bluuebunny/crossref_metadata_2025_split huggingface dataset:
Aprotic phosphonium‐based ionic liquid as electrolyte for high CO2electroreduction to oxalate
Authors: Jiang Chongyang , Zeng Shaojuan , Ma Xifei , Feng Jiaqi , Li Guilin , Bai Lu , Li Fangfang , Ji Xiaoyan , Zhang Xiangping 
Published: August 2022

AbstractIn this study, a new CO2electroreduction electrolyte system consisting of tetrabutylphosphonium 4‐(methoxycarbonyl) phenol ([P4444][4‐MF‐PhO]) ionic liquid (IL) and acetonitrile (AcN) was designed to produce oxalate, and the electroreduction mechanism was studied. The results show that using the new IL‐based electrolyte, the electroreduction system exhibits 93.8% Faradaic efficiency and 12.6 mA cm−2partial current density of oxalate at −2.6 V. The formation rate of oxalate is 234.4 μmol cm−2 h−1, which is better than those reported in the literature. The mechanism study using density functional theory (DFT) calculations reveals that [P4444][4‐MF‐PhO] can effectively activate CO2molecule through ester and phenoxy double active sites. In addition, in the phosphonium‐based ionic environment, the potential barriers of the key intermediates *CO2−and *C2O42−are reduced by the induced electric field, which greatly facilitates the activation and conversion of CO2molecule to oxalate.
Severe neuroglycopenic symptoms due to nonketotic hypoglycemia in children with cardio‐facio‐cutaneous syndrome
Authors: Shiohama Tadashi , Fujii Katsunori , Kosaki Rika , Watanabe Yoshimi , Uchida Tomoko , Hagiwara Sho , Kinoshita Kaori , Sugita Katsuo , Aoki Yoko , Shimojo Naoki 
Published: August 2022

AbstractCardio‐facio‐cutaneous syndrome (CFC) (OMIM 115150) is a congenital disease caused by constitutive activation of the Raf/MEK/ERK signaling cascade. Unlike aspects of morphological anomalies, metabolic functions related to the disease have garnered little attention. We present severe neuroglycopenic symptoms due to nonketotic hypoglycemia in two children with CFC (Case 1, a 4‐year‐old male with c.389A > G heterozygous variant in MAP2K1; Case 2, a 3‐year‐old male with c.770A > G heterozygous variant in BRAF). Case 1 exhibited a nonketotic hypoglycemic coma and clustered left‐hemispheric convulsions despite receiving infusion therapy, leading to severe sequelae with choreoathetosis. Brain magnetic resonance imaging of Case 1 showed T2‐elongation with restricted diffusion on the bilateral basal ganglia and thalamus, with the dominance of the right putamen. Case 2 presented a prolonged generalized seizure as an initial clinical symptom but fully recovered. The presence of growth hormone and cortisol deficiency was ruled out in both cases. Blood spots acylcarnitine profiles excluded the co‐occurrence of mitochondrial HMG‐CoA synthase deficiency and HMG‐CoA lyase deficiency. These cases demonstrate the potential vulnerability to nonketotic hypoglycemia, especially during lipid shortages. As children with CFC frequently have difficulties feeding, we suggest great attention should be paid to the potential risk of severe nonketotic hypoglycemia.
How individual, social, and ecological conditions influence dispersal decisions in male vervet monkeys
Authors: L'Allier Simon , Schwegel Megan A. , Filazzola Alessandro , Mastromonaco Gabriela , Chapman Colin A. , Schoof Valérie A. M. 
Published: August 2022

AbstractDispersal between social groups reduces the risk of inbreeding and can improve individuals' reproductive opportunities. However, this movement has costs, such as increased risk of predation and starvation, loss of allies and kin support, and increased aggression associated with entering the new group. Dispersal strategies, such as the timing of movement and decisions on whether to transfer alone or in parallel with a peer, involve different costs and benefits. We used demographic, behavioral, hormonal, and ecological data to examine the causes and consequences of 36 dispersal events from 29 male vervet monkeys (Chlorocebus pygerythrus) at Lake Nabugabo, Uganda. Adult males' secondary dispersal coincided with the conception season in females, and males improved their potential access to females by moving to groups with higher female‐to‐male sex ratios and/or by increasing their dominance rank. Males that dispersed with a peer had lower fecal glucocorticoid and androgen metabolite levels than lone dispersers. Subadult males were not more likely to engage in parallel dispersals compared to adult males. Dispersal was also used as a mechanism to avoid inbreeding, but changes in hormone levels did not seem to be a trigger of dispersal in our population. Our findings illustrate the complex individual strategies used during dispersal, how many factors can influence movement decisions, as well as the value of dominance and hormone analyses for understanding these strategies.
Enhancing Hydrogen Oxidation and Evolution Kinetics by Tuning the Interfacial Hydrogen‐Bonding Environment on Functionalized Platinum Surfaces
Authors: Zhao Kaiyue , Chang Xiaoxia , Su Hai‐Sheng , Nie Yiming , Lu Qi , Xu Bingjun 
Published: August 2022

AbstractDeveloping efficient catalytic systems for the hydrogen oxidation and evolution reactions (HOR/HER) is essential in the world's transition to renewable energy. There is a growing recognition that the HOR/HER activity depends on properties of the electrochemical interface, rather than just the composition and structure of the catalyst. Herein, we demonstrate that specifically adsorbed organic additives (theophylline derivatives) could enhance the intrinsic HOR/HER activity in base on polycrystalline Pt by up to a factor of 3 via introducing weakly hydrogen‐bonded water, as confirmed by in situ surface enhanced infrared and Raman spectroscopies. Optimal HOR/HER activity is achieved on a 7‐n‐butyltheophylline decorated Pt surface, which sufficiently disrupts the hydrogen bonding network in the double layer without depleting the interfacial water. This work demonstrates the promise of electrochemical interfacial engineering as a strategy to boost electrocatalytic performance.
A Rebuilding‐Free Nucleic Acid Detection Strategy Enables Ultrasensitive Genotyping, N‐in‐1 Logic Screening and Accurate Multiplex Assay of Dangerous Pathogens
Authors: Li Huan , Lu Huiying , Tang Yidan , Wang Huaning , Xiao Yao , Li Bingling 
Published: August 2022

AbstractSensitive, rapid and low‐cost nucleic acid detection is critical for controlling infectious pathogens. Here, we develop a ready‐to‐use and multimodal detection based on a rebuilding‐free, ultrasensitive and selective strategy named dual hairpin ligation‐induced isothermal amplification pro (DHLApro). Taking influenza A, influenza B, MERS‐CoV, SARS‐CoV‐2 as model targets, we demonstrate DHLApro provides ≈zM level ultra‐sensitivity, being equaling to 0.45 copy/μL in original sample. By simply changing the recognition module, a set of DHLApro components can be applied to a new target without performance loss. Moreover, DHLApro innovatively allows flexible logic/multiplex assay using one set of primer, for example, the “N pathogens‐in‐1” OR gate screening and accurate multi‐channel multiplex assay. Compared with traditional methods, the cost of this logic/multiplex assay has been largely reduced and the cross‐interference between the multiple primer sets is also avoided.
Direct Arene Trifluoromethylation Enabled by a High‐Valent CuIII−CF3Compound
Authors: Zhang Hao‐Ran , Feng Cong‐Cong , Chen Ning , Zhang Song‐Lin 
Published: August 2022

AbstractDirect C−H trifluoromethylation of arenes and heteroarenes poses an important synthetic challenge that is highly desirable. High‐valent CuIII−CF3compounds have often been invoked in copper‐mediated trifluoromethylation reactions, but the fundamental reactivity toward arenes is elusive. Herein, direct C−H trifluoromethylation of arenes/heteroarenes by a high‐valent CuIII−CF3compound is disclosed for the first time. The CuIII−CF3compound serves CF3radical and a CuIIoxidant by homolytic cleavage of a CuIII−CF3bond, which engage synergistically in a SEAr type reaction with arenes. The presence of K2S2O8co‐oxidant can significantly improve the reaction yields. This reaction shows good efficiency, broad functional group tolerance, and the potential in late‐stage functionalization. The reactivity of high‐valent CuIII−CF3compounds disclosed in this study represents an important progress in organofluorine and CuIIIchemistry.
1,4‐Dihydropyridinebutyrolactone‐derived ring‐opened ester and amide analogs targeting BET bromodomains
Authors: Jiang Jiewei , Zhao Pei‐Liang , Sigua Logan H. , Chan Alice , Schönbrunn Ernst , Qi Jun , Georg Gunda I. 
Published: August 2022

AbstractBased on a previously reported 1,4‐dihydropyridinebutyrolactone virtual screening hit, nine lactone ring‐opened ester and seven amide analogs were prepared. The analogs were designed to provide interactions with residues at the entrance of the ZA loop of the testis‐specific bromodomain (ZA) channel to enhance the affinity and selectivity for the bromodomain and extra‐terminal (BET) subfamily of bromodomains. Compound testing by AlphaScreen showed that neither the affinity nor the selectivity of the ester and lactam analogs was improved for BRD4‐1 and the first bromodomain of the testis‐specific bromodomain (BRDT‐1). The esters retained affinity comparable to the parent compound, whereas the affinity for the amide analogs was reduced 10‐fold. A representative benzyl ester analog was found to retain high selectivity for BET bromodomains as shown by a BROMOscan. X‐ray analysis of the allyl ester analog in complex with BRD4‐1 and BRDT‐1 revealed that the ester side chain is located next to the ZA loop and solvent exposed.
The synthesis and evaluation of thiolated alginate as the barrier to block nutrient absorption on small intestine for body‐weight control
Authors: Chen Tzu‐Chien , Tang Rui‐Chian , Lin Jhih‐Ni , Kuo Wei‐Ting , Yang I‐Hsuan , Liang Ya‐Jyun , Lin Feng‐Huei 
Published: August 2022

AbstractObesity is the most common health concern all over the world. However, till now, there is no promising way to manage obesity or body‐weight control. The aim of the study is to develop an edible gel as a health supplement that temporarily attaches to the mucus of the intestines, forming an absorption barrier to block the nutrients. We modify the alginate with the thiol group as thiolated alginate (TA) that may stay on the mucosa layer for a much longer time to reduce nutrient absorption. In this study, the TA is synthesized successfully and proved a good mucosal adhesion to serve as a barrier for nutrient absorption both in vitro and in vivo. The results of in vivo imaging system (IVIS) show that the synthesized TA can be exiled from the gastrointestinal tract within 24 h. The animal study shows that the TA by daily oral administration can effectively reduce body weight and fat deposition. The biosafety is evaluated in vitro at the cellular level, based on ISO‐10993, and further checked by animal study. We do believe that the TA could have a greater potential to be developed into a safe health supplement to manage obesity and for body‐weight control.
Phenolic Glycosides from the Leaves of Iodes cirrhosa Turcz. with Cytotoxic and Antimicrobial Effects
Authors: Thi Ngoc Ninh , Hong Quang Tran , Thi Hong Hanh Tran , Xuan Cuong Nguyen , The Cuong Nguyen , Hoang Ha Chu , Hoai Nam Nguyen , Van Minh Chau 
Published: August 2022

AbstractIn the present study, 14 phenolic glycosides, including one new neolignan glycoside, iodescirrhoside A (1), three new flavonol glycosides, iodescirrhosides B–D (2–4), and 10 known metabolites were obtained from the methanol extract of Iodes cirrhosa leaves. Structural elucidation was performed by interpretating the 1D‐ and 2D‐ NMR, HR‐ESI‐MS, and CD spectra in comparison with literature data. All compounds were noncytotoxic to LU‐1, HepG2, MCF‐7, SK‐Mel‐2, and LNCaP cancer cell lines. Compound 11 significantly inhibited the growth of E. faecalis. In contrast, weak inhibition was observed for 1–9 and 14 against E. faecalis, for 1, 6–8, and 11 against S. aureus, for 6 and 13 against B. cereus, and 2, 4, and 6–9 against C. albicans.
Premature ventricular complexes as a first manifestation in left ventricular non‐compaction cardiomyopathy: A case report and focused review of the literature
Authors: Sánchez Velásquez Alejandro , Álvarez Ortiz Alexander , Porras Bueno Cristian Orlando 
Published: August 2022

AbstractLeft ventricular non‐compaction (LVNC) cardiomyopathy is an uncommon unclassified or genetic myocardial disorder. Frequent premature ventricular complexes (PVCs) as unique finding in LVNC cardiomyopathy are rare. We report a case of a 36‐year‐old woman in whom isolated LVNC was diagnosed due to an incidental finding of PVCs in pre‐operative consultation.
Carbon Dioxide Hydrogenation to Formic Acid with Self‐Separating Product and Recyclable Catalyst Phase
Authors: Ehmann Kira R. , Nisters Arne , Vorholt Andreas J. , Leitner Walter 
Published: August 2022

AbstractThe homogeneously catalyzed hydrogenation of carbon dioxide to formic acid is a promising route for carbon dioxide utilization and power‐to‐X concepts. Separation of the product and the catalyst under retention of the performance of the catalyst remains a major challenge, however. Herein, we present a Ru‐phosphine catalyzed reaction system comprising only a hydrophobic solvent as the catalyst phase and N‐methyldiethanolamine as a base. The formation of formic acid causes a spontaneous separation of the monophasic reaction mixture into a pure formic acid/amine product and a recyclable catalyst phase. By optimizing the reaction conditions, a turnover number of 1590 in a single reaction and a total turnover number of 5590 after four recycling runs were achieved.
Nutrients Release Evaluation on NPK Fertilizer Coated by a Carbon Microspheres Superabsorbent Polymer
Authors: Che Ani Norlirabiatuladawiyah , Ghazali Suriati , Ahmed Khan Tanveer , Kim Hyun-Joong , Jamari Saidatul Shima 
Published: August 2022

AbstractThe release of nutrients and the diffusion coefficients of an NPK fertilizer coated by carbon microspheres superabsorbent polymer (SCC) were evaluated. The morphology, chemical structure, water absorbency, release behavior in soil, and kinetic parameters of release behavior were studied. The maximum water absorbency was observed at 2 wt % of carbon microspheres in the polymer. The release rate of NPK‐coated superabsorbent polymer (SAP) was 12 % slower than that of uncoated NPK fertilizer but 24 % faster than that of NPK fertilizer coated by SCC. NPK coated by SCC fitted well with the Korsmeyer‐Peppas model compared to NPK coated by SAP. The addition of carbon microspheres enhanced the functionality of the superabsorbent polymer and release behavior of the fertilizer solutions.
Experimental and Theoretical Investigation of an Azaoxyallyl Cation‐Templated Intramolecular Aryl Amination Leading to Oxindole Derivatives
Authors: Bera Tishyasoumya , Singh Bandana , Gandon Vincent , Saha Jaideep 
Published: August 2022

AbstractHerein, development and detailed investigation of a SN′‐type intramolecular aromatic substitution reaction involving α‐arylazaoxyallyl cation intermediate, is disclosed. The study showcased that while α‐aryl‐α‐chlorohydroxamate could be activated by a combination of base and 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) into the corresponding azaoxyallyl cations, it could further emerge into a π‐extended species involving the adjacent α‐aryl moiety, and this transition is contingent on electronic effects of the aromatic ring as well as on α‐substituents. An effective activation of the α‐aromatic ring could pave the path for intramolecular Ar(Csp2)‐N bond formation towards oxindoles. Control experiments and DFT calculations suggested that a non‐pericyclic nucleophilic amination pathway is most likely operative and precluded the possibility of concerted or electrophilic amination mechanism. HFIP as the reaction solvent plays pivotal roles in the transformation.
Infusion of Variable Chemical Structure to Tune Stacking among Metal‐Organic Layers in 2D Nano MOF
Authors: Manna Biplab , Yokoi Hiroyuki , Yamashita Akihiro , Sato Shota , Ohyama Junya , Kunitake Masashi , Ida Shintaro 
Published: August 2022

AbstractThickness of two‐dimensional (2D) metal‐organic frameworks (MOFs) govern their intriguing functionalities. Primarily this thickness is controlled by the stacking between the metal‐organic layers (MOL). It is observed that until now such modulating factors for stacking efficiency of MOL are not well studied. Here, we report a fundamental hypothesis to comprehend regulation of stacking efficiency among MOLs as a function of chemical structure of organic ligands (dicarboxylic acids and pillar linkers). This basically involves a series of isostructural three‐dimensional (3D) MOFs which contain linkers of variable chemical nature that could be depillared to generate 2D stacked MOFs of different thickness. Depending on the linkers, we encountered the formation of single MOL to stacked multiple MOLs as evidenced from atomic force microscopic and other experimental analysis. The present study gives a concrete correlation between the stacking within 2D MOFs (from monolayer to multilayers), and their 3D counter parts, which may provide a thickness tuning pathway for 2D MOFs.
Free Aluminylenes: An Emerging Class of Compounds
Authors: Zhang Xin , Mei Yanbo , Liu Liu Leo 
Published: August 2022

AbstractAluminylenes (R−Al) are aluminium analogs of carbenes. In contrast to isolable carbenes, aluminylenes are extremely rare species. In the past years, pioneered by Schnöckel, Roesky and Power, a few free aluminylenes and their complexes have been reported. Such compounds have the aluminium atom in the oxidation state +I, which contrasts with classical organoaluminium derivatives that contain the element in the +III oxidation state. Aluminylenes, either in their free state or in the coordination sphere of a Lewis base, are capable of coordinating to transition metals and activating inert chemical bonds. Free aluminylenes are emerging as potent synthetic platforms for unusual aluminium species.
Two Rhodium(III) Ions Confined in a [18]Porphyrin Frame: 5,10,15,20‐Tetraaryl‐21,23‐dirhodaporphyrin
Authors: Vetter Grzegorz , Białońska Agata , Krzyszowska Paulina , Koniarz Sebastian , Pacholska‐Dudziak Ewa 
Published: August 2022

AbstractInvited for the cover of this issue is the group of Ewa Pacholska‐Dudziak at the University of Wroclaw. The image depicts two rhodium atoms being fixed into the skeleton of 21,23‐dirhodaporphyrin in place of two core nitrogen donors. Read the full text of the article at 10.1002/chem.202201513.
Diastereoselectivity on Intramolecular Alder‐ene Reaction of 1,6‐Dienes
Authors: de Cózar Abel 
Published: August 2022

AbstractA detailed computational study of the intramolecular Alder‐ene reaction of different 1,6‐dienes at M06‐2X(PCM)/TZ2P level of theory has been performed. We want to understand the influence of enophile‐geminal substitution pattern in the cis : trans selectivity of the cyclization process. Our analysis of the reaction coordinate by means of activation strain model of chemical reactivity (ASM‐distortion interaction model) reveals that the cis‐selectivity observed for unactivated reagents is related with high stabilizing orbital interaction and lower strain energy, consequence of an early transition structure. On the other hand, the presence of activating groups increases the asynchronicity of the transition structures and reduces the activation barrier due to more stabilizing orbital and electrostatic interactions, favoring trans‐selectivity.
Coherence and Efficient Energy Transfer in Molecular Wires: Insights from Surface Hopping Simulations
Authors: Sindhu Aarti , Jain Amber 
Published: August 2022

AbstractUnderstanding the dynamics of electronic energy transfer through a molecular wire is essential to understand the working of natural processes like photosynthesis. We investigate simpler 2 and 3‐site model Hamiltonians in this work to understand the importance of coherence to efficient energy transfer. We compare the results of surface hopping simulation with that of numerically exact results and rate theories. Different parameters are analyzed, motivated by a photosynthetic molecular wire – the FMO complex. A comparison of results from different theories shows that coherence can play an important role towards efficient energy transfer for certain parameters. When these coherences are important, even small couplings (of the order of 5 cm−1) in the Hamiltonian can significantly affect rates. Surface hopping simulations capture all the results correctly qualitatively. Rate theories, on the other hand, can differ significantly from numerically exact results when coherences become important. The results of this work should provide design guidelines for efficient energy transfer in molecular wires.
Boosting Hydrolysis of Cellulose at High Temperature by β‐Glucosidase Induced Metal–Organic Framework In‐Situ Co‐Precipitation Encapsulation
Authors: Jiao Rui , Pang Yuxia , Yang Dongjie , Li Zhixian , Lou Hongming 
Published: August 2022

AbstractDue to the poor enzyme thermal stability, the efficient conversion of high crystallinity cellulose into glucose in aqueous phase over 50 °C is challenging. Herein, an enzyme‐induced MOFs encapsulation of β‐glucosidase (β‐G) strategy was proposed for the first time. By using various methods, including SEM, XRD, XPS, NMR, FTIR and BET, the successful preparation of a porous channel‐type flower‐like enzyme complex (β‐G@MOFs) was confirmed. The prepared enzyme complex (β‐G@MOFs) materials showed improved thermal stability (from 50 °C to 100 °C in the aqueous phase) and excellent resistance to ionic liquids (the reaction temperature was as high as 110 °C) compared to the free enzyme (β‐G). Not only the catalytic hydrolysis of cellulose by single enzyme (β‐G) in ionic liquid was realized, but also the high‐temperature continuous reaction performance of the enzyme was significantly improved. Benefiting from the significantly improved heat resistance, the β‐G@MOFs exhibited 32.1 times and 34.2 times higher enzymatic hydrolysis rate compared to β‐G for cellobiose and cellulose substrates, respectively. Besides, the catalytic activity of β‐G@MOFs was retained up to 86 % after five cycles at 110 °C. This was remarkable because the fixation of the enzyme by the MOFs ensured that the folded structure of the enzyme would not expand at high temperatures, allowing the native conformation of the encapsulated protein well‐maintained. Furthermore, we believe that this structural stability was caused by the confinement of flower‐like porous MOFs.
Benign cytology does not rule out malignancy in thyroid nodules larger than 4 cm
Authors: Baser Ozden Ozdemir , Koseoglu Derya , Cetin Zeynep , Catak Merve , Kizilkaya Hafize 
Published: August 2022

AbstractBackgroundFor thyroid nodules ≥4 cm, the accuracy of fine‐needle aspiration biopsy (FNAB) is controversial and the approach is unclear. We aimed to compare FNAB and operation of thyroid nodules and to determine the accuracy of FNAB.Material and MethodsAll total thyroidectomies performed between January 2015 and December 2021 were evaluated. In the study, 301 patients were included. Euthyroid patients with preoperative thyroid ultrasound, FNAB results and operation results were recorded retrospectively.ResultsThe nodule size was <4 cm in 79.1% of the patients, and ≥4 cm in 20.9%. In patients with nodule size ≥4 cm, 50.8% of FNAB results were reported as benign, and 43.7% of these patients were found to be malignant at the end of the operation. In nodules <4 cm, 36.8% of the patients whose FNAB results were found to be benign were malignant. False‐negativity rate was found to be quite high in ≥4 cm nodules.ConclusionsFor thyroid nodules, diagnostic lobectomy may be necessary because the false‐negative rate of FNAB was high, especially in nodules ≥4 cm. In addition, intermediate results, such as AUS/FN, have a higher risk of malignancy in nodules of ≥4 cm compared to nodules of <4 cm.