g−1 were obtained for the first cycle in the case of the c‐VPO4 /ox‐MWCNT 50 % w/w and a‐VPO4/ox‐MWCNT 50 % w/w anodes, respectively. The capacity of these composite materials significantly decreases in the second cycle, reaching a stable capacity performance. The limiting capacity was 328 mAh g−1 for composites containing 50 % w/w ox‐MWCNTs.
Synthesis of Mono‐fluoroallenes through Copper‐Catalyzed Defluorinative Silylation of α,α‐Difluoroalkylalkynes
Authors: Tang Luning , Pei Bing‐Bing , Song Yang , Xue Fei , Yue Yanni , Feng Chao 
Published: May 2022

Comprehensive SummaryA straightforward protocol for the synthesis of mono‐fluorinated allenes via catalytic defluorinative silylation of the readily available α,α‐difluoroalkylalkynes with commercially available copper catalyst and phosphine ligand is described. A broad scope of α,α‐difluoroalkylalkynes were well accommodated and a gram‐scale synthesis demonstrated the synthetic utility of this methodoglogy.
A Crystalline Supramolecular Rotor Functioned by Dual Ultrasmall Polar Rotators†
Authors: Li Wang , Liu De‐Xuan , Hu Wei‐Yu , Liu Qing‐Yan , Du Zi‐Yi , He Chun‐Ting , Zhang Wei‐Xiong , Chen Xiao‐Ming 
Published: May 2022

Comprehensive SummaryAs an extended model of conventional molecular rotors, a conceived construction of novel crystalline molecular rotor that simultaneously contains two discrete polar rotators is presented here. The supramolecular self‐assembly of 18‐crown‐6 host and two rotator‐containing ion‐pair guests affords a three‐in‐one cocrystal, (2‐NH3‐iBuOH)(18‐crown‐6)[ZnBr3(H2O)], in which the hydroxyl group and aqua ligand both function as ultrasmall polar rotators. On the basis of the variable‐temperature single‐crystal X‐ray diffraction, variable‐temperature/frequency dielectric response, density functional theory calculations, and molecular dynamics simulations, it is found that such dual polar rotators experience a gradually enhanced rotation with increasing temperature, and more importantly, could be controlled by a reversible polar‐to‐polar structural phase transition, i.e., from a “single‐(polar rotator)” state at low‐temperature phase to a “mixed‐dual‐(polar rotator)” state in the vicinity of transition, and to an unusual “synchronized‐dual‐(polar rotator)” state at high‐temperature phase.
ChemPlot, a Python Library for Chemical Space Visualization**
Authors: Cihan Sorkun Murat , Mullaj Dajt , Koelman J. M. Vianney A. , Er Süleyman 
Published: May 2022

AbstractVisualizing chemical spaces streamlines the analysis of molecular datasets by reducing the information to human perception level, hence it forms an integral piece of molecular engineering, including chemical library design, high‐throughput screening, diversity analysis, and outlier detection. We present here ChemPlot, which enables users to visualize the chemical space of molecular datasets in both static and interactive ways. ChemPlot features structural and tailored similarity methods, together with three different dimensionality reduction methods: PCA, t‐SNE, and UMAP. ChemPlot is the first visualization software that tackles the activity/property cliff problem by incorporating tailored similarity. With tailored similarity, the chemical space is constructed in a supervised manner considering target properties. Additionally, we propose a metric, the Distance Property Relationship score, to quantify the property difference of similar (i. e. close) molecules in the visualized chemical space. ChemPlot can be installed via Conda or PyPI (pip) and a web application is freely accessible at https://www.amdlab.nl/chemplot/.
A three‐dimensional atlas of the honeybee central complex, associated neuropils and peptidergic layers of the central body
Authors: Kaiser Andreas , Hensgen Ronja , Tschirner Katja , Beetz Evelyn , Wüstenberg Hauke , Pfaff Marcel , Mota Theo , Pfeiffer Keram 
Published: May 2022

AbstractThe central complex (CX) in the brain of insects is a highly conserved group of midline‐spanning neuropils consisting of the upper and lower division of the central body, the protocerebral bridge, and the paired noduli. These neuropils are the substrate for a number of behaviors, most prominently goal‐oriented locomotion. Honeybees have been a model organism for sky‐compass orientation for more than 70 years, but there is still very limited knowledge about the structure and function of their CX. To advance and facilitate research on this brain area, we created a high‐resolution three‐dimensional atlas of the honeybee's CX and associated neuropils, including the posterior optic tubercles, the bulbs, and the anterior optic tubercles. To this end, we developed a modified version of the iterative shape averaging technique, which allowed us to achieve high volumetric accuracy of the neuropil models. For a finer definition of spatial locations within the central body, we defined layers based on immunostaining against the neuropeptides locustatachykinin, FMRFamide, gastrin/cholecystokinin, and allatostatin and included them into the atlas by elastic registration. Our honeybee CX atlas provides a platform for future neuroanatomical work.
Forensics chain for evidence preservation system: An evidence preservation forensics framework for internet of things‐based smart city security using blockchain
Authors: Kamal Randa , Hemdan Ezz El‐Din , El‐Fishway Nawal 
Published: May 2022

AbstractIn recent times, the new revolution of IoT facilitates communication and information sharing among people in different domains like a smart city. This revolution came with a risk of cyber‐attacks that target devices and shared data. The digital evidence resulting from the digital forensics process applied to IoT devices must be kept safe for later analysis. Preserving digital evidence on a centralized server raises the risk of a single point of failure. Evidence preserving on cloud servers raises the tampering risk with the evidence or even sharing them with malicious third parties. Therefore, this paper presents a novel framework called Forensics Chain for Evidence Preservation System for IoT‐based smart city security. The proposed framework aims to integrate blockchain with digital forensics to overcome the problems faced by forensic investigators; single point of failure and/or evidence modifications and enhance the security of preserving digital evidence via applying blockchain. Applying blockchain guarantees the immutability and data integrity of the preserved evidence. Furthermore, preserving the digital evidence among the forensic participant nodes eliminates the possibility of the single‐point failure of a centralized storage server. The results provided a Proof of Concept for forensic evidence preservation based on blockchain and evaluated its performance.
Unveiling the Migration and Transformation Mechanism of Lignin in Eucalyptus During Deep Eutectic Solvent Pretreatment
Authors: Hong Si , Li Han‐Yin , Shen Xiao‐Jun , Sun Shao‐Ni , Sun Zhuohua , Yuan Tong‐Qi 
Published: May 2022

AbstractDeep eutectic solvents (DESs) have unique advantages in biomass conversion. However, the migration and transformation mechanism of lignin in the cell wall during the DES pretreatment is still elusive. In this work, Eucalyptus blocks were pretreated in choline chloride/lactic acid DES to reveal the lignin migration. Meanwhile, the remaining lignin in the pretreated residue, the regenerated DES lignin, and the solubilized degraded lignin in the recovered DES were investigated to decipher the lignin transformation. Results showed that the DES pretreatment resulted in the penetration of DES from the cell lumen to the cell wall, and lignin in the secondary wall was more easily dissolved than that in the cell corner middle lamella. The syringyl unit of lignin was better stabilized in the DES than the guaiacyl unit of lignin. The condensed lignin fraction mainly remained in the pretreated residue, while the solubilized degraded lignin fraction was monomeric aromatic ketone compounds. This study elucidates the fate of lignin during the DES pretreatment, which could also promote the development of a modern lignocellulosic pretreatment technique.
Hepatic pannexin‐1 mediates ST2+ regulatory T cells promoting resolution of inflammation in lipopolysaccharide‐induced endotoxemia
Authors: Wang Pusen , Shi Baojie , Wang Chunguang , Wang Yuanyuan , Que Weitao , Jiang Zhongyi , Liu Xueni , Jiang Qianwei , Li Hao , Peng Zhihai , Zhong Lin 
Published: May 2022

AbstractSepsis remains the most lethal infectious disease and substantially impairs patient prognosis after liver transplantation (LT). Our previous study reported a role of the pannexin 1 (PANX1)–interleukin‐33 (IL‐33) axis in activating innate immunity to protect against methicillin‐resistant Staphylococcus aureus infection; however, the role of PANX1 in regulating adaptive immunity in sepsis and the underlying mechanism are unclear. In this study, we examined the role of the PANX1–IL‐33 axis in protecting against sepsis caused by a gram‐negative bacterial infection in an independent LT cohort. Next, in animal studies, we assessed the immunological state of Panx1−/‐ mice with lipopolysaccharide (LPS)‐induced endotoxemia and then focused on the cytokine storm and regulatory T cells (Tregs), which are crucial for the resolution of inflammation. To generate liver‐specific Panx1‐deficient mice and mimic clinical LT procedures, a mouse LT model was established. We demonstrated that hepatic PANX1 deficiency exacerbated LPS‐induced endotoxemia and dysregulated the immune response in the mouse LT model. In hepatocytes, we confirmed that PANX1 positively regulated IL‐33 synthesis after LPS administration. We showed that the adenosine triphosphate‐P2X7 pathway regulated the hepatic PANX1–IL‐33 axis during endotoxemia in vitro and in vivo. Recombinant IL‐33 treatment rescued LPS‐induced endotoxemia by increasing the numbers of liver‐infiltrating ST2+ Tregs and attenuating the cytokine storm in hepatic PANX1‐deficient mice. In conclusion, our findings revealed that the hepatic PANX1–IL‐33 axis protects against endotoxemia and liver injury by targeting ST2+ Tregs and promoting the early resolution of hyperinflammation.