bluuebunny/crossref_metadata_2025_split huggingface dataset:
Machine Learning to Predict Quasicrystals from Chemical Compositions
Authors: Liu Chang , Fujita Erina , Katsura Yukari , Inada Yuki , Ishikawa Asuka , Tamura Ryuji , Kimura Kaoru , Yoshida Ryo 
Published: July 2021

AbstractQuasicrystals have emerged as the third class of solid‐state materials, distinguished from periodic crystals and amorphous solids, which have long‐range order without periodicity exhibiting rotational symmetries that are disallowed for periodic crystals in most cases. To date, more than one hundred stable quasicrystals have been reported, leading to the discovery of many new and exciting phenomena. However, the pace of the discovery of new quasicrystals has lowered in recent years, largely owing to the lack of clear guiding principles for the synthesis of new quasicrystals. Here, it is shown that the discovery of new quasicrystals can be accelerated with a simple machine‐learning workflow. With a list of the chemical compositions of known stable quasicrystals, approximant crystals, and ordinary crystals, a prediction model is trained to solve the three‐class classification task and its predictability compared to the observed phase diagrams of ternary aluminum systems is evaluated. The validation experiments strongly support the superior predictive power of machine learning, with the overall prediction accuracy of the phase prediction task reaching ≈0.728. Furthermore, analyzing the input–output relationships black‐boxed into the model, nontrivial empirical equations interpretable by humans that describe conditions necessary for stable quasicrystal formation are identified.
High Sensitive and Broadband Photodetectors Based on Hybrid PbI2 Nanosheet/CdSe Nanobelt
Authors: Li Chenyan , Li Weijun , Cheng Mingming , Yang Weiye , Tan Qiuhong , Wang Qianjin , Liu Yingkai 
Published: July 2021

AbstractThe limited detection of lead iodide (PbI2) to visible light hinders the further development of PbI2 in the field of optoelectronic applications. A photodetector based on PbI2 nanosheet/CdSe nanobelt (PbI2 NS/CdSe NB) is prepared for the first time. This composite structure exhibits broadband spectral photoresponse from ultraviolet (400 nm) to red (730 nm). More importantly, PbI2 NS/CdSe NB can promote the effective separation of electron–hole pairs and improve the photoelectric performance. Compared to single PbI2 NS, the PbI2 NS/CdSe NB photodetector exhibits higher light–dark current ratio (6.778 × 103 A), responsivity (347.57 A W−1), and detectivity (3.625 × 1015 Jones) under 490 nm illumination. A new strategy is provided here to design broadband and high‐performance photodetectors.
Biodegradable and Dual‐Responsive Polypeptide‐Shelled Cyclodextrin‐Containers for Intracellular Delivery of Membrane‐Impermeable Cargo
Authors: Kudruk Sergej , Pottanam Chali Sharafudheen , Linard Matos Anna Livia , Bourque Cole , Dunker Clara , Gatsogiannis Christos , Ravoo Bart Jan , Gerke Volker 
Published: July 2021

AbstractThe transport of membrane impermeable compounds into cells is a prerequisite for the efficient cellular delivery of hydrophilic and amphiphilic compounds and drugs. Transport into the cell's cytosolic compartment should ideally be controllable and it should involve biologically compatible and degradable vehicles. Addressing these challenges, nanocontainers based on cyclodextrin amphiphiles that are stabilized by a biodegradable peptide shell are developed and their potential to deliver fluorescently labeled cargo into human cells is analyzed. Host–guest mediated self‐assembly of a thiol‐containing short peptide or a cystamine‐cross‐linked polypeptide shell on cyclodextrin vesicles produce short peptide‐shelled (SPSVss) or polypeptide‐shelled vesicles (PPSVss), respectively, with redox‐responsive and biodegradable features. Whereas SPSVss are permeable and less stable, PPSVss effectively encapsulate cargo and show a strictly regulated release of membrane impermeable cargo triggered by either reducing conditions or peptidase treatment. Live cell experiments reveal that the novel PPSVSS are readily internalized by primary human endothelial cells (human umbilical vein endothelial cells) and cervical cancer cells and that the reductive microenvironment of the cells’ endosomes trigger release of the hydrophilic cargo into the cytosol. Thus, PPSVSS represent a highly efficient, biodegradable, and tunable system for overcoming the plasma membrane as a natural barrier for membrane‐impermeable cargo.
UV‐Sinterable Silver Oxalate‐Based Molecular Inks and Their Application for In‐Mold Electronics
Authors: Liu Xiangyang , Li Derek , Fukutani Hiroshi , Trudeau Paul , Khoun LoleÏ , Mozenson Olga , Sampson Kathleen L. , Gallerneault Mary , Paquet Chantal , Lacelle Thomas , Deore Bhavana , Ferrand Olivier , Ferrigno Julie , Malenfant Patrick R. L. , Kell Arnold J. 
Published: July 2021

AbstractA new broadband UV light‐based processing method for a screen printable silver oxalate molecular ink is developed that enables structural electronics to be produced on complex thermoformed 3D objects. The production of these 3D devices is driven by the light‐induced reduction of silver oxalate to form an interfacial silver nanoparticle layer that allows the ink to transition to a viscous liquid intermediate and elongate up to 50% without cracking during thermoforming. Ultimately, this enables the development of 3D electronics devices with significantly less limitations on geometry, shape, size, and depth in comparison to commercially available inks. UV processing is also effective for 2D traces on low temperature PET substrate, where in situ produced silver nanoparticles can subsequently absorb light and further facilitate the rapid conversion of the silver oxalate to metallic silver through a self‐limiting thermal decomposition. The resulting traces have superior electrical properties and are produced in significantly less time in comparison to thermal sintering. Together, UV processing and the silver oxalate molecular ink serve as a platform for both the rapid production of conductive silver traces on low temperature substrates and the development of novel thermoformed 3D human‐machine interface devices, areas of interest for both academia and industry.
Genomic Insights into Myasthenia Gravis Identify Distinct Immunological Mechanisms in Early and Late Onset Disease
Authors: Handunnetthi Lahiru , Knezevic Bogdan , Kasela Silva , Burnham Katie L. , Milani Lili , Irani Sarosh R. , Fang Hai , Knight Julian C. 
Published: July 2021

ObjectiveThe purpose of this study was to identify disease relevant genes and explore underlying immunological mechanisms that contribute to early and late onset forms of myasthenia gravis.MethodsWe used a novel genomic methodology to integrate genomewide association study (GWAS) findings in myasthenia gravis with cell‐type specific information, such as gene expression patterns and promotor‐enhancer interactions, in order to identify disease‐relevant genes. Subsequently, we conducted additional genomic investigations, including an expression quantitative analysis of 313 healthy people to provide mechanistic insights.ResultsWe identified several genes that were specifically linked to early onset myasthenia gravis including TNIP1, ORMDL3, GSDMB, and TRAF3. We showed that regulators of toll‐like receptor 4 signaling were enriched among these early onset disease genes (fold enrichment = 3.85, p = 6.4 × 10−3). In contrast, T‐cell regulators CD28 and CTLA4 were exclusively linked to late onset disease. We identified 2 causal genetic variants (rs231770 and rs231735; posterior probability = 0.98 and 0.91) near the CTLA4 gene. Subsequently, we demonstrated that these causal variants result in low expression of CTLA4 (rho = −0.66, p = 1.28 × 10−38 and rho = −0.52, p = 7.01 × 10−22, for rs231735 and rs231770, respectively).InterpretationThe disease‐relevant genes identified in this study are a unique resource for many disciplines, including clinicians, scientists, and the pharmaceutical industry. The distinct immunological pathways linked to early and late onset myasthenia gravis carry important implications for drug repurposing opportunities and for future studies of drug development. ANN NEUROL 2021;90:455–463
Development and Mechanistic Studies of the Iridium‐Catalyzed C−H Alkenylation of Enamides with Vinyl Acetates: A Versatile Approach for Ketone Functionalization
Authors: Zhou Bo , Qi Xiaotian , Liu Peng , Dong Guangbin 
Published: July 2021

AbstractKetone functionalization is a cornerstone of organic synthesis. Herein, we describe the development of an intermolecular C−H alkenylation of enamides with the feedstock chemical vinyl acetate to access diverse functionalized ketones. Enamides derived from various cyclic and acyclic ketones reacted efficiently, and a number of sensitive functional groups were tolerated. In this iridium‐catalyzed transformation, two structurally and electronically similar alkenes—enamide and vinyl acetate—underwent selective cross‐coupling through C−H activation. No reaction partner was used in large excess. The reaction is also pH‐ and redox‐neutral with HOAc as the only stoichiometric by‐product. Detailed experimental and computational studies revealed a reaction mechanism involving 1,2‐Ir‐C migratory insertion followed by syn‐β‐acetoxy elimination, which is different from that of previous vinyl acetate mediated C−H activation reactions. Finally, the alkenylation product can serve as a versatile intermediate to deliver a variety of structurally modified ketones.
Monolayer‐to‐Multilayer Dimensionality Reconstruction in a Hybrid Perovskite for Exploring the Bulk Photovoltaic Effect Enables Passive X‐ray Detection
Authors: Ji Chengmin , Li Yezhan , Liu Xitao , Wang Yaxing , Zhu Tingting , Chen Qin , Li Lina , Wang Shuao , Luo Junhua 
Published: July 2021

AbstractHalide hybrid perovskites are attracting considerable attention as highly promising candidates for directly sensing X‐ray radiation, but it is challenging to realize passive X‐ray detection without an external power supply. However, the bulk photovoltaic effect (BPVE) in ferroelectrics promotes the independent separation of photoexcited carriers. Herein, by dimensionality reconstruction of a pure‐two‐dimensional (P‐2D) monolayered perovskite (CH3OC3H9N)2PbBr4, we obtained a quasi‐two‐dimensional (Q‐2D) ferroelectric (CH3OC3H9N)2CsPb2Br7. Converting P‐2D into Q‐2D perovskite stimulates a significant BPVE associated with robust ferroelectricity, as well as an enhanced mobility lifetime product. These features show the potential of the first passive X‐ray detector based on ferroelectrics with an impressive sensitivity up to 410 μC Gy−1 cm−2 at zero bias, which is even superior to the value of the state‐of‐the‐art α‐Se detector operated at relatively high bias.
Preparation and characterization of high strength and high modulusPVAfiber via dry‐wet spinning with cross‐linking of boric acid
Authors: Hong Xinqiu , He Junwei , Zou Liming , Wang Yanli , Li Yan Vivian 
Published: July 2021

AbstractTo improve the mechanical properties of polyvinyl alcohol (PVA) fibers, a series of PVA fibers were prepared via dry‐wet spinning with cross‐linking of boric acid (BA) (PVA/BA fibers), and using the mixed solvent of dimethyl sulfoxide and water. Moreover, the final PVA/BA fibers were characterized by Fourier transform infrared spectra (FTIR), scanning electron microscopy (SEM), differential scanning calorimetery (DSC), thermogravimetric analyzer (TGA), powder X‐ray diffraction (XRD) and yarn strength tester. Furthermore, with the increasing of BA content, FTIR analysis showed that the degree of crosslinking of BA with PVA increased. SEM images of final PVA/BA fibers presented smooth surfaces, and the diameters decreased firstly and then increased. DSC, TGA, and XRD analysis indicated that the melting temperatures, thermal properties and crystallinities first increased and then decreased with the increasing of BA content. In addition, mechanical properties measurements illustrated that the cross‐linking existed at an optimal BA content of 0.3 wt%, and PVA/BA‐0.3 fiber had the highest tensile strength and Young's modulus of 13.1 ± 0.4 and 360.2 ± 10.4 cN/dtex, respectively.
Predicting plasmid persistence in microbial communities by coarse‐grained modeling
Authors: Wang Teng , Weiss Andrea , Ha Yuanchi , You Lingchong 
Published: July 2021

AbstractPlasmids are a major type of mobile genetic elements (MGEs) that mediate horizontal gene transfer. The stable maintenance of plasmids plays a critical role in the functions and survival for microbial populations. However, predicting and controlling plasmid persistence and abundance in complex microbial communities remain challenging. Computationally, this challenge arises from the combinatorial explosion associated with the conventional modeling framework. Recently, a plasmid‐centric framework (PCF) has been developed to overcome this computational bottleneck. This framework enables the derivation of a simple metric, the persistence potential, to predict plasmid persistence and abundance. Here, we discuss how PCF can be extended to account for plasmid interactions. We also discuss how such model‐guided predictions of plasmid fates can benefit from the development of new experimental tools and data‐driven computational methods.
Anterior wall adenocarcinoma of bladder with similar clinicopathological and prognostic characteristics as common bladder carcinomas should not be treated as or classified into urachal adenocarcinomas
Authors: Zhou Yu‐Wen , Long Yi‐Xiu , Song Kun , Liang Li‐Bo , Cheng Ke , Chen Ye , Liu Ji‐Yan 
Published: July 2021

AbstractPurposeTo discuss whether the dome or anterior wall of bladder adenocarcinoma (BAC) should be classified into urachal carcinoma (UrC) and the relationship of primary tumor location (PTL) as well as treatment with survival.MethodsSurveillance, Epidemiology, and End Results 18 database was examined for eligible patients from 1975 to 2016. Patients were classified into adenocarcinoma originating from the urachus (UAC), the dome (D‐BAC), the anterior wall (A‐BAC), and the other sites adenocarcinoma of the bladder (O‐BAC). The clinicopathological features, treatment, and survival were compared among the groups.ResultsComparable clinicopathologic features were obtained between UAC and D‐BAC, which were different from those of A‐BAC and O‐BAC; otherwise, the latter two had similar clinicopathologic features. Univariable and multivariable Cox regression analyses indicated that PTL was an independent predictor for survival. O‐BAC conferred the worst prognosis then followed by A‐BAC, D‐BAC, and UAC. For non‐metastatic UAC or D‐BAC, partial cystectomy (with an en bloc resection of the urachus and umbilicus) is optimal for survival. However, the worse survival of non‐metastatic D‐BAC (compared with UAC) suggested different modalities, maybe more intensive surgery approaches, should be considered for D‐BAC.ConclusionThis study illustrates that PTL of UAC and BAC was an independent predictor for survival. A‐BAC had comparable characters and prognosis with O‐BAC and should not be classified into and treated as UrC. For non‐metastatic disease, non‐metastatic D‐BAC may need more intensive modality.
The Reactivity of α‐Fluoroketones with PLP Dependent Enzymes: Transaminases as Hydrodefluorinases
Authors: García‐Ramos Marina , Cuetos Aníbal , Kroutil Wolfgang , Grogan Gideon , Lavandera Iván 
Published: July 2021

AbstractA chemical method for the treatment of harmful halogenated compounds that has recently become of interest is the reductive dehalogenation of carbon‐halogen bonds. In the case of a fluorine atom, this process is called hydrodefluorination. While many transition metal‐based approaches now exist to reductively defluorinate aromatic fluoroarenes, the cleavage of C−F bonds in aliphatic compounds is not so well‐developed. Here we propose a biocatalytic approach exploiting a promiscuous activity exhibited by transaminases (TAs). Hence, a series of α‐fluoroketones have been defluorinated with excellent conversions using Chromobacterium violaceum and Arthrobacter sp. TAs under mild conditions and in aqueous medium, using a stoichiometric amount of an amine (e. g. 2‐propylamine) as reagent and formally releasing its oxidized form (e. g. acetone), with ammonia and hydrogen fluoride as by‐products. It is also demonstrated that this process can be performed in a regio‐ or stereoselective fashion.
Multireversible Redox Processes in a Self‐Assembled Nickel Pentanuclear Bis(Triple‐stranded Helicate): Structural and Spectroscopic Characterizations in the NiII5 and NiINiII4 Redox States
Authors: Gouré Eric , Gerey Bertrand , Pécaut Jacques , Thomas Fabrice , Fortage Jérôme , Collomb Marie‐Noëlle 
Published: July 2021

AbstractWe previously reported the multireversible redox behavior of bis(triple‐helicate) pentanuclear complexes of the type [{M(μ‐bpp)3}2M(μ3‐X)]n+ (M=Mn, Fe with X=O and Co with X=OH) with rigid tetradentate binucleating 3,5‐bis(pyridine‐2‐yl)pyrazole (bpp−) ligand. In this article, we focus on the nickel derivative of this family, [{NiII(μ‐bpp)3}2NiII3(μ‐OH)]3+ (13+), which exhibits up to five reversible or quasi‐reversible one‐electron waves in CH3CN solution. The two one‐electron oxidized species as well as the one‐electron reduced species with respective compositions of 4NiII1NiIII (14+), 3NiII2NiIII (15+) and 1NiI4NiII (12+), were quantitatively generated by bulk electrolyses and spectroscopically characterized highlighting the high stability of this family of complexes in several redox states. In addition to the initial complex 13+, the mixed‐valence 12+ was also successfully characterized by single‐crystal X‐ray diffraction, allowing to locate the sites of successive reversible one‐electron events. 12+ is an unusual example of a multinuclear complex including the low‐valent Ni(I) state.
Screening for monogenic subtypes of gestational diabetes in a high prevalence island population – A whole exome sequencing study
Authors: Pace Nikolai Paul , Vella Barbara , Craus Johann , Caruana Ruth , Savona‐Ventura Charles , Vassallo Josanne 
Published: July 2021

AbstractAimsThe reported frequency of monogenic defects of beta cell function in gestational diabetes (GDM) varies extensively. This study aimed to evaluate the frequency and molecular spectrum of variants in genes associated with monogenic/atypical diabetes in non‐obese females of Maltese ethnicity with GDM.Methods50 non‐obese females who met the International Association of the Diabetes and Pregnancy Study Groups (IADPSG) criteria for diagnosis of GDM and with a first‐degree relative with non‐autoimmune diabetes were included in this study. Whole exome capture and high throughput sequencing was carried out. Rare sequence variants were filtered, annotated, and prioritised according to the American College for Medical Genetics guidelines. For selected missense variants we explored effects on protein stability and structure through in‐silico tools.ResultsWe identified three pathogenic variants in GCK, ABCC8 and HNF1A and several variants of uncertain significance in the cohort. Genotype‐phenotype correlations and post‐pregnancy follow‐up data are described.ConclusionsThis study provides the first insight into an underlying monogenic aetiology in non‐obese females with GDM from an island population having a high prevalence of diabetes. It suggests that monogenic variants constitute an underestimated cause of diabetes detected in pregnancy, and that careful evaluation of GDM probands to identify monogenic disease subtypes is indicated.
Azaphilone Pigments from Hypoxylon rubiginosum and H. texense: Absolute Configuration, Bioactivity, and Biosynthesis
Authors: Becker Kevin , Kuhnert Eric , Cox Russell J. , Surup Frank 
Published: July 2021

AbstractWe report new stromatal azaphilone pigments rubiginosins Z‐X from the ascomycete Hypoxylon rubiginosum, as well as rubiginosins Z and W from H. texense, which were isolated along with known monomeric and dimeric congeners. Structures were elucidated using comprehensive HRMS, NMR, and ECD analysis, revealing azaphilones from both fungi to be exclusively C‐8(S)‐configured. The orsellinic acid (OA)‐carrying rubiginosins A, Z and dimeric rutilins A‐B exhibited cytotoxicity. Rubiginosins X‐W bearing linear polyketide side chains as well as rutilins A‐B were antimicrobial. Structures of the differently‐substituted azaphilones were linked to two putative biosynthetic gene clusters (BGCs; hraza1/2) in H. rubiginosum, which are proposed to collaboratively synthesize the OA‐substituted azaphilones. These share high homology with the azaphilone‐forming BGCs hfaza1/2 from H. fragiforme. Comparison of hraza and hfaza suggests that lack of an FAD‐dependent monooxygenase and acyltransferase gene in hraza1 prevent formation of C‐8(R)‐configured fatty acid‐substituted azaphilones in H. rubiginosum. The polyketide synthase‐derived side chain of rubiginosins C and X‐W is not encoded in the respective BGCs, showing that a third BGC is hypothetically involved in their formation. Cross‐interaction of three BGCs which are forming a single molecule is unprecedented in fungal natural product biosynthesis.
Nickel‐Catalyzed Cascade Reactions
Authors: Bhakta Sayantika , Ghosh Tapas 
Published: July 2021

AbstractThe formation of molecules with complexity in a simple, straight forward pathway attracts great interest in organic synthesis. Recently, nickel‐catalyzed cascade reactions have grown up as a useful tool and contributed significantly to the area of synthetic methodology. In order to furnish high yielding carbo‐ and heterocycles as building blocks of pharmaceutical compounds and bioactive molecules with high selectivity, nickel‐catalyzed reactions render comprehensive coverage of different strategies through compilation of various methodological prospective, such as photoredox decarboxylative vinylation, asymmetric reductive arylalkynation, hydroacylation/ Suzuki cross‐coupling reactions, intramolecular annulation cascade reactions, hemiacetalization cascade reactions, and so on. In addition, nickel‐catalyzed cascade reactions are also useful for the synthesis of multiple C−C/C−N bonds in acyclic compounds. This Review provides in depth mechanistic insights into on crucial reactions as well as a detailed discussion and critical comments.
Metal‐Free Synthesis of Anthranils by PhIO Mediated Heterocyclization of ortho‐Carbonyl Anilines
Authors: Garia Alankrita , Grover Jatin , Jain Nidhi 
Published: July 2021

AbstractHere, we report a metal‐free synthesis of anthranils from ortho‐carbonyl anilines using PhIO as a sole additive under ambient conditions. This methodology did not require any external additives and delivered anthranils in excellent yields with broad substrate scope. The mechanistic studies suggest that the reaction proceeds via in‐situ generation of iminoiodane leading to nitrene and a subsequent nucleophilic attack from oxygen of ortho‐carbonyl aniline on nitrene results in heterocyclization.