bluuebunny/crossref_metadata_2025 huggingface dataset:
Evaluation of Different Genotypes and Genetic Virulence in Staphylococcus aureus Isolates from Clinical Samples
Authors: Ajayi D. O. , Onasanya A. A. , Daramola G. O.
Published: January 2022

Infection with Staphylococcus aureus has been considered a major problem in hospitals. The clinical importance of S. aureus isattributed to notable virulence factors and genetic diversity. The objective of this study therefore was to investigate the distribution of S, aureus virulence gene anddifferent genotypesin some isolates obtained from clinical samples from Ekiti State University Teaching Hospital, Ado Ekiti. A total of 25 isolates were screened for the presence of 16SrRNA,GeIE and asaIvirulence genes using Polymerase Chain Reaction (PCR).Virulence genes 16SrRNA, gelE, asaI) formed clusters in S. aureus isolates used in this study. 16SrRNA was absence in 5 of the isolates and only present in 21 of the isolates. GeIE virulence gene was absence in 2 of the isolates and present in 23 of the isolates. AsaI virulence gene was absence in 7 of the isolates and present in 18 of the isolates. Virulence diversity was observed among isolates. Which could be used as a guide to the pathogenicity of individual isolates and hence control spread of infection.The genetic typing was carried out by Random Amplified Polymorphic DNA (RAPD-PCR) using OPBO8, OPHO4, OPH03, OPBO5, and OPT12 Primers. Also there exist different genotypes among the S. aureus isolates used in this study revealing high level of genetic diversity occurrence among S. aureus isolates. The DNA fingerprint revealed high genetic diversity among isolates irrespective of their sources. Further work could be done considering the antibiotic resistant gene and also sequencing of virulence gene clusters peculiar to S. aureus pathogens.
Maturity Classifications Influence the Phenological Intervals of Different Maize Varieties
Authors: Ilesanmi R. Y. , Abayomi Omolara , Awosanmi F. E. , Ajayi Sola
Published: January 2022

This field trial compared the growth stages of early, intermediate and late varieties of maize and evaluated the effect of maturity group on their phenological intervals. Fifteen maize varieties belonging to three different maturity groups were evaluated in a randomized complete block design with four replicates. Data were collected on the days to leaf expansion from the early seedling stages to flowering. The results showed that maturity group effect was significant for all phenological intervals starting from the third leaf stage. Maturity group had the highest influence on the phenological intervals of the varieties during the period of seedling establishment at the fifth leaf stage. The contribution of maturity group to the total observed variability increased from seedling establishment to the late vegetative stages and peaked at the flowering stages. Varietal differences have a minimal contribution in ranking maturity in maize. In summary, maturity differences in maize varieties are initiated early, but their time-course effects on phenological intervals are more pronounced in the late vegetative and flowering stages.
Effects of Temperature, Pressure and Physico-Chemical Characteristics on the Atomization and Disintegration of Jatropha Oil and its Formulations
Authors: Téré Dabilgou , Augustin Zongo S. , Boubou Bagre , Guy Christian Tubreoumya , Sayouba Sandwidi , Kayaba Haro , Tizane Daho , Jean Koulidiati , Oumar Sanogo , Belkacem Zeghmati , Antoine Bere
Published: January 2022

The physicochemical characteristics of vegetable oils, the atomization and the particle size of the spray are fundamental aspects for the simulation of their combustion on burners.

In this study, the influence of temperature and pressure on the disintegration of the jet of jatropha oil and its mixture with gas oil was simulated on a Riello Gulliver burner with power ranging from 22.5 to 35.6 KW. The disintegration and dispersion conditions of the droplets from the burner were determined using the average Sauter diameter by equations and mathematical functions. The results showed that there is a minimum temperature and pressure (130°C and 14 bar, respectively) from which it is possible to obtain an adequate disintegration of jatropha oil and its mixtures with diesel with suitable selected type of burner. These simulation results are consistent with results obtained experimentally and show satisfactory disintegration conditions at low pressure.
Antioxidant and Antimicrobial Activities of Thymus vulgaris L. Essential Oil Growing Wild in Tunisia
Authors: Hajlaoui Hafedh , Arraouadi Soumaya , Mighri Hedi , Aouadi Kaïss , Snoussi Mejdi , Noumi Emira , Kadri Adel
Published: January 2022

The aim of this work is to investigate the chemical composition, antioxidant, and antimicrobial activities of Tunisian Thymus vulgaris essential oil (TVEO). DPPH, superoxide anion, reducing power, chelating effect on ferrous ions and β-Carotene assays have been employed to determine the antioxidant potential of TVEO. In contrast, 24 reference bacterial strains and 16 fungal strains have been used for the assessment of the antimicrobial activity. Results revealed that TVEO has as carvacrol (67.33%) chemotype, it was equipped with an important antioxidant capacity that is better (P<0.05) than synthetic antioxidants (BHT, BHA, Vitamin C and EDTA) except for superoxide anion test. A higher antimicrobial activity was also observed with IZ, MIC and MBC values of bacterial strains were ranged from 10.33±0.57 to 37.33±0.57mm; 0.019 to 0.078 mg/mL and 0.039 to 0.31 mg/mL respectively. But those of fungal strains were varied between 24.66±1-47.33±1.53 mm; 0.004-0.078 mg/mL and 0.019-0.15 mg/mL respectively. In summary, the obtained data makes TVEO as a good and suitable candidate for its use in food and pharmaceutical purposes.
Analyzing Genetic Causes of Dyslexia to Provide Implications for Early Identification
Authors: Almahrag Khalid Mohammed
Published: January 2022

Dyslexia is a severe learning disorder that has always attracted various researchers who have debated on the causes and consequences of this particular disability from different angles. Numerous scientific works and articles have been written on this issue. Even though modern technologies provide scientists and researchers with specific tools that allow them to perform accurate analyses, the subject of Dyslexia still relies on hypotheses and assumptions rather than actual scientific evidence. That can explain the fact why the received findings are somewhat contradictory. Thus, a detailed analysis is needed to evaluate the results of the conducted research. The results of the studies should provide information as to better treatment of this disorder. This paper aims two-fold, to analyze genetic causes of Dyslexia, apply specific research evidence, and provide implications for early identification.
Controllable Generation of Antiferromagnetic Skyrmions in Synthetic Antiferromagnets with Thermal Effect
Authors: Chen Ruyi , Cui Qirui , Han Lei , Xue Xiaotian , Liang Jinghua , Bai Hua , Zhou Yongjian , Pan Feng , Yang Hongxin , Song Cheng
Published: January 2022

Magnetic skyrmions have gained unprecedented attention for their potential applications in spintronic devices, such as non‐volatile memory, energy‐efficient, and non‐von Neumann devices. In particular, skyrmions in synthetic antiferromagnets (SAF) are believed to overcome the fundamental limitations of the widely studied ferromagnetic skyrmions in terms of size and effective current‐induced manipulation. Recently, several methods have been proposed to stabilize SAF skyrmions, however, the controllable creation and manipulation of skyrmions in SAF remains a challenge. Here, the generation, manipulation, and current‐driven dynamics of SAF skyrmions are studied by a thermal induced integrated device. The thermal created SAF skyrmion provides a prerequisite for the subsequent current‐driven dynamics research where apparent inhibition of skyrmion Hall effect is observed due to the effectively compensated topological charge. In addition, by tuning the heating current, the density of skyrmions in SAF can be effectively manipulated, which is a key factor for utilizing SAF skyrmions toward practical spintronic devices.
The complex Y‐chromosomal history of gorillas
Authors: Städele Veronika , Arandjelovic Mimi , Nixon Stuart , Bergl Richard A. , Bradley Brenda J. , Breuer Thomas , Cameron Kenneth N. , Guschanski Katerina , Head Josephine , Kyungu Jean C. , Masi Shelly , Morgan David B. , Reed Patricia , Robbins Martha M. , Sanz Crickette , Smith Vincent , Stokes Emma J. , Thalmann Olaf , Todd Angelique , Vigilant Linda
Published: January 2022

Studies of the evolutionary relationships among gorilla populations using autosomal and mitochondrial sequences suggest that male‐mediated gene flow may have been important in the past, but data on the Y‐chromosomal relationships among the gorilla subspecies are limited. Here, we genotyped blood and noninvasively collected fecal samples from 12 captives and 257 wild male gorillas of known origin representing all four subspecies (Gorilla gorilla gorilla, G. g. diehli, G. beringei beringei, and G. b. graueri) at 10 Y‐linked microsatellite loci resulting in 102 unique Y‐haplotypes for 224 individuals. We found that western lowland gorilla (G. g. gorilla) haplotypes were consistently more diverse than any other subspecies for all measures of diversity and comprised several genetically distinct groups. However, these did not correspond to geographical proximity and some closely related haplotypes were found several hundred kilometers apart. Similarly, our broad sampling of eastern gorillas revealed that mountain (G. b. beringei) and Grauer's (G. b. graueri) gorilla Y‐chromosomal haplotypes did not form distinct clusters. These observations suggest structure in the ancestral population with subsequent mixing of differentiated haplotypes by male dispersal for western lowland gorillas, and postisolation migration or incomplete lineage sorting due to short divergence times for eastern gorillas.
Pharmacokinetic‐based failure of a detergent virucidal for severe acute respiratory syndrome–coronavirus‐2 (SARS‐CoV‐2) nasal infections: A preclinical study and randomized controlled trial
Authors: Esther Charles R. , Kimura Kyle S. , Mikami Yu , Edwards Caitlin E. , Das Suman R. , Freeman Michael H. , Strickland Britton A. , Brown Hunter M. , Wessinger Bronson C. , Gupta Veerain C. , Von Wahlde Kate , Sheng Quanhu , Huang Li Ching , Bacon Daniel R. , Kimple Adam J. , Ceppe Agathe S. , Kato Takafumi , Pickles Raymond J. , Randell Scott H. , Baric Ralph S. , Turner Justin H. , Boucher Richard C.
Published: January 2022

Background

The nose is the portal for severe acute respiratory syndrome–coronavirus‐2 (SARS‐CoV‐2) infection, suggesting the nose as a target for topical antiviral therapies. The purpose of this study was to assess both the in vivo and in vitro efficacy of a detergent‐based virucidal agent, Johnson and Johnson's Baby Shampoo (J&J), in SARS‐CoV‐2–infected subjects.

Methods

Subjects were randomized into three treatment groups: (1) twice daily nasal irrigation with J&J in hypertonic saline, (2) hypertonic saline alone, and (3) no intervention. Complementary in vitro experiments were performed in cultured human nasal epithelia. The primary outcome measure in the clinical trial was change in SARS‐CoV‐2 viral load over 21 days. Secondary outcomes included symptom scores and change in daily temperature. Outcome measures for in vitro studies included change in viral titers.

Results

Seventy‐two subjects completed the clinical study (n = 24 per group). Despite demonstrated safety and robust efficacy in in vitro virucidal assays, J&J irrigations had no impact on viral titers or symptom scores in treated subjects relative to controls. Similar findings were observed administering J&J to infected cultured human airway epithelia using protocols mimicking the clinical trial regimen. Additional studies of cultured human nasal epithelia demonstrated that lack of efficacy reflected pharmacokinetic failure, with the most virucidal J&J detergent components rapidly absorbed from nasal surfaces.

Conclusion

In this randomized clinical trial of subjects with SARS‐CoV‐2 infection, a topical detergent‐based virucidal agent had no effect on viral load or symptom scores. Complementary in vitro studies confirmed a lack of efficacy, reflective of pharmacokinetic failure and rapid absorption from nasal surfaces.
Bimetallic Palladium/Cobalt Catalysis for Enantioselective Allylic C−H Alkylation via a Transient Chiral Nucleophile Strategy
Authors: Wang Hongkai , Xu Yang , Zhang Fangqing , Liu Yangbin , Feng Xiaoming
Published: January 2022

An asymmetric allylic C−H functionalization has been developed by making use of transient chiral nucleophiles, as well as bimetallic synergistic catalysis with an achiral Pd0 catalyst and a chiral N,N′‐dioxide‐CoII complex. A variety of β‐ketoesters and N‐Boc oxindoles coupled with allylbenzenes and aliphatic terminal alkenes were well tolerated, furnishing the desired allylic alkylation products in high yields (up to 99 %) with excellent regioselectivities and enantioselectivities (up to 99 % ee).
Structures of Silver Fingers and a Pathway to Their Genotoxicity
Authors: Kluska Katarzyna , Veronesi Giulia , Deniaud Aurélien , Hajdu Bálint , Gyurcsik Béla , Bal Wojciech , Krężel Artur
Published: January 2022

Recently, we demonstrated that AgI can directly replace ZnII in zinc fingers (ZFs). The cooperative binding of AgI to ZFs leads to a thermodynamically irreversible formation of silver clusters destroying the native ZF structure. Thus, a reported loss of biological function of ZF proteins is a likely consequence of such replacement. Here, we report an X‐ray absorption spectroscopy (XAS) study of AgnSn clusters formed in ZFs to probe their structural features. Selective probing of the local environment around AgI by XAS showed the predominance of digonal AgI coordination to two sulfur donors, coordinated with an average Ag−S distance at 2.41 Å. No Ag−N bonds were present. A mixed AgS2/AgS3 geometry was found solely in the CCCH AgI−ZF. We also show that cooperative replacement of ZnII ions with the studied Ag2S2 clusters occurred in a three‐ZF transcription factor protein 1MEY#, leading to a dissociation of 1MEY# from the complex with its cognate DNA.
Anion–π Catalysis Enabled by the Mechanical Bond**
Authors: Maynard John R. J. , Galmés Bartomeu , Stergiou Athanasios D. , Symes Mark D. , Frontera Antonio , Goldup Stephen M.
Published: January 2022

We report a series of rotaxane‐based anion–π catalysts in which the mechanical bond between a bipyridine macrocycle and an axle containing an NDI unit is intrinsic to the activity observed, including a [3]rotaxane that catalyses an otherwise disfavoured Michael addition in >60 fold selectivity over a competing decarboxylation pathway that dominates under Brønsted base conditions. The results are rationalized by detailed experimental investigations, electrochemical and computational analysis.
Amyloid‐Templated Palladium Nanoparticles for Water Purification by Electroreduction
Authors: Teng Jie , Peydayesh Mohammad , Lu Jiandong , Zhou Jiangtao , Benedek Peter , Schäublin Robin E. , You Shijie , Mezzenga Raffaele
Published: January 2022

Electrocatalysis offers great promise for water purification but is limited by low active area and high uncontrollability of electrocatalysts. To overcome these constraints, we propose hybrid bulk electrodes by synthesizing and binding a Pd nanocatalyst (nano‐Pd) to the electrodes via amyloid fibrils (AFs). The AFs template is effective for controlling the nucleation, growth, and assembly of nano‐Pd on the electrode. In addition, the three‐dimensional hierarchically porous nanostructure of AFs is beneficial for loading high‐density nano‐Pd with a large active area. The novel hybrid cathodes exhibit superior electroreduction performance for the detoxification of hexavalent chromium (Cr6+), 4‐chlorophenol, and trichloroacetic acid in wastewater and drinking water. This study provides a proof‐of‐concept design of an AFs‐templated nano‐Pd‐based hybrid electrode, which constitutes a paradigm shift in electrocatalytic water purification, and broadens the horizon of its potential engineered applications.
Molecular Dipole‐Induced Photoredox Catalysis for Hydrogen Evolution over Self‐Assembled Naphthalimide Nanoribbons
Authors: Lin Huan , Wang Junhui , Zhao Jiwu , Zhuang Yan , Liu Bingqian , Zhu Yujiao , Jia Huaping , Wu Kaifeng , Shen Jinni , Fu Xianzhi , Zhang Xuming , Long Jinlin
Published: January 2022

D‐π‐A type 4‐((9‐phenylcarbazol‐3‐yl)ethynyl)‐N‐dodecyl‐1,8‐naphthalimide (CZNI) with a large dipole moment of 8.49 D and A‐π‐A type bis[(4,4′‐1,8‐naphthalimide)‐N‐dodecyl]ethyne (NINI) with a negligible dipole moment of 0.28 D, were smartly designed and synthesized to demonstrate the evidence of a molecular dipole as the dominant mechanism for controlling charge separation of organic semiconductors. In aqueous solution, these two novel naphthalimides can self‐assemble to form nanoribbons (NRs) that present significantly different traces of exciton dissociation dynamics. Upon photoexcitation of NINI‐NRs, no charge‐separated excitons (CSEs) are formed due to the large exciton binding energy, accordingly there is no hydrogen evolution. On the contrary, in the photoexcited CZNI‐NRs, the initial bound Frenkel excitons are dissociated to long‐lived CSEs after undergoing ultrafast charge transfer within ca. 1.25 ps and charge separation within less than 5.0 ps. Finally, these free electrons were injected into Pt co‐catalysts for reducing protons to H2 at a rate of ca. 417 μmol h−1 g−1, correspondingly an apparent quantum efficiency of ca. 1.3 % can be achieved at 400 nm.
Engineering Olefin‐Linked Covalent Organic Frameworks for Photoenzymatic Reduction of CO2
Authors: Zhao Zhengfeng , Zheng Dong , Guo Menglei , Yu Jiangyue , Zhang Sainan , Zhang Zhenjie , Chen Yao
Published: January 2022

It is of profound significance concerning the global energy and environmental crisis to develop new techniques that can reduce and convert CO2. To address this challenge, we built a new type of artificial photoenzymatic system for CO2 reduction, using a rationally designed mesoporous olefin‐linked covalent organic framework (COF) as the porous solid carrier for co‐immobilizing formate dehydrogenase (FDH) and Rh‐based electron mediator. By adjusting the incorporating content of the Rh electronic mediator, which facilitates the regeneration of nicotinamide cofactor (NADH) from NAD+, the apparent quantum yield can reach as high as 9.17±0.44 %, surpassing all reported NADH‐regenerated photocatalysts constructed by crystalline framework materials. Finally, the assembled photocatalyst–enzyme coupled system can selectively convert CO2 to formic acid with high efficiency and good reusability. This work demonstrates the first example using COFs to immobilize enzymes for artificial photosynthesis systems that utilize solar energy to produce value‐added chemicals.
Autism service preferences of parents/guardians and autistic adults in five countries
Authors: Cascio M. Ariel , Racine Eric
Published: January 2022

Scholars and activists debate whether people on the autism spectrum should access autism‐specific services or general/inclusive/mainstream services. This article presents quantitative results from a mixed‐methods survey of autistic adults and parents/guardians of autistic people in Canada, France, Germany, Italy, and the United States. Respondents reported categories of services used (autism‐specific, mixed‐disability, or general/inclusive/mainstream), satisfaction, and overall service preference. Most respondents preferred autism‐specific services, followed by different categories of services for different service types. Demographic factors had little influence on overall service preferences. No significant differences were found between adults' and parents/guardians' overall service preferences. For parents/guardians, using autism‐specific services was associated with a preference for autism‐specific services. There were significant associations between the services respondents reported having previously used and their overall service preference. Parents/guardians in Italy and France reported lower satisfaction with many services. These results suggest that a preference for autism‐specific services pervades different groups. While most respondents did endorse autism‐specific services, the strong secondary preference for different service categories encourages providers and policy makers to attend to diverse needs. While satisfaction was generally middling to high, there remain areas for improvement, especially in general job training services. General services can use a Universal Design approach and collaborate with autism‐specific and mixed‐disability services to increase accessibility to diverse populations. The influence of previous service use on preferences suggests that providers can leverage strengths of existing services, leverage and create connections, and ask users about previous experiences to better address their expectations.

Lay Summary

This study asked autistic adults and parents/guardians of autistic people what they think about autism services. Most parents/guardians and adults liked services that focus on autism, but many parents/guardians and adults liked them for some things and not others. All services can ask people about services they used in the past and learn from the strengths of good services through Universal Design and working with other services.
Analyzing and Mitigating Water Utility System Vulnerabilities
Authors: Davies Augustus W. , Dubow Joel B. , Collins George , Borky John M.
Published: January 2022

Key Takeaways

Water distribution and wastewater systems are vulnerable to physical attacks and cyberattacks.

Security is critical for remote telemetry units (RTUs) because they can be a target for malicious service disruptions.

Changes to present‐day RTU designs to improve effectiveness, situational awareness, and response times should minimize potential exploitation.
Progress in the development of naturally derived active metabolites‐based drugs: Potential therapeutics for Alzheimer's disease
Authors: Mani Renuka , sha Sulthana Ahmed , Muthusamy Ganesan , Elangovan Namasivayam
Published: January 2022

Alzheimer's disease (AD) is an extensive age‐associated neurodegenerative disorder. In spite of wide‐ranging progress in understanding the AD pathology for the past 50 years, clinical trials based on the hypothesis of amyloid‐beta (Aβ) have reserved worsening particularly at late‐stage human trials. Consequently, very few old drugs are presently used for AD with inadequate clinical consequences and various side effects. We focus on widespread pharmacological and beneficial principles for existing as well as future drugs. Multitargeting approaches by means of general antioxidant and anti‐inflammatory mechanisms allied with particular receptor and/or enzyme‐mediated actions in neuroprotection and neurodegeneration. The plant kingdom comprises a vast range of species with an incredible diversity of bioactive metabolites with diverse chemical scaffolds. In recent times, an increasing body of facts recommended the use of phytochemicals to decelerate AD's onset and progression. The definitive goal of AD investigation is to avert the onset of neurodegeneration, thereby allowing successful aging devoid of cognitive decline. At this point, we discussed the neurological protective role of natural products and naturally derived therapeutic agents for AD from various natural polyphenolic compounds and medicinal plants. In conclusion, medicinal plants act as a chief source of different bioactive constituents.
Highly Efficient, Dendrite‐Free Zinc Electrodeposition in Mild Aqueous Zinc‐Ion Batteries through Indium‐Based Substrates
Authors: Tribbia Michele , Glenneberg Jens , Zampardi Giorgia , La Mantia Fabio
Published: January 2022

Quasi‐neutral aqueous zinc‐ion (Zn‐ion) batteries are nowadays among the most promising energy storage devices for smart‐grid applications. However, their practical use remains hindered by the low Zn electrodeposition efficiency at the negative electrode, which is especially reduced due to the parasitic evolution of gaseous hydrogen. Indium is a non‐toxic metal showing poor hydrogen evolution kinetics, but it is also very expensive. Therefore, an optimized mixture of bismuth and indium particles has been used as the substrate for the Zn electrodeposition and dissolution reaction to increase its reversibility and its efficiency in a quasi‐neutral ZnSO4 solution. This strategy not only allowed to prolong the cycle life of a full Zn‐ion cell of 10 times at 0.5 C due to the suppression of the hydrogen evolution reaction, as proved by the operando DEMS analysis, but also led to very homogeneous zinc deposits over prolonged cycling at realistic charge and current densities.
Dual Activities of Oxidation and Oxidative Decarboxylation by Flavoenzymes
Authors: Trisrivirat Duangthip , Sutthaphirom Chalermroj , Pimviriyakul Panu , Chaiyen Pimchai
Published: January 2022

Specific flavoenzyme oxidases catalyze oxidative decarboxylation in addition to their classical oxidation reactions in the same active sites. The mechanisms underlying oxidative decarboxylation by these enzymes and how they control their two activities are not clearly known. This article reviews the current state of knowledge of four enzymes from the l‐amino acid oxidase and l‐hydroxy acid oxidase families, including l‐tryptophan 2‐monooxygenase, l‐phenylalanine 2‐oxidase and l‐lysine oxidase/monooxygenase and lactate monooxygenase which catalyze substrate oxidation and oxidative decarboxylation. Apart from specific interactions to allow substrate oxidation by the flavin cofactor, specific binding of oxidized product in the active sites appears to be important for enabling subsequent decarboxylation by these enzymes. Based on recent findings of l‐lysine oxidase/monooxygenase, we propose that nucleophilic attack of H2O2 on the imino acid product is the mechanism enabling oxidative decarboxylation.
Benchtop NIR data standardization on handheld spectrometers to identify paracetamol tablets
Authors: Mees Corenthin , Kauffmann Jean‐Michel , Pierna Juan Antonio Fernández , De Braekeleer Kris
Published: January 2022

Near‐infrared spectroscopy (NIRS) allows innovative applications in terms of quality control, for example, in raw materials verification, in process analytical technology (PAT), and in discrimination between genuine and falsified medicines. The development of small and cheap handheld devices is expanding in the field, while trying to keep similar performances as benchtop instruments have. Considering traceability and quality control of drug compounds, this work is intended to identify 13 different paracetamol tablets on the Belgian market by using NIRS. The performances of a Fourier‐transform near‐infrared spectroscopy (FT‐NIR) benchtop and two handheld NIR spectrometers were investigated comparatively. All spectra were collected through the blister in the reflectance diffuse mode. NIR spectral fingerprints were pretreated and analyzed using principal component analysis (PCA) and classified with soft independent modeling of class analogy (SIMCA). The performances of the spectrometers were evaluated after standardization of the reference benchtop database to the handheld spectrometers. The instrumental response of the benchtop spectrometer was standardized towards the handheld device using the piecewise direct standardization (PDS) algorithm. These investigations permitted the advantages and limitations of NIR data standardization on predictive models to be pointed out. The SIMCA models based on the spectral data of the benchtop (B), handheld 1 (H1), and handheld 2 (H2) instruments had an accuracy of 99.2%, 97.7%, and 96.2%, respectively. The same accuracy was obtained with the models of the transferred benchtop spectra for the H1 and H2 devices. However, adding handheld spectra to the transferred benchtop spectra resulted in models with improved accuracy: from 97.7% to 98.5% for the H1 instrument and from 96.2% to 97.7% for the H2 instrument. The proposed strategy highlights the potential of using a reference database collected by NIRS for pharmaceutical analyses by handheld NIR spectrometers in terms of traceability.
Activation by Glutathione in Hypoxic Environment of an Azo‐based Rhodamine Activatable Photosensitizer. A Computational Elucidation
Authors: Ponte Fortuna , Mazzone Gloria , Russo Nino , Sicilia Emilia
Published: January 2022

In the present paper, density functional theory (DFT) has been applied to the study of the activation mechanism of a new selenium azo‐rhodamine (azoSeRho) in presence of the tripeptide thiol, glutathione (GSH), as potent activatable photosensitizer to be employed in photodynamic therapy. The introduction of the azo group into the conjugated system of the seleno‐rhodamine dye and its reaction with GSH allow the selective formation of the active photosensitizer, SeRho. Furthermore, DFT calculations have allowed to shed light on the activation mechanism of the azoSeRho photosensitizer when molecular oxygen is present and hydrogen peroxide is formed. This study is the first theoretical investigation revealing how the reductive cleavage of the azo moiety by GSH occurs. Time‐dependent DFT approach has been used to evaluate the chalcogen‐substitution effect on the structures and photophysical properties of the azo derivatives and, then, on the activated photosensitizers.
S‐(Trifluoromethyl)Benzothioate (TFBT): A KF‐Based Reagent for Nucleophilic Trifluoromethylthiolation
Authors: Meng Depei , Lyu Yichong , Ni Chuanfa , Zhou Min , Li Yang , Hu Jinbo
Published: January 2022

S‐(Trifluoromethyl)benzothioate (TFBT) has been developed as an inexpensive, bench‐stable, and user‐friendly trifluoromethylthiolation reagent, which can be easily synthesized by using KF as the only fluorine source. By using TFBT, trifluoromethylthiolates with various counterions can be readily obtained. The synthetic application of TFBT was demonstrated by trifluoromethylthiolation‐halogenation of arynes, bis(trifluoromethylthiolation)–halogenation of 1,2‐benzdiynes, nucleophilic substitution of alkyl halides, deoxytrifluoromethylthiolation of alcohols, and cross‐coupling with aryl and vinyl boronic acids.
Four Dibenzofuran‐Terminated High‐Triplet‐Energy Hole Transporters for High‐Efficiency and Long‐Life Organic Light‐Emitting Devices
Authors: Sasabe Hisahiro , Araki Suguru , Abe Shoki , Ito Nozomi , Kumada Kengo , Noda Taito , Sukegawa Yoshihito , Yokoyama Daisuke , Kido Junji
Published: January 2022

The weak stability of a hole‐transporter upon approaching the anion state is one of the major bottlenecks for developing long‐life organic light‐emitting devices (OLEDs). Therefore, in this study, we developed a series of thermally and electrically stable hole‐transporters that are end‐capped with four dibenzofuran units. These materials exhibit i) high bond dissociation energy (BDE) toward the anion state, ii) a high glass transition temperature (Tg>130 °C), and iii) high triplet energy (ET>2.7 eV), thereby enabling approximately 20 % high external quantum efficiency (EQE) and significantly prolonging the stability of both thermally activated delayed fluorescent (TADF) and phosphorescent OLEDs with an operation lifetime at 50 % (LT50) of 20 000–30 000 h at 1000 cd m−2. In addition, investigating their structure‐property relationship revealed that ionization potential (IP), BDE, and Tg are critical prerequisites for the hole‐transporter to prolong lifetime in OLEDs.
Mechanistic Insights on the Mechanosynthesis of Phenytoin, a WHO Essential Medicine**
Authors: Puccetti Francesco , Lukin Stipe , Užarević Krunoslav , Colacino Evelina , Halasz Ivan , Bolm Carsten , Hernández José G.
Published: January 2022

In recent years, mechanochemistry has enriched the toolbox of synthetic chemists, enabling faster and more sustainable access to new materials and existing products, including active pharmaceutical ingredients (APIs). However, molecular‐level understanding of most mechanochemical reactions remains limited, delaying the implementation of mechanochemistry in industrial applications. Herein, we have applied in situ monitoring by Raman spectroscopy to the mechanosynthesis of phenytoin, a World Health Organization (WHO) Essential Medicine, enabling the observation, isolation, and characterization of key molecular‐migration intermediates involved in the single‐step transformation of benzil, urea, and KOH into phenytoin. This work contributes to the elucidation of a reaction mechanism that has been subjected to a number of interpretations over time and paints a clear picture of how mechanosynthesis can be applied and optimized for the preparation of added‐value molecules.
Mechanistic models for liquid binder evaporation in wet granulation
Authors: Heidari Elham , Movahedirad Salman , Sobati Mohammad Amin
Published: January 2022

In this study, binder evaporation as a significant microscale phenomenon in fluidized bed wet granulation has been investigated in three situations: a single droplet, a sessile droplet, and a liquid bridge. Single droplet evaporation has been analytically modelled by mass transfer analysis from a spherical droplet subjected to the relative velocity of the medium and considering evaporation rate variations versus droplet diameter. Then, the sessile droplet evaporation model has been used from the literature. Finally, the liquid bridge evaporation has been modelled, and the rupture time of the bridge has been computed. The local temperature dependence of air physicochemical properties has been considered in all models. The single and sessile droplet evaporation rates have been successfully validated by the experimental data of the air–water system. The effects of operational conditions and liquid/particle properties on each evaporation event have been evaluated and quantified. The results indicate that both the higher relative velocity between the air and a single droplet and the smaller equilibrium contact angle in a constant volume of sessile droplets increase the evaporation rate. Also, increasing the length of the binder bridge reduces the rupture time.
Investigation of charcoal and activated charcoal for microwave absorbers
Authors: de Oliveira Gabriela Gil , Pereira Marina Seixas , Ataíde Carlos Henrique
Published: January 2022

The effects of the microwave heating process and the behaviour as absorbent materials of charcoals obtained from Eucalyptus urograndis wood, macauba endocarp, and lignin, in the activated and non‐activated forms, were investigated. The dielectric properties were measured with the coaxial probe method, and the values of loss tangent obtained for all the materials characterize them as absorbers. Heating tests were performed with materials in the raw form and also mixed with sand, a transparent material to microwave radiation. A factorial design of experiments was performed, and the effect of microwave power and mass concentration of materials over heating rate was studied. Both factors had a significant and positive influence on the heating rate of the seven analyzed materials. The carbon activation process increased the absorption and heating potential, due to the greater surface area and porosity generated by the process. The highest values of heating rate were obtained in the tests carried out with Eucalyptus‐activated carbon.
Promotion of Low‐Temperature Oxidation of Propane through Introduction of Ce into Mullite Oxide YMn2O5
Authors: Zhang Tong , Dong Anqi , Wan Xiang , Shi Guoliang , Peng Jianfei , Li Weifang , Wang Gen , Chen Da , Wang Weichao
Published: January 2022

A high‐surface‐area Ce doped mullite YMn2O5 was developed via a facile hydrothermal approach, which exhibited higher catalytic activity with a long thermal stability towards propane oxidation in regards to pristine mullite YMn2O5. T90 (the temperature at 90 % conversion of reactant) of propane over the mixed oxides is ∼40 °C lower than that over pristine YMn2O5 mullite (147 m2/g). The complete oxidation temperature occurs at as low as 225 °C (1000 ppm C3H8 and 10 % O2 balanced with N2, WHSV=30,000 mL/g h). Notably, the mixed oxides maintain superior catalytic stability at 250 °C for 120 h without noticeable loss in the activity. Fundamentally, the remarkable performance stems from the abundant oxygen defects caused by the lattice mismatch between CeO2 and YMn2O5, which is conducive to the gas phase oxygen adsorption and activation, thereby enhancing the low temperature catalytic activity of the material. In addition, the CeO2 on the catalyst's surface acts as an oxygen reservoir and provides additional adsorption sites for propane to promote the oxidation reaction. In situ DRIFTS results indicates that the dissociation of acrylate could be the key step for propane oxidation since acrylate is more difficult to decompose and desorb than formate and acetate. These findings revealed the roles of ceria on mullite oxides for propane oxidation activity.
Finding Conditions to Process Hydrate Crystals and Amorphous Solids of Disodium Guanosine 5′‐Monophosphate by an Antisolvent Crystallization Process
Authors: Kim Jungsuk , Ulrich Joachim
Published: January 2022

A screening of amorphous, heptahydrate, and tetrahydrate forms of disodium guanosine 5′‐monophosphate is investigated using an antisolvent crystallization process with the aim to selectively produce each solid form. The concentrations of the solution and solid forms are monitored by in situ Raman spectroscopy using a calibration tool. Particle sizes and particle counts are measured with elapsed time by a focal beam reflection measurement. Concentrations of amorphous and hydrates phases are determined using in‐line measurement techniques. The variables studied are temperature, initial concentration, addition rate, and solvent fraction. The results demonstrate that transformation from amorphous to hydrate forms consists of four stages, which are the nucleation of the amorphous form, predissolution of amorphous form, the nucleation of hydrate crystal and dissolution of amorphous solid, and the growth of hydrate crystal. The rate‐controlling step, in this case, is the dissolution of amorphous form. Transformation between heptahydrate to tetrahydrate crystals is a nucleation‐growth‐controlled step. It is possible to obtain selectively the solid forms of disodium guanosine 5′‐monophosphate by referring to the supersaturation and solubility data.
Tandem Thio‐Michael Addition/Remote Lactone Activation of 5‐Hydroxymethylfurfural‐Derived δ‐Lactone‐Fused Cyclopentenones
Authors: A. Gomes Rafael F. , Ravasco Joao M. J. M. , Andrade Késsia H. S. , Coelho Jaime A. S. , Moreira Rui , Oliveira Rafael , Nogueira Fátima , Afonso Carlos A. M.
Published: January 2022

The creation of structurally diverse chemical entities from fairly simple biorefinery products remains a challenge. In this work 5‐hydroxymethylfurfural (HMF) was identified as a key synthon for preparing highly complex cyclopentenones (CP) via tandem 1,4‐addition/elimination/remote lactone activation to external O‐ and N‐nucleophiles in δ‐lactone‐fused‐CPs hotspots. This scaffold was also reactive enough to be incorporated into model cysteine‐peptides in low concentrations, paving the way to a potential translation generating complexity in the synthesis of small peptides. The new enones also exhibited activity against intraerythrocytic Plasmodium falciparum (IC50=1.32 μm).
Elucidating Two Distinct Pathways for Electrocatalytic Hydrogen Production Using CoII Pincer Complexes
Authors: Brown Josh , Ovens Jeffrey , Richeson Darrin
Published: January 2022

Hydrogen gas is a sustainable energy source with water as the sole combustion product. As a result, efforts to catalyze H2 production are pertinent and widespread. The electrocatalytic H2 generating capabilities of two CoII complexes, [Co(κ3‐2,6‐{Ph2PNR}2(NC5H3))Br2] with R=H (I) or R=Me (II), were presented for a variety of proton sources including trifluoroacetic acid (TFA), acetic acid (AA), and trifluoroethanol (TFE). Cyclic voltammetry and controlled potential coulometry demonstrated that electrocatalysis from I and II occurred at two different potentials and are associated with different reduction processes. Density functional theory analysis provided insight into the identities of the catalyst and supported two distinct reaction pathways for electrocatalytic proton reduction. Specifically, stronger acids (e. g., AA, TFA) proceeded at −1.31 to −1.45 V through a MI/MIII pathway while sources with higher pKa values (e. g., TFE, H2O) generated hydrogen at −2.4 V via M0/MII ligand‐assisted metal‐centered reduction.
The impact of atopic dermatitis on the quality of life
Authors: Hund William , Logas Christopher M. , Glick Brad P. , Del Rosso James Q.
Published: January 2022

Atopic dermatitis (AD) has a significant impact on people's quality of life. Studies have further evaluated the impact of AD on patients' family members. Various tools have been used to quantify quality of life including Dermatology Life Quality Index (DLQI), Infants Dermatology Quality of Life Index (IDQOL), Children's Dermatology Life Quality Index (CDLQI), Dermatitis Family Impact Questionnaire (DFI), and many others. Several studies have found AD to have significant impairment on sleep, cognitive function, and workplace productivity. It may come to no surprise the higher rates of depression seen in patients with AD compared with those without AD. It is important that clinicians consider the utilization of quality‐of‐life measures when evaluating patients with AD.
Bis‐ethynylphosphonamidates as an Modular Conjugation Platform to Generate Multi‐Functional Protein‐ and Antibody‐Drug‐Conjugates
Authors: Kasper Marc‐André , Lassak Lukas , Vogl Annette M. , Mai Isabelle , Helma Jonas , Schumacher Dominik , Hackenberger Christian P. R.
Published: January 2022

Bis‐ethynylphosphonamidates allow for a simple chemoselective addition of two thiol‐containing modules in a row. We describe four such bis‐electrophiles that carry different functional O‐substituents with tunable hydrophilicity and enable further subsequent conjugations, thus facilitating a simple protocol for constructing protein‐protein conjugates. An increased spacer length between the two ethynylphosphonamidates simplifies the formation of a conjugate from two bulky proteins. We apply these reagents to obtain homogeneous Antibody‐Drug‐Conjugates (ADCs) from DM1 and trastuzumab with excellent cytotoxicity and selectivity for the targeted cell line. Moreover, a bis‐ethynylphosphonamidate, carrying an additional alkyne for a chemoselective triple conjugation, has been subjected to fluorescent labeling of an ADC specifically at the drug site give an Antibody‐Drug‐Fluorophore‐Conjugate (ADFC), allowing for the observation of intracellular trafficking after ADC uptake into the targeted cell.
Double standards in the COVID‐19 pandemic: The moderation of perceived threat
Authors: Wang Xue , Wang Ting , Jiang Tonglin , Chen Zhansheng , Hong Ying‐yi
Published: January 2022

This research explored whether people hold double standards in a public crisis. We proposed that during the COVID‐19 pandemic, people required others to strictly follow self‐quarantine rules and other preventive behaviours, whereas they themselves would not, demonstrating double standards. Moreover, this effect would be moderated by the perceived threat from the pandemic. Using data collected in the United States and China, three studies (N = 2180) tested the hypotheses by measuring (Study 1) and manipulating the perceived threat (Studies 2 and 3). We found that people generally applied higher standards to others than to themselves when it came to following the self‐quarantine rules. This effect was strong when a relatively low threat was perceived, but the self–other difference disappeared when the perceived threat was relatively high, as the demands they placed on themselves would increase as the perceived threat intensified, but their requirements of others would be constantly strict.
Role of Ca, Cr, Ga and Gd promotor over lanthana‐zirconia–supported Ni catalyst towards H2‐rich syngas production through dry reforming of methane
Authors: Al‐Fatesh Ahmed S. , Khatri Jyoti , Kumar Rawesh , Kumar Srivastava Vijay , Osman Ahmed I. , AlGarni Tahani S. , Ibrahim Ahmed A. , Abasaeed Ahmed E. , Fakeeha Anis H. , Rooney David W.
Published: January 2022

Hydrogen production through methane dry reforming holds the promise of lowering greenhouse gases, that is CO2 and CH4, concentrations. Herein, Ca‐, Cr‐, Ga‐ and Gd‐promoted lanthana‐zirconia–supported Ni catalysts are investigated and characterized by X‐ray diffraction, Raman, infrared and UV‐vis spectroscopy, CH4‐temperature programmed surface reaction and cyclic reduction‐desorption experiment. All promoted catalyst systems had high and constant hydrogen yield (>70%) due to pronounced reoxidation capacity of reduced ‘NiO species strongly interacted with support’ through oxygen replenishment by CO2. The presence of mixed oxide and regeneration of reduced catalyst up to optimum level through oxygen replenishment by CO2 in Gd, as well as Cr‐promoted catalyst, outperformed (80% initially) than other promotors, Ca and Ga. In the long run (440 min to 33 h), Cr‐promoted catalyst system performed better than Gd‐promoted catalyst system as H2 yield remained constant ~79% due to the smallest energy gap between valance and conduction band, Ni‐Cr interaction species for wide range CH4 decomposition and chromate species for profound carbon deposit oxidation.
No Adverse Effects of Stacked Bacillus thuringiensis Maize on the Midge Chironomus riparius
Authors: Chen Yi , Romeis Jörg , Meissle Michael
Published: January 2022

Material from genetically engineered maize producing insecticidal Cry proteins from Bacillus thuringiensis (Bt) may enter aquatic ecosystems and expose nontarget organisms. We investigated the effects on life table parameters of the midge Chironomus riparius (Diptera: Chironomidae) of SmartStax maize leaves, which contain six different Cry proteins targeting Lepidoptera and Coleoptera pests, in two plant backgrounds. For midge development and emergence, 95% confidence intervals for the means of six conventional maize lines (Rheintaler, Tasty Sweet, ES-Eurojet, Planoxx, EXP 258, and EXP 262), were used to capture the natural range of variation. For reproduction, lowest and highest means were used. The natural range of variation allows one to judge whether observed effects between Bt maize and the closest non-Bt comparator are likely to be of biological relevance. No adverse effects on C. riparius were observed with any Bt maize line compared with the respective non-Bt counterpart. Development time was shorter when females were fed Bt maize than when they were fed non-Bt maize, but this effect was not considered adverse. Development time, emergence ratio, sex ratio, and larvae/egg rope measured for Bt maize were within the natural range of variation. Fecundity for the Bt lines was equal to or higher than that for the conventional lines. Future risk assessment studies may consider plant background effects and the natural range of variation to judge the relevance of observed differences between particular genetically engineered and non-genetically engineered plants. Environ Toxicol Chem 2022;41:1078–1088. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.