bluuebunny/crossref_metadata_2025 huggingface dataset:
Mimicking Bone Extracellular Matrix: From BMP‐2‐Derived Sequences to Osteogenic‐Multifunctional Coatings
Authors: Oliver‐Cervelló Lluís , Martin‐Gómez Helena , Mandakhbayar Nandin , Jo Young‐Woo , Cavalcanti‐Adam Elisabetta Ada , Kim Hae‐Won , Ginebra Maria‐Pau , Lee Jung‐Hwan , Mas‐Moruno Carlos
Published: August 2022

Cell–material interactions are regulated by mimicking bone extracellular matrix on the surface of biomaterials. In this regard, reproducing the extracellular conditions that promote integrin and growth factor (GF) signaling is a major goal to trigger bone regeneration. Thus, the use of synthetic osteogenic domains derived from bone morphogenetic protein 2 (BMP‐2) is gaining increasing attention, as this strategy is devoid of the clinical risks associated with this molecule. In this work, the wrist and knuckle epitopes of BMP‐2 are screened to identify peptides with potential osteogenic properties. The most active sequences (the DWIVA motif and its cyclic version) are combined with the cell adhesive RGD peptide (linear and cyclic variants), to produce tailor‐made biomimetic peptides presenting the bioactive cues in a chemically and geometrically defined manner. Such multifunctional peptides are next used to functionalize titanium surfaces. Biological characterization with mesenchymal stem cells demonstrates the ability of the biointerfaces to synergistically enhance cell adhesion and osteogenic differentiation. Furthermore, in vivo studies in rat calvarial defects prove the capacity of the biomimetic coatings to improve new bone formation and reduce fibrous tissue thickness. These results highlight the potential of mimicking integrin‐GF signaling with synthetic peptides, without the need for exogenous GFs.
Mechanistic Insights of Electrochemical Cl2 and O2 Generation from Lanthanum Cobalt Manganese Oxide
Authors: Sood Kritika , Rana Supriya , Wadhwa Ritika , Bhasin Kuldeep Kumar , Jha Menaka
Published: August 2022

The chlorine evolution reaction holds a core role in the chemical industries and water‐treatment plants. To overcome the high power input supplied for Cl2 generation at an industrial scale an efficient and durable electrocatalyst is always on hunt. Double perovskite oxides have been used previously for oxygen evolution reaction (OER) and have shown outstanding results on the ground of dual surface active site mechanism. Here, La2CoMnO6 (LCMO) are explored for the electrochemical Cl2 and O2 generation. The electrocatalytic studies are performed in 5 m NaCl (pH ≈ 2.2) for chlorine evolution reaction (CER) and 1 m KOH (pH = 13.5) for OER. The LCMO shows enhanced catalytic activity with onset and overpotential of 75 and 280 mV for CER. Further, the kinetics of the catalytic reaction is determined by the Tafel slope values that is calculated to be 44 mV dec−1 for CER. The interfacial charge transfer resistance value at 11 Ω tells the insight mechanism by facilitating more interaction between electrode‐electrolyte interfaces. In addition to this, wettability analysis of LCMO shows a contact angle as low as 23°. The present study paves a way for double perovskites to be used as an electro‐catalyst for the chlor‐alkali process.
Zincate‐Mediated Remote Functionalisation of p‐Iodobenzyl Derivatives Through Metallotropy in 2‐Methyltetrahydrofuran as Key Solvent
Authors: Pierret Alexandre , Denhez Clément , Gros Philippe C. , Vasseur Alexandre
Published: August 2022

2‐MeTHF (2‐methyltetrahydrofuran) promotes the zincate‐mediated remote functionalisation of p‐iodobenzyl derivatives through metallotropy with a broad scope. This biosourced solvent remarkably impacted all the key elementary steps involved in the tandem reaction. The method tolerates a wide range of sensitive functionalities within the substrates as well as enolisable and activated or deactivated aromatic aldehydes as reaction partners. A challenging benzyl naphthalene derivative was even reacted through an original dearomatisation/rearomatisation/metallotropy chain.

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Enzyme activities as soil health indicators in relation to soil characteristics and crop production
Authors: Sainju Upendra M. , Liptzin Daniel , Dangi Sadikshya M.
Published: August 2022

Soil enzyme activities are known for early indicators of soil health but have not been related to most soil properties and crop yields. We examined the relationships among activities of four soil enzymes (β‐glucosidase [BG], N‐acetyl‐β‐glucosaminidase [NAG], arylsulfatase [AST], and phosphomonoesterase [PME]), 62 soil properties, and mean crop yields in two long‐term (14‐ and 36‐yr‐old) dryland farming sites in the northern Great Plains, USA. Treatments were no‐till and till crop rotations with spring wheat (Triticum aestivum L.), barley (Hordeum vulgare L.), pea (Pisum sativum L.), and fallow with and without N fertilization. Soil samples collected before farming operations in April 2019 were analyzed for physical, chemical, biological, and biochemical properties and mean crop yields were determined. The principal component analysis (PCA) showed that BG was associated to most soil physical, chemical, biological, and biochemical properties followed by NAG and PME at both sites. The AST was associated to limited number of soil properties. The BG related to mean crop yield across years in one site and NAG related to yields in both sites, but AS and PME were not related to yields. Because of the greater sensitivity to cropping systems and relationships with most soil properties and long‐term crop yields, BG and NAG activities may be considered as promising soil health indicators compared with other enzyme activities under dryland cropping systems in the northern Great Plains.
Concurrent improvement of durum and emmer wheat through reciprocal backcrossing and hybridization
Authors: Shoormij Fatemeh , Mirlohi Aghafakhr , Saeidi Ghodratollah , Mohammadi Majid
Published: August 2022

Emmer wheat has not been improved but is a valuable gene source for improving durum (Triticum turgidum ssp. durum). Conversely, durum is less looked upon for emmer (T. turgidum ssp. dicoccum) improvement. This study examined the possibility of concurrently improving the two species by crossing eight durum cultivars with four emmer local varieties in a half‐diallel fashion in two consecutive years. Also, emmer and two durum genotypes were reciprocally backcrossed, and their BC1F1 progeny were field‐evaluated during the wheat cropping season (November–June) at the Isfahan University of Technology research farm (32°32′ N, 51°23′ E). The results showed that durum wheat had a considerable effect on the grain yield (GY), kernel diameter, 1,000‐kernel weight (TKW), and test weight of F1 hybrids, whereas emmer contributed more to increasing the grain protein content (GPC), kernel length, and plant height (PH). A similar pattern was observed for BC1F1 hybrids from the two recurrent durum parents. The GPC was reduced with recurrent durum parents in the backcrosses compared with emmer, but was still higher than in both durum parents. In the backcrosses with the recurrent emmer parent, GY and TKW were higher than those of emmer but only slightly lower than those of the durum parents. The PH was strongly influenced by emmer in all crosses, though the lodging was significantly reduced compared with emmer, possibly through obtaining stronger stems from durum. These findings suggest the possibility of combining desirable genes from the two species and their concurrent improvement in a single breeding program.
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

In 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

Cardio‐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

Dispersal 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

Developing 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

Sensitive, 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

Direct 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

Based 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

Obesity 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

In 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

Left 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

The 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

The 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

Herein, 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

Thickness 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

Aluminylenes (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

Invited 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

A 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

Understanding 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

Due 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

Background

For 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 Methods

All 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.

Results

The 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.

Conclusions

For 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.
A fully automated method to quantitate total carbon dioxide in equine plasma by headspace GCMS
Authors: Zahra Paul W. , Jayasinghe Nirupama S. , Selvadurai Naomi S. , Willers Stewart J. , Krsta Dragan , Batty David C. , Vine John H.
Published: August 2022

Pre‐race dosing of horses with alkalinising agents to manipulate performance has been evident in racing worldwide for over 30 years. To regulate the use of alkalinising agents, racing authorities adopted thresholds for total plasma carbon dioxide (TCO2) in racehorses. Traditionally, racing laboratories have measured plasma TCO2 using ion selective electrode (ISE) technology, with the Association of Official Racing Chemists (AORC) approving the use of only three ISE instruments for measurement. Because of the manufacture and support of these instruments ceasing, racing laboratories have explored alternative techniques to measure plasma TCO2. In this study, headspace gas chromatography mass spectrometry (HSGCMS) with fully automated sample preparation was investigated as an alternative technique to ISE. Sample preparation was carried out online on a Gerstel robot, where plasma was aspirated directly from sealed vacutainer tubes before further treatment and headspace injection into a GCMS. The method was successfully cross validated against a Beckman Unicel DxC®600, meeting all criteria stipulated in the AORC cross‐validation protocol. The method achieved an accuracy of 99.8%, within‐run relative standard deviation of 0.22% and interday reproducibility of 0.04 mM, all significant improvements on the authors ISE method. A population study was also conducted to ensure the plasma TCO2 threshold, established with ISE methodology, did not change with the developed HSGCMS method. The concentrations and standard deviations for the two methods were almost identical, HSGCMS mean 30.62 mM, standard deviation 1.65 mM, and ISE 30.65 and 1.55 mM. The results indicate that the fully automated HSGCMS method is suitable for measurement of equine plasma TCO2 for regulatory purposes.
Photochemical 1,3‐Acyl Shifts in Natural Product Synthesis
Authors: Lübken Dennis , Siekmeyer Björn , Kalesse Markus
Published: August 2022

Photochemical, sigmatropic 1,3‐acyl shifts represent a powerful tool to construct quaternary carbon atoms and the backbones of complex natural products which cannot be constructed easily by conventional methods. This review highlights applications of 1,3‐acyl shifts to elegant, partly biomimetic total syntheses of natural products by discussing the underlying photochemical equilibrium.
1,3‐Dipolar Cycloaddition of Alkanone Enolates with Azides in Deep Eutectic Solvents for the Metal‐Free Regioselective Synthesis of Densely Functionalized 1,2,3‐Triazoles
Authors: Cicco Luciana , Perna Filippo Maria , Falcicchio Aurelia , Altomare Angela , Messa Francesco , Salomone Antonio , Capriati Vito , Vitale Paola
Published: August 2022

An eco‐friendly metal‐free protocol was developed for the regioselective synthesis of densely functionalized 1,2,3‐triazoles through a 1,3‐dipolar cycloaddition reaction of alkanone enolates with azides performed in the environmentally responsible choline chloride/urea or choline acetate/urea eutectic mixture. This approach displays a broad substrate scope, straightforwardly furnishing the desired triazoles (including the challenging phenolic derivatives) in yields of up to 98 %, while working at room temperature and under aerobic conditions. The practicability of the method is exemplified by the sustainable synthesis of some pharmaceutically relevant triazole derivatives carried out via telescoped, one‐pot cycloaddition/reduction processes in the same eutectic mixture without any halfway isolation/purification step of intermediates.
On occurrence disaggregation of probabilistic seismic hazard
Authors: Cito Pasquale , Iervolino Iunio
Published: August 2022

Disaggregation of probabilistic seismic hazard allows to quantify how much one or more earthquake scenarios contribute to the occurrence [exceedance] of a ground motion intensity measure threshold of interest (x) at the construction site. The scenario is usually defined in terms of magnitude (M), source‐to‐site distance (R), and possibly includes the standardized residual (ε) of the ground motion model considered in the hazard analysis. Analytically, in case occurrence is of interest, disaggregation provides the joint probability density function of or conditional on the event, that is, or . Occurrence disaggregation is important for a number of earthquake engineering applications, and it is typically addressed in the literature in an approximated manner, considering as the conditioning event , with being an arbitrary finite width of the interval. This short communication undertakes a deeper examination of occurrence disaggregation clarifying that: (i) no approximation is needed in the case of disaggregation in terms of magnitude and distance (i.e., when is sought); (ii) is theoretically degenerate, and as such, its approximation via finite can lead to misleading results; (iii) if is chosen coherently with the discretization of the domain used in the hazard integral, it leads to approximated , enabling the conclusion that occurrence disaggregation does not add information with respect to disaggregation.
A stochastic‐volatility equity‐price tree for pricing convertible bonds with endogenous firm values and default risks determined by the first‐passage default model
Authors: Dai Tian‐Shyr , Fan Chen‐Chiang , Liu Liang‐Chih , Wang Chuan‐Ju , Wang Jr‐Yan
Published: August 2022

This paper proposes a novel equity‐price‐tree‐based convertible bond (CB) pricing model based on the first‐passage default model under stochastic interest rates. By regarding equity values as down‐and‐out call options on firm values (FVs), at each tree node, we solve the implied FV and equity‐price volatility (EPV), and then endogenously settle the default probability (DP) and also the dilution effect subject to CB conversions with the implied FV and capital structure. Our model captures the stylized negative (positive) relationships between the stochastically evolving DP and FV or EP (EPV) that cannot be fully achieved by existing CB pricing models.
Microglial angiotensin type 2 receptors mediate sex‐specific expression of inflammatory cytokines independently of circulating estrogen
Authors: Garrido‐Gil Pablo , Pedrosa Maria A. , Garcia‐Garrote Maria , Pequeño‐Valtierra Ana , Rodríguez‐Castro Jorge , García‐Souto Daniel , Rodríguez‐Pérez Ana I. , Labandeira‐Garcia Jose L.
Published: August 2022

There are sex differences in microglia, which can maintain sex‐related gene expression and functional differences in the absence of circulating sex steroids. The angiotensin type 2 (AT2) receptors mediate anti‐inflammatory actions in different tissues, including brain. In mice, we performed RT‐PCR analysis of microglia isolated from adult brains and RNA scope in situ hybridization from males, females, ovariectomized females, orchiectomized males and brain masculinized females. We also compared wild type and AT2 knockout mice. The expression of AT2 receptors in microglial cells showed sex differences with much higher AT2 mRNA expression in females than in males, and this was not dependent on circulating gonadal hormones, as observed using ovariectomized females, brain masculinized females and orchiectomized males. These results suggest genomic reasons, possibly related to sex chromosome complement, for sex differences in AT2 expression in microglia, as the AT2 receptor gene is located in the X chromosome. Furthermore, sex differences in expression of AT2 receptors were associated to sex differences in microglial expression of key anti‐inflammatory cytokines such as interleukin‐10 and pro‐inflammatory cytokines such as interleukin‐1β and interleukin‐6. In conclusion, sex differences in microglial AT2 receptor expression appear as a major factor contributing to sex differences in the neuroinflammatory responses beyond the effects of circulating steroids.
The effect of community engagement on healthcare utilization and health insurance enrollment in Ghana: Results from a randomized experiment
Authors: Opoku Duku Stephen Kwasi , Nketiah‐Amponsah Edward , Fenenga Christine J. , Janssens Wendy , Pradhan Menno
Published: August 2022

Health insurance enrollment in many Sub‐Saharan African countries is low, even with highly subsidized premiums and exemptions for vulnerable populations. One possible explanation is low service quality, which results in a low valuation of health insurance. Using a randomized control trial in 64 primary health care facilities in Ghana, this study assesses the impact of a community engagement intervention designed to improve the quality of healthcare and health insurance services on households living nearby the facilities. Although the intervention improved the medical‐technical quality of health services, our results show that households' subjective perceptions of the quality of healthcare and insurance services did not increase. Nevertheless, the likelihood of illness and concomitant healthcare utilization reduced, and especially households who were not insured at baseline were more likely to enroll in health insurance. The results show that solely increasing the technical quality of care is not sufficient to increase households' subjective assessments of healthcare quality. Still, improving technical quality can directly contribute to health outcomes and further increase health insurance coverage, especially among the previously uninsured.
Distribution of the head and neck surgical oncology workforce in the United States
Authors: Talwar Abhinav , Gordon Alex J. , Bewley Arnaud F. , Fancy Tanya , Lydiatt William M. , Weed Donald , Moore Michael G. , Givi Babak
Published: August 2022

Background

The recent trends in education and geographic distribution of the head and neck surgery workforce have not been studied extensively.

Methods

We reviewed publicly available sources to locate all fellowship‐trained head and neck surgeons and recent graduates. The number of surgeons in each state was compared against head and neck cancer incidence data from the Centers for Disease Control.

Results

The number of graduates increased annually by 1 per 100 000 000 people from 2011–2020. The average number of fellowship‐trained surgeons per state was 10 (SD: 12). The average number of new head and neck cancer cases per surgeon was 247 (SD: 135). Ten states (20%) had cases >1 SD above the national average/surgeon, while 3 (6%) had cases >1 SD below the national average.

Conclusion

Head and neck surgeons are located in most states, but not uniformly. Most states have approximately average density of surgeons; however, several states are outliers.
Numerical investigation of viscoelastic boundary layer in forced convection flow on surface under prescribed heat flux
Authors: Maaitah Hussein , Quran Omar , Elayyan Mutaz , Awad Ahmad S. , Duwairi Hamzeh M.
Published: August 2022

The paper intends to analyze numerically the effect of forced convection with viscoelastic boundary on porous media subjected to constant heat flux on the surface. The modified Navier–Stokes equations in nondimensional forms are formulated and modeled with Darcy–Forchheimer–Brinkman to solve the equations using bvp4c with MATLAB package. The numerical results are found for local Nusselt number, shear stress, temperature distribution, and finally the velocity of the boundary layer over a horizontal plate. The analysis includes the influence of several parameters, such as Forchheimer, porous media, Nusselt number, and viscoelastic on distributions of velocity and temperature. Also, the effects comprise the friction and heat transfer coefficients. The numerical results under constant heat flux indicate an increase in shear stress and boundary layer velocity as the Darcy parameter increases and at the same time, the values of temperature and Nusselt number are decreased. A significant increase was observed for the values of Nusselt number, temperature, and shear stress under large values of the Forchheimer parameter. The numerical results show a good agreement with available previous works.
Non‐linearity in event runoff generation in a small agricultural catchment
Authors: Vreugdenhil Mariette , Széles Borbála , Salinas José Luis , Strauß Peter , Oismueller Markus , Hogan Patrick , Wagner Wolfgang , Parajka Juraj , Blöschl Günter
Published: August 2022

Understanding the role of soil moisture and other controls in runoff generation is important for predicting runoff across scales. This paper aims to identify the degree of non‐linearity of the relationship between event peak runoff and potential controls for different runoff generation mechanisms in a small agricultural catchment. The study is set in the 66 ha Hydrological Open Air Laboratory, Austria, where discharge was measured at the catchment outlet and for 11 sub‐catchments or hillslopes with different runoff generation mechanisms. Peak runoff of 73 events was related to three potential controls: event precipitation, soil moisture and groundwater levels. The results suggest that the hillslopes dominated by ephemeral overland flow exhibit the most non‐linear runoff generation behaviour for its controls; runoff is only generated above a threshold of 95% of the maximum soil moisture. Runoff generation through tile drains and in wetlands is more linear. The largest winter and spring events at the catchment outlet are caused by runoff from hillslopes with shallow flow paths (ephemeral overland flow and tile drainage mechanisms), while the largest summer events are caused by other hillslopes, those with deeper flow paths or with saturation areas throughout the year. Therefore, the response of the entire catchment is a mix of the various mechanisms, and the groundwater contribution makes the response more linear. The implications for hydrological modelling are discussed.
Preparation and characterization of a self‐crosslinking sodium alginate‐bioactive glass sponge
Authors: Gong Wensheng , Liu Lingling , Luo Liping , Ji Lijun
Published: August 2022

In this research, bioactive glass particles prepared by the reactive flash nanoprecipitation method (RFNP‐BG particles) are used to crosslink sodium alginate to prepare biological sponges (SA‐BG sponges) by freeze‐drying. An experiment for the cross‐linking mechanism confirms that the continuous release of Ca2+ from RFNP‐BG is promoted by the crosslinking reaction and in turn leads to the gelation process of SA. Bioactive glass particles not only provide Ca2+ for the crosslinking of sodium alginate, but also enhance the mechanical properties of the SA‐BG sponges. The results show that the elastic modulus of the SA‐BG sponges increases from 0.026 MPa to 0.641 MPa, and the resistance to external force deformation is greatly improved; the thermal decomposition temperature increases from 105°C to 166°C; compared with a pure SA sponge, the water resistance is significantly improved. In vitro cell experiments show that the SA‐BG sponges have a certain adverse effect on cell proliferation, but it is in an acceptable range. qPCR results show that the SA‐BG sponges have a certain beneficial effect on promoting osteogenic gene expression. The SA‐BG sponges have great application potential in the fields of medicine, hemostasis, and wound closure.
Impact of community well‐being on individual well‐being: A longitudinal multinational study with 155 countries
Authors: Donnelly Hayoung Kim , Solberg V. Scott H. , Zaff Jonathan F.
Published: August 2022

The purpose of the current study is to evaluate the longitudinal relationship between subjective community well‐being (CWB) (perception of freedom of choice and social support) and subjective individual well‐being (IWB) (positive and negative affect). Using the World Happiness Report (2019), this study examined the subjective IWB and subjective CWB among 155 countries across an 8‐year period. Using Latent Class Growth Analysis the results indicated that the 155 countries could be classified into three groups—countries reporting high freedom of choice and high social support, low freedom of choice and low social support, and low freedom of choice and high social support. From the results of both a multigroup Growth Mixed Model and a Growth Curve Model, the three groups were found to vary with respect to positive and negative affect with higher positive affect and lower negative affect reported in countries classified as high freedom of choice and high social support, lower positive affect and higher negative affect reported in countries classified as low freedom of choice and low social support, and lower positive and lower negative affect reported in countries classified as low freedom of choice and high social support. These results indicate that country's rated as allowing higher freedom of choice was associated with higher reported positive affect, and country's rated as having stronger social support systems was associated with lower ratings for negative affect.