bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical Activation of Nitromethane to Construct Isoxazoline Aldoximes
Authors: Ji Shuaiyu , Zhao Lixing , Miao Bingyang , Xue Meng , Pan Tao , Shao Zhichao , Zhou Xin , Fu Aiping , Zhang Yuexia 
Published: June 2023

AbstractActivation of nitromethane to endow new reactivity is an interesting and meaningful but also challenging topic. Herein, we report an electrochemical activation of nitromethane to serve as both the heterocyclic skeleton and oxime sources for the construction of isoxazoline aldoximes. The isoxazoline aldoximes that are prepared by four steps with the reported strategy are synthesized in a single step from low‐cost and readily available nitromethane and olefins with moderate to excellent yields under our electrochemical conditions. The reaction also takes advantage of high atom‐economy and E‐selectivity. Moreover, the mechanism is studied by control experiments, a kinetic isotope effect (KIE) study, cyclic voltammogram (CV) experiments, and density functional theory (DFT) calculations. The mechanistic results reveal that nitromethane may be activated under electrochemical conditions to deliver a 1,2,5‐oxadiazole 2‐oxide intermediate, which undergoes [3+2] cycloaddition with olefins to yield isoxazoline aldoximes.
Reticular Synthesis of Metal‐Organic Frameworks by 8‐Connected Quadrangular Prism Ligands for Water Harvesting
Authors: Liu Wenbo , Wu Enyu , Yu Baoqiu , Liu Zhixin , Wang Kang , Qi Dongdong , Li Bin , Jiang Jianzhuang 
Published: June 2023

AbstractUtilization of rigid, highly connected organic linkers is critical for the reticular synthesis of functional metal–organic frameworks (MOFs). However, highly‐stable MOFs (e.g. Al/Cr/Zr‐based MOFs) based on rigid ligands with more than 6 coordinating functions have been rarely achieved thus far. Herein, we describe the construction of two bcu Zr‐based MOFs (named ZrMOF‐1 and ZrMOF‐2) from peripherally extended pentiptycene ligands (H8PEP‐1 and H8PEP‐2) with rigid quadrangular prism shape possessing 8 carboxylic groups at the prism vertices. Particularly, ZrMOF‐1 exhibits microporous structure with large Bruno‐Emmett‐Teller surface area and high water stability, endowing it a promising water harvesting material with a high water uptake capacity of 0.83 gH2O gMOF−1 at P/P0=0.90 and 25 °C, a steep uptake at a low P/P0 of 0.30, and excellent durability over 500 water adsorption‐desorption cycles. Moreover, self‐consistent charge density functional tight‐binding calculations were carried out, rationalizing the water adsorbing process and amount in ZrMOF‐1.
Versatile Biocatalytic C(sp3)−H Oxyfunctionalization for the Site‐ Selective and Stereodivergent Synthesis of α‐ and β‐Hydroxy Acids
Authors: Mao Yingle , Zhang Weijie , Fu Zunyun , Liu Yanqiong , Chen Lin , Lian Xin , Zhuo Dan , Wu Jiewei , Zheng Mingyue , Liao Cangsong 
Published: June 2023

AbstractC(sp3)−H oxyfunctionalization, the insertion of an O‐atom into C(sp3)−H bonds, streamlines the synthesis of complex molecules from easily accessible precursors and represents one of the most challenging tasks in organic chemistry with regard to site and stereoselectivity. Biocatalytic C(sp3)−H oxyfunctionalization has the potential to overcome limitations inherent to small‐molecule‐mediated approaches by delivering catalyst‐controlled selectivity. Through enzyme repurposing and activity profiling of natural variants, we have developed a subfamily of α‐ketoglutarate‐dependent iron dioxygenases that catalyze the site‐ and stereodivergent oxyfunctionalization of secondary and tertiary C(sp3)−H bonds, providing concise synthetic routes towards four types of 92 α‐ and β‐hydroxy acids with high efficiency and selectivity. This method provides a biocatalytic approach for the production of valuable but synthetically challenging chiral hydroxy acid building blocks.
Observation of Confinement‐Free Neutral Group Three Transition Metal Carbonyls Sc(CO)7 and TM(CO)8 (TM=Y, La)
Authors: Wang Chong , Tian Chang‐Yi , Zhao Ya , Jiang Shuai , Wang Tiantong , Zheng Huijun , Yan Wenhui , Li Gang , Xie Hua , Li Jun , Hu Han‐Shi , Yang Xueming , Jiang Ling 
Published: June 2023

AbstractSpectroscopic characterization of neutral highly‐coordinated compounds is essential in fundamental and applied research, but has been proven to be a challenging experimental target because of the difficulty in mass selection. Here, we report the preparation and size‐specific infrared‐vacuum ultraviolet (IR‐VUV) spectroscopic identification of group‐3 transition metal carbonyls Sc(CO)7 and TM(CO)8 (TM=Y, La) in the gas phase, which are the first confinement‐free neutral heptacarbonyl and octacarbonyl complexes. The results indicate that Sc(CO)7 has a C2v structure and TM(CO)8 (TM=Y, La) have a D4h structure. Theoretical calculations predict that the formation of Sc(CO)7 and TM(CO)8 (TM=Y, La) is both thermodynamically exothermic and kinetically facile in the gas phase. These highly‐coordinated carbonyls are 17‐electron complexes when only those valence electrons that occupy metal−CO bonding orbitals are considered, in which the ligand‐only 4b1u molecular orbital is ignored. This work opens new avenues toward the design and chemical control of a large variety of compounds with unique structures and properties.
Insights into Anion‐Solvent Interactions to Boost Stable Operation of Ether‐Based Electrolytes in Pure‐SiOx||LiNi0.8Mn0.1Co0.1O2 Full Cells
Authors: Tian Yi‐Fan , Tan Shuang‐Jie , Lu Zhuo‐Ya , Xu Di‐Xin , Chen Han‐Xian , Zhang Chao‐Hui , Zhang Xu‐Sheng , Li Ge , Zhao Yu‐Ming , Chen Wan‐Ping , Xu Quan , Wen Rui , Zhang Juan , Guo Yu‐Guo 
Published: June 2023

AbstractEther solvents with superior reductive stability promise excellent interphasial stability with high‐capacity anodes while the limited oxidative resistance hinders their high‐voltage operation. Extending the intrinsic electrochemical stability of ether‐based electrolytes to construct stable‐cycling high‐energy‐density lithium‐ion batteries is challenging but rewarding. Herein, the anion‐solvent interactions were concerned as the key point to optimize the anodic stability of the ether‐based electrolytes and an optimized interphase was realized on both pure‐SiOx anodes and LiNi0.8Mn0.1Co0.1O2 cathodes. Specifically, the small‐anion‐size LiNO3 and tetrahydrofuran with high dipole moment to dielectric constant ratio realized strengthened anion‐solvent interactions, which enhance the oxidative stability of the electrolyte. The designed ether‐based electrolyte enabled a stable cycling performance over 500 cycles in pure‐SiOx||LiNi0.8Mn0.1Co0.1O2 full cell, demonstrating its superior practical prospects. This work provides new insight into the design of new electrolytes for emerging high‐energy density lithium‐ion batteries through the regulation of interactions between species in electrolytes.
Supramolecular Control of the Oxidative Addition as a Way To Improve the Catalytic Efficiency of Pincer‐Rhodium (I) Complexes
Authors: Martínez‐Vivas Sebastián , Poyatos Macarena , Peris Eduardo 
Published: June 2023

Abstract1H NMR studies using a cationic complex with a pyridine‐di‐imidazolylidene pincer ligand of formula [Rh(CNC)(CO)]+ revealed that this compound showed high binding affinity with coronene in CH2Cl2. The interaction between coronene and the planar RhI complex is established by means of π‐stacking interactions. This interaction has a strong impact on the electron‐donating strength of the pincer CNC ligand, which is increased significantly, as demonstrated by the shifting of the ν(CO) stretching bands to lower frequencies. The addition of coronene increases the reaction rate of the nucleophilic attack of methyl iodide on the rhodium (I) pincer complex, and also has a positive effect on the performance of the complex as a catalyst in the cycloisomerization of 4‐pentynoic acid. These findings highlight the importance of supramolecular interactions for tuning the reactivity and catalytic activity of square‐planar metal complexes.
Detection of Bacterial Neutral Ceramidase in Diabetic Foot Ulcers with an Optimized Substrate and Chemoenzymatic Probes
Authors: Zou Jiao Xia , Chua Wisely , Ser Zheng , Wang Shi Mei , Chiang Grace Shu Hui , Sanmugam Kavitha , Tan Boon Yeow , Sobota Radoslaw M. , Li Hao 
Published: June 2023

AbstractCeramidases (CDases) are important in controlling skin barrier integrity by regulating ceramide composition and affording downstream signal molecules. While the functions of epidermal CDases are known, roles of neutral CDases secreted by skin‐residing microbes are undefined. Here, we developed a one‐step fluorogenic substrate, S‐B, for specific detection of bacterial CDase activity and inhibitor screening. We identified a non‐hydrolyzable substrate mimic, C6, as the best hit. Based on C6, we designed a photoaffinity probe, JX‐1, which efficiently detects bacterial CDases. Using JX‐1, we identified endogenous low‐abundance PaCDase in a P. aeruginosa monoculture and in a mixed skin bacteria culture. Harnessing both S‐B and JX‐1, we found that CDase activity positively correlates with the relative abundance of P. aeruginosa and is negatively associated with wound area reduction in clinical diabetic foot ulcer patient samples. Overall, our study demonstrates that bacterial CDases are important regulators of skin ceramides and potentially play a role in wound healing.
Universal Sub‐Nanoreactor Strategy for Synthesis of Yolk‐Shell MoS2 Supported Single Atom Electrocatalysts toward Robust Hydrogen Evolution Reaction
Authors: Gong Feilong , Liu Yuheng , Zhao Yang , Liu Wei , Zeng Guang , Wang Guoqing , Zhang Yonghui , Gong Lihua , Liu Jian 
Published: June 2023

AbstractThe coordination structure determines the electrocatalytic performances of single atom catalysts (SACs), while it remains a challenge to precisely regulate their spatial location and coordination environment. Herein, we report a universal sub‐nanoreactor strategy for synthesis of yolk‐shell MoS2 supported single atom electrocatalysts with dual‐anchored microenvironment of vacancy‐enriched MoS2 and intercalation carbon toward robust hydrogen‐evolution reaction. Theoretical calculations reveal that the “E‐Lock” and “E‐Channel” are conducive to stabilize and activate metal single atoms. A group of SACs is subsequently produced with the assistance of sulfur vacancy and intercalation carbon in the yolk‐shell sub‐nanoreactor. The optimized C−Co−MoS2 yields the lowest overpotential (η10=17 mV) compared with previously reported MoS2‐based electrocatalysts to date, and also affords a 5–9 fold improvement in activity even comparing with those as‐prepared single‐anchored analogues. Theoretical results and in situ characterizations unveil its active center and durability. This work provides a universal pathway to design efficient catalysts for electro‐refinery.
Conformational Kinetics in Chiral Poly(diphenylacetylene)s: A Dynamic P/M Memory Effect
Authors: Tarrío Juan José , Rodríguez Rafael , Crassous Jeanne , Quiñoá Emilio , Freire Félix 
Published: June 2023

AbstractDynamic P/M (plus/minus) helical memory in chiral dissymmetric poly(diphenylacetylene)s (PDPA) is shown using a PDPA that bears the benzamide of (L)‐alanine methyl ester as pendant. For a single chiral polymer, it is possible to obtain either P or M helical structures in a specific solvent without the presence of any chiral external stimuli. To do that, it is necessary to combine the conformational control at the pendant group with a high steric hindrance at the backbone. In this case, by thermal annealing in low‐polar solvents, an anti‐conformer is stabilized at the pendant which commands a P helix in the PDPA. Next, solvent removal followed by addition of a polar solvent such as dimethyl sulfoxide (DMSO), results in the kinetic conformationally trapped P helix. However, in this medium, the preferred handedness and the thermodynamic macromolecular helix for poly‐(L)‐1 is M. This process also occurs in the opposite way. Electronic circular dichroism (ECD) and circularly polarized luminescence (CPL) studies show that the dynamic memory effect is present both in ground and excited states.
Interface‐Anchored Covalent Organic Frameworks@Amino‐Modified Ti3C2Tx MXene on Nylon 6 Film for High‐Performance Deformable Supercapacitors
Authors: Feng Mengyue , Zhang Yang , Zhu Xiaolin , Chen Wenxing , Lu Wangyang , Wu Guan 
Published: June 2023

AbstractDesigning deformable supercapacitors (D‐SCs) that have robust skeleton and smoothly active channels for charges kinetic migration and faradic storage are highly crucial for wearable systems. Here, we develop the high‐performance D‐SCs made of the covalent organic frameworks(COF)@amino‐modified Ti3C2Tx deposited on decorated nylon 6 (DPA) film (COF@N‐Ti3C2Tx/DPA) via layer‐by‐layer fabrication. The hierarchical COF@N‐Ti3C2Tx/DPA exhibits admirable specific capacitance, rate performance and cycling stability in three‐electrode system due to the superior H+ storage property and large interfacial charge transfer clarified by density functional theory calculations. Additionally, the solid‐state D‐SCs deliver favourable energy density and practical energy‐supply applications. Particularly, the solid‐state D‐SCs present high deformable stabilities, with regard to 80.7, 80.6 and 83.4 % capacitance retention after 5000 bending cycles, 2000 stretching cycles and 5000 folding cycles, separately.
EPA and DHA in microalgae: Health benefits, biosynthesis, and metabolic engineering advances
Authors: Jesionowska Monika , Ovadia Justin , Hockemeyer Katelyn , Clews Alyssa C. , Xu Yang 
Published: June 2023

AbstractEicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) are ω‐3 very long‐chain polyunsaturated fatty acids (VLC‐PUFAs) that offer a wide range of human health benefits impacting cardiovascular, anti‐inflammatory, and neurological health. It is widely known that humans inefficiently synthesize these compounds and as such rely on exogenous dietary sources, such as marine fish oils. Unfortunately, the production of marine fish oils is an unsustainable process and has suffered a dramatic fall in recent years due to overfishing and climate change, as the demand for EPA and DHA continues to rise. Therefore, there is an urgent need to develop alternative, sustainable sources for consumable EPA and DHA. Metabolic engineering of marine microalgae to improve their EPA and DHA productivity is regarded as a promising option that has received increasing commercial attention in recent years. In this mini‐review, we describe several notable health benefits of EPA and DHA, summarize the natural sources and biosynthesis of VLC‐PUFAS, as well as the recent advances in metabolic engineering of EPA and DHA production in representative microalgal and protist species, including Schizochytrium sp., Phaeodactylum tricornutum, and Nannochloropsis oceanica.
Structural analyses of silk fibroins based on the structures of oligoalanine, and periodic oligopeptides of L‐alanine and glycine using x‐ray diffraction and 13C solid‐state NMR methods
Authors: Asakura Tetsuo , Naito Akira 
Published: June 2023

AbstractThe structures of (A)12, (AAAG)7, (AAG)10, (AG)15, and (AGG)10 were determined using x‐ray diffraction and 13C sold‐state NMR methods after different solvent treatments to obtain knowledge about the structural changes of silk fibroins (SFs) from Samia cynthia ricini (S.c.ricini) and Bombyx mori (B. mori). Three solvent treatments were performed: precipitation from dialysis of LiSCN (LiSCN/Dialysis) or LiBr (LiBr/Dialysis) aqueous solutions, and drying from formic acid (FA) or trifluoroacetic acid (TFA) solutions. (AAAG)7 and (AAG)10 as models of S.c.ricini SF, formed antiparallel β‐sheet structure with staggered packing configuration and did not change after LiSCN/Dialysis or LiBr/Dialysis and FA treatments. (AGG)10 formed 31 helix structure and did not change with these solvent treatments either. On the other hand, (AG)15 as model of B. mori SF formed Silk I (type II β‐turn) structure after LiBr/Dialysis treatment and Silk II (lamellar packing) structure after FA treatment. Especially, B. mori SF seems useful for biomaterials.
Shaping eukaryotic epigenetic systems by horizontal gene transfer
Authors: Arkhipova Irina R. , Yushenova Irina A. , Rodriguez Fernando 
Published: June 2023

AbstractDNA methylation constitutes one of the pillars of epigenetics, relying on covalent bonds for addition and/or removal of chemically distinct marks within the major groove of the double helix. DNA methyltransferases, enzymes which introduce methyl marks, initially evolved in prokaryotes as components of restriction‐modification systems protecting host genomes from bacteriophages and other invading foreign DNA. In early eukaryotic evolution, DNA methyltransferases were horizontally transferred from bacteria into eukaryotes several times and independently co‐opted into epigenetic regulatory systems, primarily via establishing connections with the chromatin environment. While C5‐methylcytosine is the cornerstone of plant and animal epigenetics and has been investigated in much detail, the epigenetic role of other methylated bases is less clear. The recent addition of N4‐methylcytosine of bacterial origin as a metazoan DNA modification highlights the prerequisites for foreign gene co‐option into the host regulatory networks, and challenges the existing paradigms concerning the origin and evolution of eukaryotic regulatory systems.
Beyond traditional therapy: Mucoadhesive polymers as a new frontier in oral cancer management
Authors: Das Subhayan , Bhattacharya Koushik , Blaker Jonny J. , Singha Nikhil K. , Mandal Mahitosh 
Published: June 2023

AbstractIn recent times mucoadhesive drug delivery systems are gaining popularity in oral cancer. It is a malignancy with high global prevalence. Despite significant advances in cancer therapeutics, improving the prognosis of late‐stage oral cancer remains challenging. Targeted therapy using mucoadhesive polymers can improve oral cancer patients' overall outcome by offering enhanced oral mucosa bioavailability, better drug distribution and tissue targeting, and minimizing systemic side effects. Mucoadhesive polymers can also be delivered via different formulations such as tablets, films, patches, gels, and nanoparticles. These polymers can deliver an array of medicines, making them an adaptable drug delivery approach. Drug delivery techniques based on these mucoadhesive polymers are gaining traction and have immense potential as a prospective treatment for late‐stage oral cancer. This review examines leading research in mucoadhesive polymers and discusses their potential applications in treating oral cancer.
The impact of humor therapy on people suffering from depression or anxiety: An integrative literature review
Authors: Sun Xuefeng , Zhang Jindan , Wang Yidan , Zhang Xiaotu , Li Sixuan , Qu Zihan , Zhang Hongshi 
Published: June 2023

AbstractObjectivesTo identify and synthesize existing research on the effectiveness and feasibility of multiform humor therapy on people suffering from depression or anxiety, with the hope of benefiting future research.MethodsAn integrative literature review of quantitative, qualitative, and mixed studies was performed. The PubMed, Cochrane Library, Web of Science, Embase, and CINAHL databases were searched up to March 2022. Two independent reviewers conducted each stage of the review process, by assessing eligibility using preferred reporting items for systematic review and meta‐analyses (PRISMA) and quality appraisal using the Mixed Methods Appraisal Tool, and data extraction.ResultsIn this integrative review, 29 papers were included, containing 2964 participants across a diverse range of studies, including quantitative, qualitative, and mixed methods. The articles were from the United States, Australia, Italy, Turkey, South Korea, Iran, Israel, China, and Germany. The findings indicated that most of the subjects thought humor therapy was effective in improving depression and anxiety while a few participants considered the effect insignificant. However, more high‐quality studies will be needed to confirm these conclusions.DiscussionThis review collated and summarized findings from studies examining the impact of humor therapy (medical clowns, laughter therapy/yoga) on people with depression or anxiety, including children undergoing surgery or anesthesia, older people in nursing homes, patients with Parkinson's disease, cancer, mental illness, and undergoing dialysis, retired women, and college students. The results from this review may help inform future research, policy, and practice in humor therapy to improve people's symptoms of depression and anxiety.ImpactThis systematic review objectively evaluated the effect of humor therapy on depression and anxiety. As a simple and feasible complementary alternative therapy, humor therapy may provide a favorable alternative for clinicians, nurses, and patients in the future.
Mutational spectrum for guiding the decision of adjuvant treatment in patients with resected biliary tract carcinoma
Authors: Li Yunfeng , Tan Chaochao , Yin Xinmin , Zhu Siwei , Cai Rongyao , Liao Chunhong , Wu Yifei , Zeng Qihong , Cai Chengzhi , Xie Wang , He Xiangyu , Wen Hao‐quan , Lin Guomin , He Qingqing , He Tingting , Gu Peng , Liu Chang‐jun 
Published: June 2023

BackgroundSystemic chemotherapy or chemoradiation therapy has proven to be effective in treating advanced biliary tract carcinoma (BTC). However, its efficacy in the adjuvant setting remains controversial. Therefore, this study aimed to determine the prognostic significance of genomic biomarkers in resected BTC and their potential role in stratifying patients for adjuvant treatment.MethodsWe retrospectively reviewed 113 BTC patients who underwent curative‐intent surgery and had available tumor sequencing data. Disease‐free survival (DFS) was the primary outcome examined and univariate analysis was used to identify gene mutations with prognostic value. Favorable and unfavoratble gene subsets were distinguished from the selected genes through grouping, respectively. Multivariate Cox regression was used to identify independent prognostic factors of DFS.ResultsOur results indicated that mutations in ACVR1B, AR, CTNNB1, ERBB3, and LRP2 were favorable mutations, while mutations in ARID1A, CDKN2A, FGFR2, NF1, NF2, PBRM1, PIK3CA, and TGFBR1 were unfavorable mutations. In addition to age, sex, and node positive, favorable genes (HR = 0.15, 95% CI = 0.04–0.48, p = 0.001) and unfavorable genes (HR = 2.86, 95% CI = 1.51–5.29, p = 0.001) were identified as independent prognostic factors for DFS. Out of the 113 patients, only 35 received adjuvant treatment whereas the majority (78) did not. For patients with both favorable and unfavorable mutations undetected, adjuvant treatment showed negative effect on DFS (median DFS: S441 vs. 956 days, p = 0.010), but there was no significant difference in DFS among those in other mutational subgroups.ConclusionsGenomic testing might be useful in guiding the decisions regarding adjuvant treatment in BTC.