bluuebunny/crossref_metadata_2025 huggingface dataset:
The Bike-courier as an Energy Efficiency Instrument at the University of Guadalajara (Pilot Study)
Authors: Ramírez-Sánchez Hermes Ulises , Hernández-Salazar José Antonio
Published: May 2022

Introducción: The struggle and concern for climate change, the optimization of natural resources, the well-being of future generations, has permeated the public institutions of our country. In particular, the University of Guadalajara, a public body for higher education, has launched projects aimed at this direction. The year 2020 at the University of Guadalajara was declared as the "Year of the Energy Transition at the University of Guadalajara”. Likewise, the Program of Austerity, Rationality and Efficiency of Institutional Resources of the University of Guadalajara was launched, implemented and applicable to the entire University Network and of a mandatory nature, to rationalize institutional spending by establishing: A decrease in energy resources through rational, responsible and sustainable use, proposing "to reduce spending on fossil fuels and lubricants by 40%, optimizing its consumption" together with a gradual transition of the vehicle fleet, "The conversion of the vehicle fleet to the electric and hybrid type will be strengthened".

Materials and Methods: Considering the above and associated with the opportunity to take as a pilot test the Transport Office of the Rectory General, it was established to replace by bike-courier the delivery of documents and light parcels in dependencies with distances less than 5 km of radius of the administrative building of the University of Guadalajara that is currently carried out using a car, seeking energy reduction, without losing efficiency in deliveries and contributing to meet the institutional goals of resource optimization and environmental contribution. The messaging and departure requests of the agency's operational vehicles were tracked during the year 2019.

Results and Discussion: Accounting for the annual record, only the requested trips with distances less than 5 km are those considered to be made by bicycle because they are requests for delivery of documentation, being 40.88% of these those susceptible to be delivered by bicycle, representing 2,237.54 kilometers and 187.05 liters of fuel saved, contributing to the fulfillment of the institutional goal of reducing fossil fuels by 40%. It was also evidenced that the efficiency of the bike-courier, in most cases is higher than the automotive, under the criteria and variables analyzed, using the Data Enveloping Analysis (DEA).
Evolution of neurologic symptoms in non‐hospitalized COVID‐19 “long haulers”
Authors: Ali Sareen T. , Kang Anthony K. , Patel Tulsi R. , Clark Jeffrey R. , Perez‐Giraldo Gina S. , Orban Zachary S. , Lim Patrick H. , Jimenez Millenia , Graham Edith L. , Batra Ayush , Liotta Eric M. , Koralnik Igor J.
Published: May 2022

Objective

We characterized the evolution of neurologic symptoms and self‐perceived recovery of non‐hospitalized COVID‐19 “long haulers” 6–9 months after their initial Neuro‐COVID‐19 clinic evaluation.

Methods

In this follow‐up study on the first 100 patients, 50 SARS‐CoV‐2 laboratory‐positive (SARS‐CoV‐2+), and 50 laboratory‐negative (SARS‐CoV‐2−), evaluated at our Neuro‐COVID‐19 clinic between May and November 2020, patients completed phone questionnaires on their neurologic symptoms, subjective impression of recovery and quality of life.

Results

Of 52 patients who completed the study (27 SARS‐CoV‐2+, 25 SARS‐CoV‐2−) a median 14.8 (range 11–18) months after symptom onset, mean age was 42.8 years, 73% were female, and 77% were vaccinated for SARS‐CoV‐2. Overall, there was no significant change in the frequency of most neurologic symptoms between first and follow‐up evaluations, including “brain fog” (81 vs. 71%), numbness/tingling (69 vs. 65%), headache (67 vs. 54%), dizziness (50 vs. 54%), blurred vision (34 vs. 44%), tinnitus (33 vs. 42%), and fatigue (87 vs. 81%). However, dysgeusia and anosmia decreased overall (63 vs. 27%, 58 vs. 21%, both p < 0.001). Conversely, heart rate and blood pressure variation (35 vs. 56%, p = 0.01) and gastrointestinal symptoms (27 vs. 48%, p = 0.04) increased at follow‐up. Patients reported improvements in their recovery, cognitive function, and fatigue, but quality of life measures remained lower than the US normative population (p < 0.001). SARS‐CoV‐2 vaccination did not have a positive or detrimental impact on cognitive function or fatigue.

Interpretation

Non‐hospitalized COVID‐19 “long haulers” continue to experience neurologic symptoms, fatigue, and compromised quality of life 14.8 months after initial infection.
A learning framework of modified deep recurrent neural network for classification and recognition of voice mood
Authors: Agarwal Gaurav , Om Hari , Gupta Sachi
Published: May 2022

Recognition of human emotions is a basic requirement in many real‐time applications. Detection of exact emotions through voice provides relevant information for various purposes. Several computational methods have been employed for the clear analysis of human emotions. Most of the previous approaches face complexities due to certain drawbacks like degraded signal quality, a requirement of high storage space, increased computational complexity, and deteriorated outcomes of classification accuracy. The proposed work was implemented to gather the accurate classification result of embedded emotions and minimize the computational complexities of MDDTRNN (modified deep duck and traveler recurrent neural network). The proposed work includes four steps: preprocessing, feature extraction, feature selection, and classification. In feature extraction, the spectral and frequency features are extracted using the adopting boosted MFCC (Mel frequency cepstral coefficients) method to improve training speed. In feature selection, the best features are selected using an algorithm of AAVOA (adaptive African vulture optimization algorithm). To provide optimal emotion results, the classification step is undertaken by the MDDTRNN technique. The proposed work shows better classification outcomes of emotions when compared to the existing approaches by holding the accuracy of (95.86%), precision as (93.79%), specificity as (94.28%), sensitivity as (92.89%) and the error rate is attained to be 5.266 in terms of IEMOCAP dataset. The accuracy result (96.27%), precision (94.83%), specificity (93.16%), sensitivity (94%) and the error rate is achieved to be 4.982 in terms of the EMODB dataset.
Churn in the older adult SNAP population
Authors: Heflin Colleen , Hodges Leslie , Arteaga Irma , Ojinnaka Chinedum O.
Published: May 2022

Using administrative records from Missouri, we investigate the characteristics of Supplemental Nutrition Assistance Program (SNAP) participants aged 60 and older who experience administrative churn. Among these adults, one in four experienced administrative churn, and one in five experienced more than one spell of churn. Risk of churn, frequency, duration of churn spells, and the value of foregone SNAP benefits varied with individual, household, and geographic characteristics, and was more common among non‐Whites, members of larger households, and those living in urban areas. Our findings suggest that a significant portion of older adults experience gaps in SNAP benefit receipt.
Current clinical practice for familial adenomatous polyposis in Japan: A nationwide multicenter study
Authors: Matsubara Takaaki , Beppu Naohito , Ikeda Masataka , Ishida Hideyuki , Takeuchi Yoji , Nagasaki Toshiya , Takao Akinari , Sasaki Kazuhito , Akagi Kiwamu , Sudo Tomoya , Ueno Hideki , Yamaguchi Tatsuro , Tomita Naohiro , Ajioka Yoichi
Published: May 2022

Introduction

In Japanese patients with familial adenomatous polyposis (FAP), colectomy tends to be postponed or avoided.

Aim

This study aimed to clarify the current clinical practice from a Japanese multicenter cohort study database.

Methods

We analyzed the records of 250 patients with non‐dense FAP who did not require colorectal cancer removal. The clinical outcomes were compared between patients who received colectomy (n = 142) (Group A) and those who did not receive colectomy (n = 108) (Group B).

Results

The colectomy rate based on the age at the final follow‐up examination was 46%, 60%, 54%, 65%, at ≤29, 30–39, 40–49, and ≥ 50 years, respectively (P = .11). The development of colorectal cancer did not differ between Groups A and B (25% vs 22% P = .67); however, colorectal cancer was diagnosed at the Tis stage in 88% of the patients with colorectal cancer in Group B, and 34% of the patients with colorectal cancer in Group A (P < .01). Regarding survival, all patients in Group B were alive at the final follow‐up examination. In contrast, six patients in Group A died, including three patients with desmoid tumors and one with colon cancer.

Conclusion

Over one‐third of patients with non‐dense FAP (polyps ≤ 1000) in Japan did not receive colectomy at >30 years of age, and patients who managed without colectomy showed acceptable survival with the early diagnosis of colorectal cancer, and a very low incidence of desmoid tumor development, indicating that this approach represents a potential option for the management of selected non‐dense FAP patients.
Holding on or falling off: The attachment mechanism of epiphytic Anthurium obtusum changes with substrate roughness
Authors: Tay Jessica Y. L. , Kovalev Alexander , Zotz Gerhard , Einzmann Helena J. R. , Gorb Stanislav N.
Published: May 2022

Premise

For vascular epiphytes, secure attachment to their hosts is vital for survival. Yet studies detailing the adhesion mechanism of epiphytes to their substrate are scarce. Examination of the root hair–substrate interface is essential to understand the attachment mechanism of epiphytes to their substrate. This study also investigated how substrate microroughness relates to the root–substrate attachment strength and the underlying mechanism(s).

Methods

Seeds of Anthurium obtusum were germinated, and seedlings were transferred onto substrates made of epoxy resin with different defined roughness. After 2 months of growth, roots that adhered to the resin tiles were subjected to anchorage tests, and root hair morphology at different roughness levels was analyzed using light and cryo scanning electron microscopy.

Results

The highest maximum peeling force was recorded on the smooth surface (glass replica, 0 µm). Maximum peeling force was significantly higher on fine roughness (0, 0.3, 12 µm) than on coarse (162 µm). Root hair morphology varied according to the roughness of the substrate. On smoother surfaces, root hairs were flattened to achieve large surface contact with the substrate. Attachment was mainly by adhesion with the presence of a glue‐like substance. On coarser surfaces, root hairs were tubular and conformed to spaces between the asperities on the surface. Attachment was mainly via mechanical interlocking of root hairs and substrate.

Conclusions

This study demonstrates for the first time that the attachment mechanism of epiphytes varies depending on substrate microtopography, which is important for understanding epiphyte attachment on natural substrates varying in roughness.
A Photoswitchable Ligand Targeting the β1‐Adrenoceptor Enables Light‐Control of the Cardiac Rhythm**
Authors: Duran‐Corbera Anna , Faria Melissa , Ma Yuanyuan , Prats Eva , Dias André , Catena Juanlo , Martinez Karen L. , Raldua Demetrio , Llebaria Amadeu , Rovira Xavier
Published: May 2022

Catecholamine‐triggered β‐adrenoceptor (β‐AR) signaling is essential for the correct functioning of the heart. Although both β1‐ and β2‐AR subtypes are expressed in cardiomyocytes, drugs selectively targeting β1‐AR have proven this receptor as the main target for the therapeutic effects of beta blockers in the heart. Here, we report a new strategy for the light‐control of β1‐AR activation by means of photoswitchable drugs with a high level of β1‐/β2‐AR selectivity. All reported molecules allow for an efficient real‐time optical control of receptor function in vitro. Moreover, using confocal microscopy we demonstrate that the binding of our best hit, pAzo‐2, can be reversibly photocontrolled. Strikingly, pAzo‐2 also enables a dynamic cardiac rhythm management on living zebrafish larvae using light, thus highlighting the therapeutic and research potential of the developed photoswitches. Overall, this work provides the first proof of precise control of the therapeutic target β1‐AR in native environments using light.
Ligand‐Controlled NiH‐Catalyzed Regiodivergent Chain‐Walking Hydroalkylation of Alkenes
Authors: Zhao Lei , Zhu Yuqin , Liu Mengyuan , Xie Leipeng , Liang Jimin , Shi Haoran , Meng Xiao , Chen Zhengyang , Han Jian , Wang Chao
Published: May 2022

A NiH‐catalyzed migratory hydroalkylation of alkenyl amines with predictable and switchable regioselectivity is reported. By utilizing a ligand‐controlled, directing group‐assisted strategy, various alkyl units are site‐selectively installed at inertsp3C−H sites far away from the original C=C bonds. A range of structurally diverse α‐ and β‐branched protected amines are conveniently synthesized via stabilization of 5‐ and 6‐membered nickelacycles respectively. This method exhibits broad scope and high functional group tolerance, and can be applied to late‐stage modification of medicinally relevant molecules.
Total Synthesis of Complex Peptidyl Nucleoside Antibiotics: Asymmetric De Novo Syntheses of Miharamycin B and Its Biosynthetic Precursor
Authors: Huang Wenjun , Fan Shuai , Gao Jiahui , Luo Shangwen , Tang Shouchu , Liu Jian , Wang Xiaolei
Published: May 2022

Miharamycins belong to a class of peptidyl nucleoside antibiotics with a unique nine‐carbon pyranosyl amino acid core and a rare 2‐aminopurine moiety. Herein, we report the de novo total synthesis of miharamycin B and its biosynthetic precursor from 3‐bromofuran and Garner's aldehyde through a modified Achmatowicz reaction. Many challenges were resolved toward the de novo synthesis of miharamycin B, including the introduction of a dense array of functional groups, the stereoselective construction of consecutive stereocenters, dealing with the variability of the anomeric positions, and promoting site‐selectivity in the cyclization to form the tetrahydrofuran ring. This de novo synthesis strategy enables efficient preparation of 3′‐substituted saccharides, allowing the study of their structure–activity relationships and mode of action, and meets the growing demand for the development of novel antibiotics inspired by miharamycin natural products.
Cobalt‐Catalyzed Regio‐, Diastereo‐ and Enantioselective Intermolecular Hydrosilylation of 1,3‐Dienes with Prochiral Silanes
Authors: Wang Lei , Lu Wenxin , Zhang Jiwu , Chong Qinglei , Meng Fanke
Published: May 2022

One of the most straightforward approaches to access chiral silanes is catalytic enantioselective hydrosilylation. Although significant advances have been achieved in enantioselective construction of either a carbon‐stereogenic center or a silicon‐stereogenic center through enantioselective hydrosilylation, simultaneous establishment of a carbon‐ and a silicon‐stereogenic center in an acyclic molecule through a single intermolecular hydrosilylation remained undeveloped. Herein, an unprecedented cobalt‐catalyzed regio‐, diastereo‐ and enantioselective hydrosilylation of 1,3‐dienes is presented, enabling construction of a carbon‐ and a silicon‐stereogenic center in a single intermolecular transformation. A wide range of chiral silanes bearing a carbon‐ and a silicon‐stereogenic center were generated in high efficiency and stereoselectivity. Functionalization of the enantioenriched silanes delivered a variety of valuable chiral building blocks that are otherwise difficult to access.
Dissecting Solvent Effects on Hydrogen Bonding
Authors: Meredith Nicole Y. , Borsley Stefan , Smolyar Ivan V. , Nichol Gary S. , Baker Christopher M. , Ling Kenneth B. , Cockroft Scott L.
Published: May 2022

The experimental isolation of H‐bond energetics from the typically dominant influence of the solvent remains challenging. Here we use synthetic molecular balances to quantify amine/amide H‐bonds in competitive solvents. Over 200 conformational free energy differences were determined using 24 H‐bonding balances in 9 solvents spanning a wide polarity range. The correlations between experimental interaction energies and gas‐phase computed energies exhibited wild solvent‐dependent variation. However, excellent correlations were found between the same computed energies and the experimental data following empirical dissection of solvent effects using Hunter's α/β solvation model. In addition to facilitating the direct comparison of experimental and computational data, changes in the fitted donor and acceptor constants reveal the energetics of secondary local interactions such as competing H‐bonds.
Rhodium(II)‐Catalyzed C(sp3)−H Diamination of Arylcyclobutanes
Authors: Liu Xinyu , Wang Zhifan , Wang Qiwei , Wang Yuanhua
Published: May 2022

Activated by multiple consecutive oxidative radical‐polar crossover and desaturation processes, the selective diamination of arylcyclobutanes, which is difficult to perform by classical metallonitrene C−H insertion, was achieved in a short time by rhodium(II) catalysis using N‐fluorobenzenesulfonimide (NFSI) as the oxidant and nitrogen source.
Cobalt‐Catalyzed Asymmetric Sequential Hydroboration/Isomerization/Hydroboration of 2‐Aryl Vinylcyclopropanes
Authors: Chen Chenhui , Wang Hongliang , Li Tongtong , Lu Dongpo , Li Jiajing , Zhang Xie , Hong Xin , Lu Zhan
Published: May 2022

A cobalt‐catalyzed asymmetric sequential hydroboration/isomerization/hydroboration of 2‐aryl vinylcyclopropanes was for the first time reported for the preparation of valuable chiral 1,5‐bis(boronates) in good yields with excellent enantioselectivity via asymmetric sequential isomerization/hydroboration of a trisubstituted alkene intermediate. The reaction was carried out smoothly and this protocol was used for asymmetric syntheses of (−)‐preclamol in gram‐scale. The two primary C(sp3)−B bonds in chiral 1,5‐bis(boronates) could be distinguished in iterative Suzuki–Miyaura cross‐coupling reaction, delivering chiral 1,2,5‐triaryl alkanes with excellent enantioselectivity. Based on experimental and computational studies, a cobalt‐hydride species was proposed as the active intermediate in hydroboration, isomerization, and second hydroboration reactions.
Electrochemical Migratory Cyclization of N‐Acylsulfonamides
Authors: Shi Zhaojiang , Li Yuanyuan , Li Nan , Wang Wei‐Zhen , Lu Hao‐Kuan , Yan Hong , Yuan Yaofeng , Zhu Jun , Ye Ke‐Yin
Published: May 2022

Benzoxathiazine dioxide, as a bioisostere of the clinically widely used diazoxide, exhibits interesting biological activity. However, limited success has been achieved in terms of its concise and direct synthesis. We report herein a facile electrochemical migratory cyclization of N‐acylsulfonamides to access a diverse array of benzoxathiazine dioxides. The inclusion of electrochemistry is crucial for realizing such a novel transformation, which is substantiated both by the experiments and density‐functional‐theory calculations.
Dynamics of rotation in two‐coordinate thiazolyl copper(I) carbazolyl complexes
Authors: Ma Jie , Kapper Savannah C. , Ponnekanti Aamani , Schaab Jonas , Djurovich Peter I. , Thompson Mark E.
Published: May 2022

Two‐coordinate carbene Cu(Ι) amide complexes with sterically bulky groups such as the diisopropyl phenyl (dipp) on the carbenes have been shown to have comparable performance to the phosphorescent emitters bearing heavy atoms such as iridium and platinum. These bulky groups enforce a coplanar molecular structure and suppress the nonradiative decay rates. Here, three different two‐coordinate Cu(Ι) complexes were investigated that bear a common thiazole carbene, 3‐(2,6‐diisopropylphenyl)‐4,5‐dimethylthiazol‐2‐ylidene, with only a single dipp group, and carbazolyl ligands with substituents of varying steric bulk ortho to N. These substituents have a negligible impact on luminescence energies of the complexes but serve to modulate the rotation barriers along the metal–ligand coordinate bond. The geometric arrangement of ligands (syn‐ or anti‐conformer) in complexes with alkyl substituents were found to differ, being syn in the solid state versus anti in solution as revealed by crystallographic analysis and nuclear magnetic resonance spectroscopy. In addition, calculations were performed to determine potential energy surfaces for different conformations of the three complexes to provide a theoretical evaluation of rotation barriers around the metal–ligand bond axis. The relationship between rotation barriers and photophysical properties demonstrate that rates for nonradiative decay decrease with increasing bulk of the substituents on the carbazolyl ligand.
A new ternary Eu(III) β‐diketonate complex with diimine ligand and its application as fluorescent probe for highly sensitive and selective ammonia sensor
Authors: Wang You‐Yu , Song Li , Wang Jian‐Teng , Zhou Yi‐Ming , Dai Ze‐Qi , Liu Wei , Guo Jia‐Yu , Shen Hang‐Yan , Chai Wen‐Xiang
Published: May 2022

The rapid and accurate detection of ammonia is very important for manufacture and environmental monitoring, which needs to be developed urgently. Herein, a thin film‐based fluorescence sensor is fabricated by using a ternary europium (III) complex probe for ammonia. The new complex Eu(TPM)3(2‐PBO) (1) was designed and synthesized by utilizing a trifluoromethyl substituted β‐diketone ligand TPM and a diimine ligand 2‐PBO (TPM = 1,1,1‐trifluoro‐5,5‐dimethyl‐2,4‐hexanedione, 2‐PBO = 2‐(2′‐pyridyl)‐benzoxazole). This complex probe was synthetically characterized by elemental analysis, crystallographic and spectroscopic analysis, and photoluminescence (PL) study. The crystallographic analysis revealed complex 1 as a neutral complex structure with the Eu(III) center in a distorted square antiprism EuO6N2 coordination polyhedron. Based on this complex probe, a thin film fluorescence sensor with highly sensitive and selective response to ammonia was developed by polymethyl methacrylate (PMMA): complex composite and cellulose paper support. When the paper‐based sensor was exposed to ammonia, its PL emission showed a sensing behavior of rapid quenching. Surprisingly, this new method can achieve excellent limit of detection as low as 2.740 × 10−6 ppm.
Removal of carbon dioxide using zeolitic imidazolate frameworks: Adsorption and conversion via catalysis
Authors: Abdelhamid Hani Nasser
Published: May 2022

Carbon dioxide (CO2) is one of the culprit causes of global climatic changes. Furthermore, the efficient separation of CO2 from other gaseous mixtures using zeolitic imidazolate framework (ZIF)‐based materials is vital for several processes such as flue gas separation, gas sweetening, and natural gas processing. ZIF‐based materials are emerging adsorbents and catalysts for CO2 gas removal via adsorption and conversion into valuable chemicals. ZIF‐based adsorbents with high‐adsorption/conversion efficiencies and tunable properties can be achieved by judicious synthesis and fabrication methods. We reviewed ZIF‐based materials for CO2 removal via adsorption and catalysis (e.g., cycloaddition, carboxylation, hydrogenation, N‐formylation, electrocatalysis, and photocatalysis). In addition, recent development methods such as membrane technologies and ways to improve the gas separation performance of ZIF membranes were highlighted. The prospective point of view to promote industrial applications and commercialization of ZIF‐based materials was briefly discussed. Once challenges such as low performance and reproducibility for ZIF‐based materials are solved, scalability and cost‐effectiveness should not become issues.
Preparation and characterization of polyethylene glycol‐based form‐stable phase change materials supported by poly (vinyl formal) foams
Authors: Chen Kexuan , Liu Yuan , He Ren , Wang Qi
Published: May 2022

Phase change materials (PCMs) are a kind of materials that provide latent heat at a constant temperature. They have great potential in thermoregulation scopes and thermal energy storage. However, liquid leakage during phase transition restricts their applications in practice severely. In this work, a novel strategy is proposed to prepare form‐stable phase change materials with polyvinyl formal (PVF) foam shape‐stabilized poly (ethylene glycol)‐based material. The PEG exhibits good interfacial compatibility with the PVF framework and the phase transition enthalpy ranges from 104.1 to 158.4 J/g. The PEG/PVF‐C2 increases the residue amount from 0.1% to 4.2% and enhances the thermal degradation temperature at the same time. The mass retention rates of PEG/PVF composites depend on their pore structure, which are 75.4%, 89.5%, and 95.3%, respectively. This study may open a new door for the development of advanced PCMs with good leakage prevention and flame retardancy, thus further contributing to extending the application scopes.
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

Inspired 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

The 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

Radioactive 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

Iron‐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

In 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

Public 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

Hydrology 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

Background

The 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).

Methods

First, 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.

Results

We 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.

Conclusions

The 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

Honey 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

Extended 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

Controlling 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

Public 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 Summary

Five‐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

Precision 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

Current 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

This 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.