bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractNear‐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

AbstractIn 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

AbstractS‐(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

AbstractThe 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

AbstractIn 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

AbstractIn 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

AbstractThe 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

AbstractA 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

AbstractA 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

AbstractThe 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

AbstractHydrogen 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

AbstractAtopic 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

AbstractBis‐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

AbstractThis 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

AbstractHydrogen 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

Abstract
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.
Identification of superior late‐blooming apricot (Prunus armeniacaL.) genotypes among seedling‐originated trees
Authors: Mashhadi Zeinab , Khadivi Ali 
Published: January 2022

AbstractOne of the major limiting factors in the intensive spread of apricot (Prunus armeniacaL.) in most of the countries is spring frost. Thus, the breeding efforts have concentrated on the use of late‐blooming genotypes as a means of frost avoidance. The aim of the present study was to identify late‐blooming genotypes with high fruit quality among seedling‐originated trees. Firstly, pre‐selections were done according to blooming time within 278 apricot seedling‐originated trees. Secondly, the late‐blooming selections were further evaluated according to their vegetative and fruit characteristics to determine superior types. Significant differences were observed among the late‐blooming genotypes in terms of the traits recorded. Fruit ground color was strongly variable, including white, yellow, yellow–green, light orange, orange, and dark orange. Fruit weight ranged from 27.37 to 33.99 g, fruit flesh thickness varied from 11.16 to 13.47 mm, and total soluble solids varied between 17.00% and 23.87%. Hierarchical cluster analysis (HCA) performed with Euclidean distance and Ward's method divided the genotypes into two main clusters based on morphological traits and in some cases, the genotypes belonging to an area were clustered into different clusters. All the 48 late‐blooming date genotypes selected could be useful as a parent to improve flowering season of cultivars. Also, among them, 10 genotypes were superior in terms of fruit quality‐related characters, such as fruit weight, fruit color, fruit taste, and TSS, and thus they can be singled out for cultivation.