bluuebunny/crossref_metadata_2025_split huggingface dataset:
Negative allosteric modulators of NMDA receptors with GluN2B subunit: Alanine‐derived benzoxazolone bioisosteres of 2‐methyl‐3‐benzazepine‐1,7‐diols
Authors: Markus Alexander , Frehland Bastian , Schepmann Dirk , Wünsch Bernhard 
Published: May 2022

AbstractInspired by besonprodil, the phenol of potent negative allosteric modulators of GluN2B‐N‐methyl‐d‐aspartate (NMDA) receptors was replaced by a benzoxazolone system. To increase the similarity to the lead compounds, an additional methyl moiety was installed in the 8‐position of tricyclic oxazolobenzazepines, resulting in compounds 6. The additional methyl moiety originates from alanine, which was introduced by a Mitsunobu reaction of benzoxazolylethanol 7 with N‐triflyl‐protected alanine methyl ester. A crucial feature of the synthesis was the protection of the oxazolone ring by an allyl moiety, which was cleaved off at the end of the synthesis by RhCl3‐catalyzed isomerization. Due to the additional methyl moiety, the intramolecular Friedel–Crafts acylation of acid 10 to afford ketone 11 required careful optimization to minimize the formation of the side product tetrahydroisoquinoline 16. Alkylation or reductive alkylation of secondary amine 13 led to diastereomeric oxazolobenzazepines cis‐14 and trans‐14, which were separated by flash chromatography. Phenylbutyl derivatives cis‐6a and trans‐6a revealed twofold higher GluN2B affinity than analog 5a without 8‐CH3 group. The methylated oxazolobenzazepines 6 and 14 did not interact with the phencyclidine binding site of NMDA receptors and σ2 receptors. However, the σ1 receptor preferred cis‐configured oxazolobenzazepines. The highest σ1 receptor affinities were obtained for cis‐14a (Ki = 26 nM) and cis‐6b (Ki = 30 nM).
Domino synthesis of functionalized pyridine carboxylates under gallium catalysis: Unravelling the reaction pathway and the role of the nitrogen source counter anion
Authors: Kumar Dinesh , Sharma Himanshu , Saha Nirjhar , Chakraborti Asit K. 
Published: May 2022

AbstractThe catalytic potential of various metal Lewis acid catalysts have been assessed to derive a high‐yielding, multi‐component domino synthesis of functionalized pyridines from (E)‐3‐(dimethylamino)‐1‐aryl/heteroaryl‐prop‐2‐en‐1‐ones, 1,3‐dicarbonyl compounds, and an ammonium salt (as the nitrogen precursor). Amongst the various metal halides, tetrafluoroborates, perchlorates, and triflates used as the catalyst, GaI3 proved to be the most effective. The mechanistic course of the most plausible pathway has been outlined as the intermediate formation of imine/enamine by the reaction of the 1,3‐dicarbonyl compound with ammonia (liberated in situ from the ammonium salt used as the nitrogen source), which participates in the domino nucleophilic Michael reaction to the (2E)‐3‐(dimethylamino)‐1‐aryl/hetroarylprop‐2‐en‐1‐one by its active methylene carbon through its enamine form followed by intramolecular cyclization and aromatization. The effect of different ammonium salts as the nitrogen source has been investigated and NH4OAc was found to be best. The influence of the acetate counter anion of NH4OAc on the progress of the reaction was studied and its specific role in the cyclization and subsequent aromatization has been revealed. This work offers distinct advantages compared to the literature reported methodologies on the count of several green index parameters.
Highly Conjugated Two‐dimensional Covalent Organic Frameworks for Efficient Iodine Uptake
Authors: Zhou Mingan , Li Zhongping , Munyentwali Alexis , Li Chunzhi , Shui Hengfu , Li He 
Published: May 2022

AbstractRadioactive iodine in nuclear waste would be harmful to nature and human health. The design of adsorbents for iodine capture with high efficiency still remains a challenge. Herein, two highly conjugated two‐dimensional covalent organic frameworks (TFPB‐BPTA‐COF and TFPB‐PyTTA‐COF) have been successfully constructed. Both COFs possess high porosity, stability, and a high π‐conjugated framework. Impressively, TFPB‐PyTTA‐COF exhibits an excellent iodine uptake value of up to 5.6 g g−1, which is superior to most reported COF‐based adsorbents for iodine capture.
An Efficient Route to 3,3′‐Biindolinylidene‐diones by Iron‐Catalyzed Dimerization of Isatins
Authors: Jagtap Rahul A. , Pradhan Chandini , Gonnade Rajesh G. , Punji Benudhar 
Published: May 2022

AbstractIron‐catalyzed dimerization of various isatin derivatives is described for the efficient synthesis of 3,3′‐biindolinylidene‐diones (isoindigos). The reaction provides easy access to self‐coupled and cross‐coupled 3,3′‐indolinylidene‐diones that have high relevance to biology and materials. This Fe(0)‐ or Fe(II)‐catalyzed dimerization reaction tolerates a wide range of functionalities, such as fluoro, chloro, bromo, alkenyl, nitrile, ether, ester, pyrrolyl, indolyl and carbazolyl groups, including cyclic and acyclic alkyls as well as an alkyl‐bearing fatty‐alcohol moiety. Especially, the coupling between two distinct isatins provided excellent selectivity for the cross‐dimerization with trace of self‐couplings. The single‐crystal X‐ray diffraction study established the molecular structure of eight dimerized products. A preliminary mechanistic study of the Fe‐catalyzed dimerization supported the radical pathway for the reaction.
Upgrading rice husk biochar characteristics through microwave‐assisted phosphoric acid pretreatment followed by co‐pyrolysis with LDPE
Authors: Binnal Prakash , Kumar Darsi Jayaprasanna , Sasalu Parameshwaraiah Manjunath , Patil Jagadish 
Published: May 2022

AbstractIn the present study, an attempt was made to upgrade the characteristics of rice husk biochar through a combination of two strategies: (i) microwave‐assisted phosphoric acid pretreatment (MAPP) of rice husk followed by (ii) co‐pyrolysis of pretreated rice husk with low‐density polyethylene (LDPE). The analysis of pretreated rice husk through biochemical composition, proximate analysis, ultimate analysis, thermogravimetric analysis (TGA), and X‐ray diffraction (XRD) showed that MAPP significantly improved the properties of rice husk. The pretreated rice husk had higher fixed carbon and volatile matter as compared with untreated rice husk (19.65% v/s 13.35% and 66.24% v/s 61.93%) and its ash content was lower than untreated rice husk (9.75% v/s 16.85%). The TGA analysis showed that MAPP improved the thermal stability of rice husk. At 719.65 °C, the residual masses of rice husk and pretreated rice husks were 13.76% and 23.75% respectively. An analysis of properties of biochars revealed that, biochar produced through combined mode had the highest carbon content (86.14%), the least ash content (1.29%), the least H/C and O/C values (0.29 and 0.09), and the highest Brunauer Emmett and Teller (BET) surface area (35.022 m2/g). Raman spectroscopy and XRD results showed that the biochar had a more orderly structure and less structural defects as compared to biochar produced from rice husk alone. © 2022 Society of Chemical Industry and John Wiley & Sons, Ltd.
Public procurement for innovation through supplier firms' sustainability lens: A systematic review and research agenda
Authors: Adjei‐Bamfo Peter , Djajadikerta Hadrian Geri , Jie Ferry , Brown Kerry , Kiani Mavi Reza 
Published: May 2022

AbstractPublic sector purchasing processes are gaining increasing prominence as a demand‐side innovation tool for addressing national sustainability challenges. Accordingly, there has been growing research attention to this topic. Prior studies suggest three key rationales that underlie the use of public sector procurement to drive innovation: (i) the buyer–user rationale (for creating new needs); (ii) the market/system failure rationale (for improving suppliers' capacity to innovate); and (iii) the public services rationale (for improving public services). However, operational activities at the upstream supply chain affecting the sustainable innovation capacities of supplier firms appear to be under‐researched in the public procurement for innovation (PPI) scholarship, despite knowledge about innovation capacity being critical to successfully implementing PPI. This paper adopts a systematic literature review approach to synthesise existing fragmented literature on sustainability‐oriented PPI, focusing on supplier perspectives. Findings from a synthesis of 41 relevant articles suggest, among others conditions, that a procurement framework that maintains a good balance of competition and innovation, builds buyer–supplier relationship and urges strong supply networks, maintains a stable political commitment, offers security for niche markets with effective innovation risk management culture would enhance suppliers' sustainability capacity and propensity to innovate. This paper contributes to the PPI literature and the literature on determinants of sustainable innovation systems from supplier firms' sustainability lens.
The application of spreadsheets for teaching hydrological modeling and climate change impacts on streamflow
Authors: Pérez‐Sánchez Julio , Senent‐Aparicio Javier , Jimeno‐Sáez Patricia 
Published: May 2022

AbstractHydrology teaching currently relies upon educators' background, requiring a change in training future professionals to manage water resources to address climate change, among other issues. In the teaching experience described in this paper, traditional lectures in a postgraduate civil engineering master's degree were replaced by the development and assessment of a lumped hydrological model implemented into an Excel spreadsheet. Although the primary activity evaluated the long‐term impacts of climate change on streamflow in a watershed, the students were required to address several specific issues such as calibration and validation processes, goodness‐of‐fit metrics, uncertainties of parameters, and sensitivity analysis. The learning experience's efficacy was assessed by conducting two surveys comparing the participants' knowledge before and after the exercise. The results revealed that 92.3% of the students considered that their hydrological skills had improved significantly following the exercise. Furthermore, the acquisition of hydrological modeling concepts was satisfactorily appreciated by all the participants, 97.6% of whom considered it useful or highly useful. Using a spreadsheet as a complementary tool in hydrology teaching increases student participation and motivation provided it is a contemporary and appealing issue, and the teacher clearly defines, monitors, and follows up on the class objectives.
A novel prognostic model for papillary thyroid cancer based on epithelial–mesenchymal transition‐related genes
Authors: Liu Rui , Cao Zhen , Pan Meng , Wu Mengwei , Li Xiaobin , Yuan Hongwei , Liu Ziwen 
Published: May 2022

AbstractBackgroundThe frequent incidence of postsurgical recurrence issues in papillary thyroid cancer (PTC) patients is a primary concern considering the low cancer‐related mortality. Previous studies have demonstrated that epithelial–mesenchymal transition (EMT) activation is closely related to PTC progression and invasion. In this study, we aimed to develop a novel EMT signature and ancillary nomogram to improve personalized prediction of progression‐free interval (PFI).MethodsFirst, we carried out a differential analysis of PTC samples and pairwise normal thyroid samples to explore the differentially expressed genes (DEGs). The intersection of the DEGs with EMT‐related genes (ERGs) were identified as differentially expressed EMT‐related genes (DE‐ERGs). We determined PFI‐related DE‐ERGs by Cox regression analysis and then established a novel gene classifier by LASSO regression analysis. We validated the signature in external datasets and in multiple cell lines. Further, we used uni‐ and multivariate analyses to identify independent prognostic characters.ResultsWe identified 244 prognosis‐related DE‐ERGs. The 244 DE‐ERGs were associated with several pivotal oncogenic processes. We also constructed a novel 10‐gene signature and relevant prognostic model for recurrence prediction of PTC. The 10‐gene signature had a C‐index of 0.723 and the relevant nomogram had a C‐index of 0.776. The efficacy of the signature and nomogram was satisfying and closely correlated with relevant clinical parameters. Furthermore, the signature also had a unique potential in differentiating anaplastic thyroid cancer (ATC) samples.ConclusionsThe novel EMT signature and nomogram are useful and convenient for personalized management for thyroid cancer.
Chemical Profile, Antioxidant and Enzyme Inhibition Activities of Natural Saudi Sidr and Talh Honeys
Authors: Al Qahtani Hayfa W. S. , Yagi Sakina , Yılmaz Mustafa Abdullah , Cakır Oguz , Tarhan Abbas , Mustafa Ahmed Ali , Zengin Gokhan 
Published: May 2022

AbstractHoney is used since ancient time as a food and to cure many diseases. The present study investigated the chemical constituents, antioxidant and enzyme inhibition activities of natural Saudi Sidr (SH) and Talh (TH) honeys. Beside entire honey samples, ethyl acetate, ethanol and water extracts were prepared. The total polyphenolic content of SH, TH and their extracts was in the range of 2.86–7.21 and 3.80–17.33 mg gallic acid equivalents/g, respectively and the total flavonoids content was in the range of 0.05–1.17 and 0.18–2.38 mg rutin equivalents/g, respectively. Out of the 53 standards analyzed by HPLC, 27 compounds were detected with highest number of compounds identified in the ethyl acetate extract of TH (45 %, 24/53) and SH (26 %, 14/53), respectively. Quinic acid was dominant compound identified in all honey samples with the highest content determined in TH ethanol extract (4454 μg/g). The majority of tested samples possessed considerable anti‐radicals and reducing ions capacity with the ethyl acetate extract from TH exerted significantly (p<0.05) the highest activity. All honey samples did not show chelating iron metal property. Honey samples revealed variable enzyme inhibition activity with TH (entire and/or ethyl acetate extract) showed significantly (p<0.05) the highest acetylcholinesterase, butyrylcholinesterase, tyrosinase and α‐amylase inhibition activity. In conclusion, ethyl acetate is the best solvent for extraction of bioactive molecules from the two honey types. Moreover, the dark‐colored TH contained the highest number of molecules and consequently exerted the best antioxidant and enzyme inhibition activities in most assays.
Neurosurgery in a patient with severe hemophilia B: an experience using eftrenonacog alfa as perioperative management
Authors: Benitez Hidalgo Olga , Martinez Garcia M. Fernanda , Bescos Cabestre Agustin , Juarez Gimenez Juan Carlos , Gironella Mesa Mercedes , Bosch Albareda Francesc 
Published: May 2022

AbstractExtended half‐life FIX (EHL‐FIX) concentrates have been developed with the purpose of reducing the frequency of infusions in patients with severe or moderate hemophilia B. We describe the case of a 63‐year‐old patient with severe hemophilia B (sHB) treated with FIX‐Fc fusion protein (rFIXFc) who underwent neurosurgery.
Visible‐Light Augmented Lithium Storage Capacity in a Ruthenium(II) Photosensitizer Conjugated with a Dione‐Catechol Redox Couple
Authors: Gupta Deepak , Lakraychi Alae E. , Boruah Buddha D. , De Kreijger Simon , Troian‐Gautier Ludovic , Elias Benjamin , De Volder Michael , Vlad Alexandru 
Published: May 2022

AbstractControlling redox activity of judiciously appended redox units on a photo‐sensitive molecular core is an effective strategy for visible light energy harvesting and storage. The first example of a photosensitizer ‐ electron donor coordination compound in which the photoinduced electron transfer step is used for light to electrical energy conversion and storage is reported. A photo‐responsive Ru‐diimine module conjugated with redox‐active catechol groups in [Ru(II)(phenanthroline‐5,6‐diolate)3]4− photosensitizer can mediate photoinduced catechol to dione oxidation in the presence of a sacrificial electron acceptor or at the surface of an electrode. Under potentiostatic condition, visible light triggered current density enhancement confirmed the light harvesting ability of this photosensitizer. Upon implementation in galvanostatic charge‐discharge of a Li battery configuration, the storage capacity was found to be increased by 100 %, under 470 nm illumination with output power of 4.0 mW/cm−2. This proof‐of‐concept molecular system marks an important milestone towards a new generation of molecular photo‐rechargeable materials.
Virtual forums for public accountability: How internet and communication technologies are influencing citizen interactions with a local government
Authors: Bahramirad Sina 
Published: May 2022

AbstractPublic accountability forums can be useful mechanisms for ensuring that governments are responsive to the perspectives, preferences, and needs of citizens. This study explores how ICTs are affecting public accountability forums and how citizens interact with elected and appointed government officials. A case study of a municipal government in Ontario, Canada, describes how a virtual public accountability forum emerged and functioned based on social media data and interviews with public officials. The case demonstrates that social media can facilitate new channels of interaction between citizens and public officials. Key features of these virtual forums include anonymous participation, variable duration, and dynamic audience size. The case also demonstrates that the demand for information provision within accountability relationships is not just a singular type of ex‐post exchange. There is a new channel of information exchange that is continuous and malleable because it can evolve and change instantaneously over ICTs.
Neutral Five‐Coordinate Arylated Copper(III) Complex: Key Intermediate in Copper‐Mediated Arene Trifluoromethylation
Authors: Wang Guangyu , Li Man , Leng Xuebing , Xue Xiaosong , Shen Qilong 
Published: May 2022

Comprehensive SummaryFive‐coordinate neutral Cu(III) complexes have long been considered as the key intermediates in copper‐mediated/catalyzed arene trifluoromethylative reactions, but the identity of these complexes remains elusive. Herein, we reported, for the first time, the preparation and characterization of these putative complexes [(bpy)Cu(CF3)2(C6F4R)] and investigation of their C(sp2)‐CF3 bond‐forming reductive elimination. Our mechanistic studies including kinetic studies, the effect of temperature and solvents, the effect of the para‐substitution of the ligand as well as DFT calculations suggest that C(sp2)‐CF3 reductive elimination process proceeds via synchronous bond‐breaking/bond‐forming process.
Dynamic treatment regimes with interference
Authors: Jiang Cong , Wallace Michael P. , Thompson Mary E. 
Published: May 2022

AbstractPrecision medicine describes health care where patient‐level data are used to inform treatment decisions. Within this framework, dynamic treatment regimes (DTRs) are sequences of decision rules that take individual patient information as input data and then output treatment recommendations. DTR estimation from observational data typically relies on the assumption of no interference: i.e., the outcome of one individual is unaffected by the treatment assignment of others. However, in many social network contexts, such as friendship or family networks, and for many health concerns, such as infectious diseases, this assumption is questionable. We investigate the DTR estimation method of dynamic weighted ordinary least squares (dWOLS), which boasts of easy implementation and the so‐called double‐robustness property, but relies on the assumption of no interference. We define a network propensity function and build on it to establish an implementation of dWOLS that remains doubly robust under interference associated with network links. The method's properties are demonstrated via simulation and applied to data from the Population Assessment of Tobacco and Health (PATH) study to investigate cigarette dependence within two‐person household networks.
Breaking the Linear Relation in the Dissociation of Nitrogen on Iron Surfaces
Authors: Liu Dexin , Zhao Wei , Yuan Qinghong 
Published: May 2022

AbstractCurrent industrial ammonia synthesis depends on the Haber‐Bosch process, in which the activity of the catalyst is limited by the Brønsted‐Evans‐Polanyi (BEP) principle and Fe is used as a commercial catalyst. Herein, we found that the dissociation barriers of N2 on Fe(111), Fe(211), Fe(110), and Fe(100) surfaces do not follow the widely accepted BEP principle. N2 dissociation on Fe(111) surface has the smallest adsorption energy and the lowest energetic barrier. Such an abnormal phenomenon can be attributed to charge transfer from Fe surfaces to the anti‐bonding orbital (π*) of the absorbed N2. More charges transferred from the Fe surface to π* of N2 leads to a weaker N≡N triple bond and a lower adsorption energy of N atoms. However, the hydrogenation of N atoms and desorption of NH3 on the four Fe surfaces follow the BEP principle. Therefore, Fe(111) is found to be the most active surface to promote ammonia synthesis, and such a conclusion is also applicable to Ni and Mo surfaces.
The buffering effect of continuous corporate social responsibilities engagement on negative consumer responses toward brand crises
Authors: Jung Sojin , Lee Stacy H. 
Published: May 2022

AbstractThis study aims to investigate how the extent of skepticism toward a firm's overall CSR practices spills over to consumers' evaluations of an actual incident, through examining recent crises involving Gucci and H&M. A total of 531 responses obtained through an online survey method were analyzed, and the results revealed that a low level of consumer skepticism toward a firm's corporate social responsibilities (CSR) practices increased trust, which in turn encouraged resilience (forgiveness) intentions for the firm's misconduct. Moreover, the resilience intention mitigated the extent to which consumers attributed the incident to the firm, perceived the severity of the incident, and perceptions of the firm's self‐interest motives. The findings suggest that a firm's continuous and consistent CSR engagement can play a buffering role in alleviating negative consequences when brand crises occur. Therefore, the findings of this study will inform risk management by highlighting the protective effect of a firm's continuous CSR efforts.
LPTM: Lightweight and privacy‐preserving traffic monitoring scheme
Authors: Jiang Sheng , Cheng Hongyuan , Liu Yining 
Published: May 2022

SummaryIn the traffic monitoring system, the transportation department generates the traffic map to report the real‐time traffic conditions, so as to provide more efficient service for drivers. However, if the vehicle obtains the local traffic conditions that the driver is more concerned about from the remote server, it will consume a heavy bandwidth and incurs an increased response delay. Generating and broadcasting local traffic conditions through fog computation is a feasible method to reduce communication costs, and most existing traffic monitoring systems based on fog computation are implemented using Bilinear Pairing operations. In this paper, we propose Lightweight and Privacy‐preserving Traffic Monitoring (LPTM) scheme with Elliptic Curve Cryptosystem, an optimized Timed Efficient Stream Loss‐tolerant Authentication protocol is adopted to achieve efficient and secure communication, and we also use an identity‐based signature scheme with partial message recovery to effectively shorten the length of the fog node broadcast message. Detailed security proofs show that the requirements of security and privacy are all achieved, and better simulation performance is presented in both computation and communication overhead.