bluuebunny/crossref_metadata_2025 huggingface dataset:
HiGee strategy towards large‐scale synthesis of soluble covalent organic frameworks
Authors: Zhao Yun , Yu Xiaogang , Wen Xin , Luo Yong , Xiang Zhonghua , Chen Jian‐feng
Published: August 2022

The scale‐up synthesis of covalent organic frameworks (COFs) with uniform structure and properties is of great importance for their practical applications. Here, we proposed a facile way to massively produce phthalocyanine‐like COFs (COFBTC) via high‐gravity intensified synthesis. Alcoholic solvent and basic catalyst were discovered synergically improved the formation of COFBTC. High concentration and reaction temperature were beneficial for high production as well. The intensified mass and heat transfer at high‐gravity promoted the scaling‐up of COFBTC with homogeneous structures and properties. A high space time yield of 305.9 kg∙(m3 D)−1 was achieved for Fe‐COFBTC under optimized condition. The massively produced Fe‐COFBTC presented good solubility in alkaline and polar organic solvents, thus allow to process as homogeneous or heterogenous electrocatalyst for oxygen reduction reaction. The catalyst exhibited good performance of 0.79 V (vs. RHE, half‐wave) and >95% recovery in homogeneous electroreduction of O2 in 0.1 M KOH. A superior performance of 0.86 V was achieved by sol–gel‐like processing of Fe‐COFBTC on carbon paper due to the enhanced conductivity. The scale‐up soluble catalysts with uniform properties provide more opportunities for practical applications of COFBTC.
CO2‐Assisted Stereocontrolled Multi‐Component Coupling Reactions Promoted by Ni‐Catalytic System
Authors: Mori Takamichi , Noba Nao , Munakata Miho , Kimura Masanari
Published: August 2022

A combination of Ni‐catalyst and PPh3 promotes the three‐component coupling reaction of vinyl epoxide, alkyne, and dimethylzinc under a carbon dioxide atmosphere to provide 2,5‐heptadienyl alcohols with excellent E‐stereoselectivity. The stereochemistry of the products from the multi‐component coupling reaction is controlled via an oxanickelacycle intermediate, which is formed by the insertion of carbon dioxide.
Oxidative Fluorination of Selenium and Tellurium Compounds using a Thermally Stable Phosphonium SF5−Salt Accessible from SF6
Authors: Eder Tobias , Buß Florenz , Wilm Lukas F. B. , Seidl Michael , Podewitz Maren , Dielmann Fabian
Published: August 2022

Fluorinated group 16 moieties are attractive building blocks in synthetic chemistry but only few synthetic methods are available to prepare them. Herein, we report a new oxidative fluorination reagent capable of stabilizing reactive fluorinated anions. It consists of an SF5−anion and a chemically inert phosphonium cation and is exceptionally thermally stable. Accordingly, it was used to generate the SeF5−and TeF5−anions from the elemental chalcogens and to prepare the unknown tetrafluoro(phenyl)‐λ5‐selenate PhSeF4−and ‐tellurate PhTeF4−from the corresponding diphenyl dichalcogenides. In addition, we show that further derivatization of [PhTeF4]−by oxidation totrans‐PhTeF4O−and subsequent alkylation gives access to a new class oftrans‐(alkoxy)(phenyl)tetrafluoro‐λ6‐tellanes (trans‐PhTeF4OR), thus providing an approach to introduce the functional group into organic molecules.
Dual‐Modulated Release of a Cytotoxic Photosensitizer Using Photogenerated Reactive Oxygen Species and Glutathione
Authors: Lee Chae Gyu , Lee Chaiheon , Lee Joonhee , Nam Jung Seung , Kim Byeong‐Su , Kwon Tae‐Hyuk
Published: August 2022

Reversible thiol‐disulfide exchange chemistry is of particular interest in drug delivery systems. However, high levels of glutathione (GSH) in cancer cells are hard to distinguish from GSH in normal cells, resulting in unmanageable cytotoxic drug release. This study investigates the spatiotemporally‐controlled irreversible degradation of Ir‐based photosensitizer (TIr3)‐encapsulating nanogels (IrNG) through the hyperoxidation of resulting intracellular thiols using reactive oxygen species (ROS). A highly cytotoxic TIr3 was stably encapsulated within IrNG through hydrophobic interactions and reversible crosslinking between its disulfide bonds and thiols in the absence of light, resulting in high biocompatibility under normal cellular conditions. However, upon photoirradiation, TIr3 generated high levels of ROS, irreversibly oxidizing the thiols to induce electrostatic repulsion between the polymer molecules, resulting in the TIr3 release and induction of cancer cell apoptosis.
Torsional Strain‐Independent Catalytic Enantioselective Synthesis of Biaryl Atropisomers
Authors: Luo Zhang‐Hong , Wang Wen‐Tao , Tang Tian‐Yi , Zhang Sen , Huang Fen , Hu Dan , Tao Ling‐Fei , Qian Linghui , Liao Jia‐Yu
Published: August 2022

Catalytic asymmetric dynamic kinetic resolution of configurationally labile bridged biaryls is emerging as a powerful strategy for atropisomer synthesis. However, the reported examples suffer from an inherent challenge as the reactivity is highly dependent on the torsional strain of the biaryl substrates, which significantly narrows down the scope and hampers the application. Herein, we report our discovery and development of a torsional strain‐independent reaction between biaryl thionolactones and activated isocyanides. By employing auto‐tandem silver catalysis, a universal synthesis of bothtri‐ andtetra‐ortho‐substituted thiazole‐containing biaryls was realized in high yields with high enantioselectivities. In addition, these products could be facilely converted to a novel type of bridged biaryls bearing an eight‐membered lactone. Mechanistic studies were carried out to elucidate the cause of this unusual torsional strain‐independent reactivity.
Reimplementing Guest Shape Sorting of Nonporous Adaptive Crystals via Substituent‐Size‐Dependent Solid‐Vapor Postsynthetic Modification
Authors: Li Errui , Zhu Weijie , Fang Shuai , Jie Kecheng , Huang Feihe
Published: August 2022

Postsynthetic modification (PSM) has been widely used in porous crystalline materials to gain better performance in adsorptive separation of gases or hydrocarbons. We here report that guest adsorption selectivity in a kind of nonporous crystalline materials, namely nonporous adaptive crystals (NACs), can be readily and precisely tuned via a facile substituent‐size‐dependent solid‐vapor PSM method. Before PSM, NACs of pillar[4]arene[1]quinone EtP4Q1 show negligible selectivity for C5 hydrocarbons. PSM with a larger substituent, cyclopentylamine, onto EtP4Q1 NACs does not improve the selectivity, while EtP4Q1 NACs after PSM with a slightly smaller substituent, cyclobutylamine, is endowed with very high preference of n‐pentane over cyclopentane. Comprehensive structural analyses confirm that the intermolecular interactions among the host compounds and host–guest interactions between the adsorbent and the adsorbate are the two major factors in determining the guest selectivity.
Cascades of Evolved Enzymes for the Synthesis of Complex Molecules
Authors: Rosenthal Katrin , Bornscheuer Uwe T. , Lütz Stephan
Published: August 2022

Thanks to advances in enzyme discovery and protein engineering combined with the development of enzymatic multistep reaction cascades, new efficient routes for drug synthesis have been created that are superior to chemical syntheses. This supports the goal of the chemical and pharmaceutical industries to move to more sustainable and environmentally friendly processes. Recently described outstanding examples include the biocatalytic cascade syntheses of the cyclic dinucleotide MK‐1454, molnupiravir, and islatravir, as well as the efficient fixation of CO2 to make starch using an artificial enzyme cascade.
Reactive Solubilization of Heterometallic Clusters by Treatment of (TrBi3)2− Anions (Tr=Ga, In, Tl) with [Mn{N(SiMe3)2}2]
Authors: Rienmüller Julia , Schmidt Andreas , Yutronkie Nathan J. , Clérac Rodolphe , Werncke C. Gunnar , Weigend Florian , Dehnen Stefanie
Published: August 2022

Lowering the charge of Zintl anions by (element‐)organic substituents allows their use as sources of (semi)metal nanostructures in common organic solvents, as realized for group 15 anions or Ge94− and Sn94−. We developed a new strategy for other anions, using low‐coordinate 3d metal complexes as electrophiles. [K(crypt‐222)]+ salts of (TrBi3)2− anions dissolved in situ in Et2O and/or THF when reacted with [Mn(hmds)2]. Work‐up afforded soluble [K(crypt‐222)]+ salts of [{(hmds)2Mn}2(TlBi3)]2− (in 1), [{(hmds)2Mn}2(Bi2)]2− (in 2), and [{(hmds)Mn}4(Bi2)2]2− (in 3) (crypt‐222=4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane; Tr=Ga, In, Tl; hmds=N(SiMe3)2), representing rare cases of Zintl clusters with open‐shell metal atoms. 1 comprises the first coordination compound of the (TlBi3)2− anion, 2 features a diamond‐shaped {Pn2M2} unit, and 3 is a mixed‐valent MnI/MnII compound. The uncommon electronic structures in 1–3 and magnetic coupling were studied by comprehensive DFT calculations.
[8]Cyclo‐para‐phenylmethine as a Super‐Cyclooctatetraene: Dynamic Behavior, Global Aromaticity, and Open‐Shell Diradical Character in the Neutral and Dicationic States
Authors: Li Zhengtao , Hou Xudong , Han Yi , Fan Wei , Ni Yong , Zhou Qifeng , Zhu Jun , Wu Shaofei , Huang Kuo‐Wei , Wu Jishan
Published: August 2022

An [8]cyclo‐para‐phenylmethine derivative ([8]CPPM‐Mes) was synthesized. X‐ray analysis revealed a tub‐shaped geometry similar to the cyclooctatetraene, with alternating benzenoid/quinoid structure. Variable‐temperature NMR measurements disclosed a slow valence tautomerization process with an interconversion energy barrier of about 11.7 kcal mol−1 at coalescence temperature (273 K), and two more lower‐barrier dynamic processes involving flipping of the 1,4‐phenyl rings on the backbone and rotation of the mesityl substituents. Its dication ([8]CPPM‐Mes2+) adopts a bowl‐like geometry with a smaller depth of the cavity, and a slow bowl inversion process was observed by dynamic NMR. The bond lengths of the benzenoid/quinoid rings are more averaged via electron delocalization and the molecule shows global aromaticity, which was further validated by NMR and theoretical analysis. [8]CPPM‐Mes2+ exhibits open‐shell diradical character with a small singlet‐triplet energy gap (−1.8 kcal mol−1).
A Hybrid Antiperovskite with Strong Linear and Second‐Order Nonlinear Optical Responses
Authors: Li Minjuan , Zhang Xu , Xiong Zheyao , Li Yanqiang , Zhou Yang , Chen Xin , Song Yipeng , Hong Maochun , Luo Junhua , Zhao Sangen
Published: August 2022

Antiperovskites have been studied since the 1980s because of their rich physical and chemical properties, but their linear and second‐order nonlinear optical responses remain largely unknown. Here we report a new polar crystal, Cs3Cl(HC3N3S3) (I), which features a quasi‐one‐dimensional antiperovskite structure composed of ClCs6 polyhedra and A‐site [HC3N3S3]2− rings. To our best knowledge, this kind of antiperovskite structure is reported for the first time. Remarkably, I exhibits a very strong nonlinear optical response up to 11.4 times that of the benchmark KH2PO4 and exceptionally large birefringence of 0.52. The first‐principles calculations and structural analyses reveal that [HC3N3S3]2− is the “material gene” while the antiperovskite structural feature making it in a favorable arrangement. This work provides a new structural platform for the rational design of integrated optoelectronic materials with linear and second‐order nonlinear optical responses.
A Systemic Model of Outreach Care for Adolescents Experiencing Obsessive‐Compulsive Disorder: Targeting Family Emotions
Authors: Assan Ben , Caruana Emma , Sutton Chloe , Coffey Catherine
Published: August 2022

The paper presents a model of care focusing on family emotions in the treatment of adolescent obsessive‐compulsive disorder, which is illustrated by a case study. It is concluded that augmenting current treatments by targeting family emotions may enhance adolescent outcomes and improve family functioning. The model is illustrated by a case study, and further systematic research with a larger sample size is recommended.
Synthesis of ruthenium‐based metal ionic liquid polymer microspheres as an artificial enzyme for colorimetric detection of prochloraz residues in strawberries
Authors: Yang Yongqiang , Cao Zhijun , Xie Yilin , Wang Qinsheng , Wang Qun , Li Zaijun
Published: August 2022

Metal nanomaterial as artificial enzyme has high oxidase‐like activity, good stability, and low cost. The ruthenium‐based salicylic acid vinyl imidazole ionic liquid is subjected to radical polymerization to obtain ruthenium‐based ionic liquid polymer microspheres. The oxidative activity‐like artificial enzyme was synthesized by reducing the ruthenium‐based ionic liquid polymer microspheres with sodium borohydride. The research shows that the artificial enzyme based on ionic liquid polymer microspheres has excellent dispersibility, the average particle size is 1 μm, and the ruthenium are distributed on the surface of the polymer microspheres, showing high oxidase‐like activity. Based on the inhibitory effect of prochloraz on the artificial enzyme activity of ruthenium‐based ionic liquid polymer microspheres, a colorimetric detection method for the determination of prochloraz was established. The presence of prochloraz will inhibit the activity of the artificial enzyme of the ruthenium‐based ionic liquid polymer microspheres to promote the oxidation of 3,3′,5,5′‐Tetramethylbenzidine (TMB) to blue products, resulting in decrease in the absorbance of the TMB oxidation product, and the absorbance of the reaction system varies with the concentration of prochloraz between 0.01 and 100 μM increased and decreased linearly with a detection limit of 8 nM. The detection method is simple and quick, and can be used for the rapid determination of prochloraz residues in strawberries.
Preparation of boron nitride hybrid containing phosphorus and silicon and its effect on flame retardant, smoke suppression, and thermal conductivity properties of styrene‐butadiene rubber
Authors: Cheng Zihao , Xu Wenzong , Ding Ding , Xu Chengwen , Xie Yunlong , Qiao Mengxia
Published: August 2022

In this study, a nanofiller (M‐DOPO‐BN) was synthesized by surface modification of hexagonal boron nitride with vinyltrimethoxysilane (KH‐171) and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO), and compounded with aluminum diethyl phosphinate (ADP) to study their effects on flame retardant, smoke suppression and thermal conductivity properties of styrene‐butadiene rubber (SBR). The results showed that the composites with an ADP content of 20 parts per hundred of rubber (phr) have good flame retardant properties, but the total smoke production increased significantly. The flame retardant properties of SBR composites compounded with 3 phr M‐DOPO‐BN and 17 phr ADP were not only further improved, but also the peak carbon monoxide production rate (pCOP) and peak carbon dioxide production rate (pCO2P) were reduced by 37.0% and 67.5%, respectively, compared with pure samples, showing a good smoke inhibition effect. In addition, the thermal conductivity of the composites have also been improved to a certain extent. The variable temperature infrared and residual char analysis of SBR composites showed that the reasons for its flame retardancy and smoke suppression are that M‐DOPO‐BN can catalyze the formation of carbon, and the silica and boron nitride generated by decomposition during combustion can improve the density of residual char.
Data‐based iterative learning control for multiphase batch processes
Authors: Geng Yan , Ruan Xiaoe , Yang Xuan , Zhou Qinghua
Published: August 2022

In order to cope with the problem of the robustness conditions dependence on system parameters information, this paper investigates a data‐based iteration learning control (ILC) for multiphase batch processes with different dimensions and system uncertainty. Firstly, by minimizing the residual between the actual subsystem output and the approximated subsystem output, a gradient‐type approximation law is designed to approximate the system lower triangular parameters matrix and initial state. Secondly, by minimizing the approximated tracking error between the desired trajectory and the approximated output, a data‐based ILC is constructed in an interactive mode with the approximation law. Finally, the boundedness of the approximation error of the real system parameters from the approximated parameters is derived by means of vector norm theory, while the unconditional robustness of the proposed data‐based ILC is proved. Simulation results illustrate the effectiveness and practicability of the proposed data‐based ILC.
Fatigue and cognitive impairment in neuroborreliosis patients posttreatment—A neuropsychological retrospective cohort study
Authors: Sigurdardottir Anna Helena , Knudtzen Fredrikke Christie , Nymark Anita , Bang Malcolm
Published: August 2022

Background

The aim of this study was to determine the prevalence of fatigue and cognitive impairment in patients with neuroborreliosis (NB) posttreatment and to determine whether delayed treatment initiation led to higher levels of fatigue and cognitive impairment.

Methods

The study population consisted of 88 patients with NB included between October 10, 2014, and August 21, 2020, at the Clinical Center for Emerging and Vector‐borne Infections at Odense University Hospital, Denmark. The Symbol Digit Modalities Test (SDMT) was used as a cognitive screening test, and the Modified Fatigue Impact Scale (MFIS) was used to assess the patients’ level of fatigue over the course of a year.

Results

Overall, 14.3% of patients had an SDMT score indicative of cognitive impairment, and 38.8% of patients reported experiencing fatigue 12 months posttreatment. We found no statistically significant differences in fatigue or cognitive impairment when comparing the patients who had a treatment delay of ≤14 days and those with a treatment delay of >14 days (p > .05) 12 months posttreatment. A random effects regression model showed a significant positive correlation between longer treatment delay and higher MFIS scores, indicating higher levels of fatigue.

Conclusions

The results of this study show that both the early and late treatment groups improved significantly over a 12‐month period in terms of both cognitive symptoms and fatigue. However, it also showed that a substantial subgroup of patients with NB still suffer from fatigue and cognitive impairment 12 months posttreatment.
Deacetylepoxyazadiradione Derived from Epoxyazadiradione of Neem (Azadirachta indica A. Juss) Fruits Mitigates LPS‐Induced Oxidative Stress and Inflammation in Zebrafish Larvae
Authors: Murugan Raghul , Rajesh Ravi , Guru Ajay , Haridevamuthu B. , Almutairi Bader O. , Almutairi Mikhlid H. , Juliet Annie , Renganayagi S. , Gopinath Pushparathinam , Arockiaraj Jesu
Published: August 2022

Reactive oxygen species (ROS) produced by cell metabolism have a duplex role in oxidation and inflammation reactions which involve cell damage or repair responses. Excess ROS production has detrimental effects on the survival of cells. We examined the protective effect of a semi‐natural compound NF2 (deacetylepoxyazadiradione), for its protective activity against free radical‐mediated stress and inflammatory response to lipopolysaccharide (LPS) using zebrafish larvae. Preliminary antioxidant assays indicated an increase in scavenging of free radicals from NF2 than NF1 (Epoxyazadiradione) in a concentration‐dependent manner. Cell cytotoxicity was determined using rat myoblast cell lines (L6), and more than 95 % of cell viability was obtained. Zebrafish developmental toxicity test indicated that NF2 is not toxic even at 150 μM. The percentage of ROS, lipid peroxidation, nitric oxide and apoptosis were reduced significantly in NF2 treated LPS‐stressed zebrafish larvae. The reduced number of employed macrophages on NF2 treatment was observed in neutral red dye‐marked macrophage localization images. Relative expression of antioxidant genes in zebrafish larvae after treatment with NF2 is significantly increased. The RT‐PCR quantification of antioxidant and anti‐inflammatory gene expression indicated decreased relative folds of pro‐inflammatory cytokines, iNOS and increased relative folds of mitochondrial antioxidant genes (GR, GST and GPx) in LPS stressed zebrafish larvae after treatment with NF2. From the overall obtained results, it can be concluded that NF2 reduced the oxidative stress and inflammatory response by scavenging free radicals caused by LPS.
Native Mass Spectrometry‐Guided Screening Identifies Hit Fragments for HOP‐HSP90 PPI Inhibition**
Authors: Vaaltyn Michaelone C. , Mateos‐Jimenez Maria , Müller Ronel , Mackay C. Logan , Edkins Adrienne L. , Clarke David J. , Veale Clinton G. L.
Published: August 2022

Contemporary medicinal chemistry considers fragment‐based drug discovery (FBDD) and inhibition of protein‐protein interactions (PPI) as important means of expanding the volume of druggable chemical space. However, the ability to robustly identify valid fragments and PPI inhibitors is an enormous challenge, requiring the application of sensitive biophysical methodology. Accordingly, in this study, we exploited the speed and sensitivity of nanoelectrospray (nano‐ESI) native mass spectrometry to identify a small collection of fragments which bind to the TPR2AB domain of HOP. Follow‐up biophysical assessment of a small selection of binding fragments confirmed binding to the single TPR2A domain, and that this binding translated into PPI inhibitory activity between TPR2A and the HSP90 C‐terminal domain. An in‐silico assessment of binding fragments at the PPI interfacial region, provided valuable structural insight for future fragment elaboration strategies, including the identification of losartan as a weak, albeit dose‐dependent inhibitor of the target PPI.
Structure Activity Relationship of the Stem Peptide in Sortase A Mediated Ligation from Staphylococcus aureus**
Authors: Apostolos Alexis J. , Kelly Joey J. , Ongwae George M. , Pires Marcos M.
Published: August 2022

The surfaces of most Gram‐positive bacterial cells, including that of Staphylococcus aureus (S. aureus), are heavily decorated with proteins that coordinate cellular interactions with the extracellular space. In S. aureus, sortase A is the principal enzyme responsible for covalently anchoring proteins, which display the sorting signal LPXTG, onto the peptidoglycan (PG) matrix. Considerable efforts have been made to understand the role of this signal peptide in the sortase‐mediated reaction. In contrast, much less is known about how the primary structure of the other substrate involved in the reaction (PG stem peptide) could impact sortase activity. To assess the sortase activity, a library of synthetic analogs of the stem peptide that mimic naturally existing variations found in the S. aureus PG primary sequence were evaluated. Using a combination of two unique assays, we showed that there is broad tolerability of substrate variations that are effectively processed by sortase A. While some of these stem peptide derivatives are naturally found in mature PG, they are not known to be present in the PG precursor, lipid II. These results suggest that sortase A could process both lipid II and mature PG as acyl‐acceptor strands that might reside near the membrane, which has not been previously described.
Cardiorenal syndrome type I recovery following heart rate correction: Cardiac output is not only stroke volume
Authors: Maadarani Ossama , Bitar Zouheir , Zaalouk Tamer , Hanna Boutros , Elhabibi Mohamad , Aldaher Moataz , Hajjia Adnan
Published: August 2022

Bradyarrhymias can result in low cardiac output state despite having a normal left ventricular ejection fraction and stroke volume. Because cardiac output is defined as the product of heart rate and stroke volume, a low cardiac output state caused by bradyarrhythmias may result in type I cardiorenal syndrome.
Mitral valve plasty in a patient with multiple cerebral cavernous malformations: A case report
Authors: Yamashita Shigeyuki , Nagao Kanetsugu , Doi Toshio , Yokoyama Shigeki , Yamashita Akio , Fukahara Kazuaki , Yoshimura Naoki
Published: August 2022

Cerebral cavernous malformations (CCMs) are blood vessel malformations, often untreated if asymptomatic. However, upon cardiac surgery with cardiopulmonary bypass, cerebral edema/hemorrhage may occur. We successful performed mitral valve plasty for a case of severe mitral regurgitation with multiple CCMs. Preoperative head magnetic resonance imaging and strict perioperative management are important.
Catalytic Hydrogenolysis of Lignin into Phenolics by Internal Hydrogen over Ru Catalyst
Authors: Hossain Md. Anwar , Saelee Tinnakorn , Tulaphol Sarttrawut , Rahaman Mohammad Shahinur , Phung Thanh Khoa , Maihom Thana , Praserthdam Piyasan , Praserthdam Supareak , Yelle Daniel J. , Sathitsuksanoh Noppadon
Published: August 2022

Lignin is a by‐product of biorefineries and pulp and paper manufacturers. Lignin is a renewable source of phenolic precursors for fuels and chemicals. Hydrogenolysis of lignin cleaves the abundant β‐O‐4 bonds and releases phenolics. However, selective hydrogenolysis of lignin's β‐O‐4 bonds is challenging because it requires high‐pressure H2. Here we show efficient hydrogenolysis of lignin model compounds and technical lignin by Ru/C catalyst and internal hydrogen. The aliphatic hydroxyl groups (Cα−OH) in lignin enabled Ru‐catalyzed dehydrogenation of internal hydrogen and the formation of reactive keto intermediate, which facilitated the β‐O‐4 cleavage into phenolic monomers. Furthermore, solvents that had a high donor number (Lewis basicity) enhanced the yield of phenolic monomers, equal to 27.9 wt.% from technical lignin. These findings offer a novel approach for biorefineries to design lignin isolation processes and/or solvent systems to maximize phenolic monomers and to control product selectivity/stability.
Defect‐Decorated NiFe Bimetallic Nanocatalysts for the Enhanced Hydrodeoxygenation of Guaiacol
Authors: Zhang Yaowen , Wang Wenyun , Fan Guoli , Yang Lan , Li Feng
Published: August 2022

Series of Ni‐based nanocatalysts were fabricated for the HDO of lignin‐derived guaiacol to cyclohexane via a single‐source Ni−Fe−Al layered double hydroxide precursor route and characterized by XRD, BET, TEM, XAS, XPS, H2‐TPR, H2‐TPD, NH3‐TPD, and pyridine absorbedin situFT‐IR. As‐fabricated bimetallic NiFe nanocatalyst bearing a Fe/Ni molar ratio of 0.5 : 3 attained a higher cyclohexane yield of 70.5 % under mild reaction conditions (i. e., 230 °C and 1.0 MPa of initial hydrogen pressure), compared to monometallic Ni and other NiFe bimetallic nanocatalysts, as well as monometallic Ni and bimetallic NiFe catalysts prepared by the impregnation method. Combination of experimental results and density functional theory calculations manifested that interfacial FeOxspecies profoundly facilitated the demethoxylation processes of guaiacol and 2‐methoxycyclohexanol intermediate, while both bimetallic NiFe sites and interfacial FeOxspecies greatly promoted the dehydroxylation of cyclohexanol intermediate.
“Activated Borane” – A Porous Borane Cluster Network as an Effective Adsorbent for Removing Organic Pollutants
Authors: Bůžek Daniel , Škoch Karel , Ondrušová Soňa , Kloda Matouš , Bavol Dmytro , Mahun Andrii , Kobera Libor , Lang Kamil , Londesborough Michael G. S. , Demel Jan
Published: August 2022

The unprecedented co‐thermolysis of decaborane(14) (nido‐B10H14) and toluene results in a novel porous material (that we have named “activated borane”) containing micropores between 1.0 and 1.5 nm in diameter and a specific surface area of 774 m2 g−1 (Ar, 87 K) that is thermally stable up to 1000 °C. Solid state 1H, 11B and 13C MAS NMR, UV‐vis and IR spectroscopies suggest an amorphous structure of borane clusters interconnected by toluene moieties in a ratio of about three toluene molecules for every borane cluster. In addition, the structure contains Lewis‐acidic tri‐coordinated boron sites giving it some unique properties. Activated borane displays high sorption capacity for pollutants such as sulfamethoxazole, tramadol, diclofenac and bisphenol A that exceed the capacity of commercially‐available activated carbon. The consistency in properties for each batch made, and the ease of its synthesis, make activated borane a promising porous material worthy of broad attention.
C−H Activation of Inert Arenes using a Photochemically Activated Guanidinato‐Magnesium(I) Compound
Authors: Mullins Jeremy C. , Yuvaraj K. , Jiang Yixiao , Van Trieste Gerard P. , Maity Asim , Powers David C. , Jones Cameron
Published: August 2022

UV irradiation of solutions of a guanidinate coordinated dimagnesium(I) compound, [{(Priso)Mg}2]3(Priso=[(DipN)2CNPri2]−, Dip=2,6‐diisopropylphenyl), in either benzene, toluene, the three isomers of xylene, or mesitylene, leads to facile activation of an aromatic C−H bond of the solvent in all cases, and formation of aryl/hydride bridged magnesium(II) products, [{(Priso)Mg}2(μ‐H)(μ‐Ar)]4–9. In contrast to similar reactions reported for β‐diketiminate coordinated counterparts of3, these C−H activations proceed with little regioselectivity, though they are considerably faster. Reaction of3with an excess of the pyridine,p‐NC5H4But(pyBut), gave [(Priso)Mg(pyButH)(pyBut)2]10, presumably via reduction of the pyridine to yield a radical intermediate, [(Priso)Mg(pyBut⋅)(pyBut)2]11, which then abstracts a proton from the reaction solvent or a reactant. DFT calculations suggest two possible pathways to the observed arene C−H activations. One of these involves photochemical cleavage of the Mg−Mg bond of3, generating magnesium(I) doublet radicals, (Priso)Mg⋅. These then doubly reduce the arene substrate to give “Birch‐like” products, which subsequently rearrange via C−H activation of the arene. Circumstantial evidence for the photochemical generation of transient magnesium radical species includes the fact that irradiation of a cyclohexane solution of3leads to an intramolecular aliphatic C−H activation process and formation of an alkyl‐bridged magnesium(II) species, [{Mg(μ‐Priso−H)}2]12. Furthermore, irradiation of a 1 : 1 mixture of3and the β‐diketiminato dimagnesium(I) compound, [{(DipNacnac)Mg}2] (DipNacnac=[HC(MeCNDip)2]−), effects a “scrambling” reaction, and the near quantitative formation of an unsymmetrical dimagnesium(I) compound, [(Priso)Mg−Mg(DipNacnac)]13. Finally, the EPR spectrum (77 K) of a glassed solution of UV irradiated3is dominated by a broad featureless signal, indicating the presence of a doublet radical species.
Persistent varicella zoster virus infection following mRNA COVID‐19 vaccination was associated with the presence of encoded spike protein in the lesion
Authors: Yamamoto Mayuko , Kase Misaki , Sano Hozumi , Kamijima Reiko , Sano Shigetoshi
Published: August 2022

Background

Since the campaign of vaccination against COVID‐19 was started, a wide variety of cutaneous adverse effects after vaccination has been documented worldwide. Varicella zoster virus (VZV) reactivation was reportedly the most frequent cutaneous reaction in men after administration of mRNA COVID‐19 vaccines, especially BNT162b2.

Aims

A patient, who had persistent skin lesions after BNT162b2 vaccination for such a long duration over 3 months, was investigated for VZV virus and any involvement of vaccine‐derived spike protein.

Materials & Methods

Immunohistochemistry for detection of VZV virus and the spike protein encoded by mRNA COVID‐19 vaccine. PCR analysis for VZV virus.

Results

The diagnosis of VZV infection was made for these lesions using PCR analyses and immunohistochemistry. Strikingly, the vaccine‐encoded spike protein of the COVID‐19 virus was expressed in the vesicular keratinocytes and endothelial cells in the dermis.

Discussion

mRNA COVID‐19 vaccination might induce persistent VZV reactivation through perturbing the immune system, although it remained elusive whether the expressed spike protein played a pathogenic role.

Conclusion

We presented a case of persistent VZV infection following mRNA COVID‐19 vaccination and the presence of spike protein in the affected skin. Further vigilance of the vaccine side effect and investigation for the role of SP is warranted.
A non‐cross‐linked CO2 foam fracturing fluid with low friction
Authors: Sun Wenan , Zhao Zhongcong , Xiong Junjie , Rong Yujian , Bao Jin , Liu Baolei , Chen Zhihao
Published: August 2022

The hydrophobic associating polymer (MXN‐1) was used as a foam stabilizer with optimized supporting additives to solve the problem of high friction in foam fracturing fluid. The basic formula was 0.3% MXN‐1 + 0.08% sodium dodecyl sulphate (SDS) + 0.3% B‐14 + 1% potassium chloride (KCl) + 0.03% ammonium persulphate (APS). The friction reduction, sand‐carrying capacity, gel‐breaking performance, and core damage of the fracturing fluid system were studied. The results showed that the proposed system had a unique friction reduction advantage compared with the cross‐linked guar gum foam fracturing fluid, and the friction reduction percent reached 62% at a high flow rate. The surface tension of the gel breaking solution was lower than 25 mN/m, and the residue content was about 7 mg/L.
SiO2‐Supported Ni(II) and Fe(II) Catalysts Bearing Sodium‐Sulfonate Group for Olefin Polymerization†
Authors: Sun Yao , Wang Quan , Pan Yao , Pang Wenmin , Zou Chen , Chen Min
Published: August 2022

Comprehensive Summary

Heterogeneous catalysts have been dominant for industrial polyolefin production, offering many distinct advantages, such as controlling the morphology of the polymer and preventing reactor fouling. In this contribution, we designed several types of imine ligands bearing sodium‐sulfonate ionic groups and the corresponding nickel/iron catalysts. These catalysts could be immobilized on SiO2 with strong affinity and high catalyst loadings. The SiO2‐supported catalysts behaved better than their homogeneous counterparts during ethylene polymerization with extremely high activity (2.6 × 104 kg·mol−1·h−1) and high thermal stability. In addition, the supported nickel catalysts generated free‐flowing polyethylene with high molecular weight (Mn up to 2.65 × 103 kg·mol–1) and excellent morphology control, indicating no reactor fouling due to the leaching of catalyst. Moreover, for copolymerization, immobilized nickel catalysts showed a higher tolerance of polar monomers, and the efficient copolymerization of ethylene with undecylenic acid was achieved with high activity (450 kg·mol−1·h−1) and a high incorporation ratio (up to 12.3%).
The health economic impact of cow's milk allergy in childhood: A retrospective cohort study
Authors: Cawood Abbie L. , Meyer R. , Grimshaw Kate E. , Sorensen Katy , Acosta‐Mena Dionisio , Stratton Rebecca J.
Published: August 2022

Background

Cow's milk allergy (CMA) is one of the most common food allergies among children. Whilst avoidance of cow's milk protein is the cornerstone of management, further treatment of symptoms including those affecting the gastrointestinal, skin and respiratory systems plus other allergic comorbidities, maybe required. This study aimed to quantify the wider economic impact of CMA and its management in the United Kingdom (UK).

Methods

We conducted a retrospective matched cohort study on children with CMA (diagnosis read code and/or hypoallergenic formula prescription for ≥3 months) examining healthcare data (medication prescriptions and healthcare professional contacts) from case records within The Health Improvement Network (A Cegedim Proprietary Database) in the UK. A comparative cost analysis was calculated based on healthcare tariff and unit costs in the UK.

Results

6998 children (54% male; mean observation period 4.2 years) were included (n = 3499 with CMA, mean age at diagnosis 4.04 months; n = 3499 matched controls without CMA). Compared to those without CMA, medications were prescribed to significantly more children with CMA (p < 0.001) at a higher rate (p < 0.001). Children with CMA also required significantly more healthcare contacts (p < 0.001) at higher rate (p < 0.001) compared to those without CMA. CMA was associated with additional potential healthcare costs of £1381.53 per person per year.

Conclusion

The findings of this large cohort study suggest that CMA and its associated co‐morbidities presents a significant additional healthcare burden with economic impact due to higher prescribing of additional medications. Further research into management approaches that may impact these clinical and economic outcomes of CMA is warranted.
Pharmacokinetic and Bioequivalence Study of Eldecalcitol Soft Capsules in Healthy Chinese Subjects
Authors: Li Ting , Sun Feifei , Liu Yanping , Su Lingping , Shi Ping , Li Xin , Liu Shuqin , Wang Chenjing , Shen Linjing , Cao Yu , Wang Shumin
Published: August 2022

Eldecalcitol is a novel active vitamin D3 1,25(OH)2D3 derivative used in the treatment of osteoporosis. To investigate and compare the pharmacokinetic and bioequivalent profiles of two eldecalcitol soft capsule formulations at a single dose of 0.75 µg in healthy Chinese volunteers, we conducted a randomized single‐dose, open‐label, two‐period crossover study under fasting and fed conditions. Eligible subjects were randomly assigned to receive reference eldecalcitol soft capsules or test capsules in the first treatment period and to receive another formulation in the second period. Serial blood samples were collected for pharmacokinetic analysis. Adverse events were recorded. In total, 28 healthy subjects were enrolled in the fasting trial and 30 subjects were enrolled in the fed trial. The geometric mean ratios of the test formulation to the reference formulation for Cmax, AUC0‐t, and AUC0‐∞ were 94.2%, 94.0%, and 103.3%, respectively, under fasting conditions and 100.1%, 97.3%, and 96.0%, respectively, under fed conditions. No severe adverse events were observed. The results showed that the test and reference eldecalcitol formulations were bioequivalent and well tolerated in healthy Chinese subjects under fasting and fed conditions.
Solar Hydrogen Generation over Carbon Nitride Photocatalyst Promoted by Water‐Soluble Carbon Dots
Authors: Wang Zhongyi , Pei Guang Xian , Qi Haifeng , Zhang Shengxin , Liu Chengcheng , Li Zhen , Han Keli
Published: August 2022

Solar hydrogen generation from water is one of the promising routes to alleviate the current environmental and energy issues. Graphitic carbon nitride (g‐C3N4) has emerged as a promising photocatalyst for hydrogen evolution using visible light while withstanding harsh chemical environments. However, the high occurrence of trapped unreactive charges seriously affects the catalytic performance of g‐C3N4 in photocatalysis applications. Herein, we show that the addition of water‐soluble carbon dots (CDs) to the reaction solution will promote the relaxation of photogenerated electrons in g‐C3N4, thus effectively improving the photocatalytic performance for hydrogen evolution by two times (983.7 vs. 490.7 μmol ⋅ h−1 ⋅ g−1 for with and without CDs, respectively). The steady state properties of the reaction system are studied by ultraviolet‐visible (UV‐vis) and photoluminescence (PL) excitation/emission spectroscopy, which show that the introduction of CDs enhances the visible light absorption of the reaction system. Furthermore, the charge trapping and detrapping processes in g‐C3N4 are further revealed by using time‐resolved photoluminescence (tr‐PL) spectroscopy. The correlation between charge transfer and photocatalytic activity provides new insights into the charge separation dynamics and activity of carbon‐based photocatalysts.
Exploring discordant low amyloid beta and high neocortical tau positron emission tomography cases
Authors: Krishnadas Natasha , Doré Vincent , Laws Simon M. , Porter Tenielle , Lamb Fiona , Bozinovski Svetlana , Villemagne Victor L , Rowe Christopher C.
Published: August 2022

Introduction

Neocortical 3R4R (3‐repeat/4‐repeat) tau aggregates are rarely observed in the absence of amyloid beta (Aβ). 18F‐MK6240 binds specifically to the 3R4R form of tau that is characteristic of Alzheimer's disease (AD). We report four cases with negative Aβ, but positive tau positron emission tomography (PET) findings.

Methods

All Australian Imaging, Biomarkers and Lifestyle study of aging (AIBL) study participants with Aβ (18F‐NAV4694) and tau (18F‐MK6240) PET scans were included. Centiloid <25 defined negative Aβ PET (Aβ–). The presence of neocortical tau was defined quantitatively and visually.

Results

Aβ– PET was observed in 276 participants. Four of these participants (one cognitively unimpaired [CU], two mild cognitive impairment [MCI], one AD) had tau tracer retention in a pattern consistent with Braak tau stages V to VI. Fluid biomarkers supported a diagnosis of AD. In silico analysis of APP, PSEN1, PSEN2, and MAPT genes did not identify relevant functional mutations.

Discussion

Discordant cases were infrequent (1.4% of all Aβ– participants). In these cases, the Aβ PET ligand may not be detecting the Aβ that is present.
A new index for quantifying the ornamentational complexity of animals with shells
Authors: Miao Luyi , Dai Xu , Song Hanchen , Backes André Ricardo , Song Haijun
Published: August 2022

Morphological complexity reflects the biological structure of an organism and is closely linked to its associated functions and phylogenetics. In animals with shells, ornamentation is an important characteristic of morphological complexity, and it has various functions. However, because of the variations in type, shape, density, and strength of ornamentation, a universal quantitative measure of morphological complexity for shelled animals is lacking. We propose an ornamentation index (OI) derived from 3D scanning technology and a virtual model for quantifying ornamentation complexity. This index is designed to measure the extent of folding associated with ornamentation, regardless of shape and size. Ornamentation indices were measured for 15 ammonite specimens from the Permian to Cretaceous, 2 modern bivalves, 2 gastropods from the Pliocene to the present, and a modern echinoid. Compared with other measurements, such as the fractal dimension, rugosity, and surface‐volume ratio, the OI displayed superiority in quantifying ornamentational complexity. The present study demonstrates that the OI is suitable for accurately characterizing and quantifying ornamentation complexity, regardless of shape and size. Therefore, the OI is potentially useful for comparing the ornamentational complexity of various organisms and can be exploited to provide further insight into the evolution of conchs. Ultimately, the OI can enhance our understanding of morphological evolution of shelled organisms, for example, whether shell ornaments simplify under ocean acidification or extinction, and how predation pressure is reflected in ornamentation complexity.
Titanium‐Catalyzed Intermolecular Hydroaminoalkylation of Allenes and Methylenecyclopropanes
Authors: Kaper Tobias , Elma Aylişa , Thye Hermann , Knupe‐Wolfgang Paula , Zimmering René , Schmidtmann Marc , Doye Sven
Published: August 2022

Intermolecular hydroaminoalkylation reactions of 1,1‐ and 1,3‐disubstituted allenes as well as methylenecyclopropanes with secondary amines can be achieved in the presence of a 2,6‐bis(phenylamino)pyridinato titanium catalyst at 140 °C within 2–8 h. Corresponding reactions of allenes with N‐benzylanilines deliver branched allylamine products in very good yields (up to 83 %) and with branched‐linear‐ratios between 75 : 25 and 95 : 5. In contrast, bicyclic methylenecyclopropanes undergo hydroaminoalkylation with N‐benzylanilines or N‐alkylbenzylamines to give linear products in good to excellent yields (up to 98 %) with perfect regio‐ and diastereoselectivity. The corresponding 1,2,3‐trisubstituted (2‐aminoethyl)cyclopropane products exhibit a structurally interesting cis‐orientation of all three cyclopropane hydrogen atoms.
Policy styles and pandemic management: The case of Turkey
Authors: Oztig Lacin Idil
Published: August 2022

Using the concept of a policy style developed by Howlett and Tosun, this article explores the linkages between Turkey's policy style and its pandemic management. Turkey took both preemptive and restrictive measures with respect to the COVID‐19 pandemic. Before the virus hit the country, flights to and from various countries including China were suspended, the Scientific Advisory Board (SAB) was established, and a COVID‐19 disease guide was prepared. After the virus entered the country, immediate restrictive measures, such as national lockdowns and international and intercity travel restrictions were put in place. Turkey adopted a centralized response to the pandemic with the President, the Ministry of Interior, the Ministry of Health, and the SAB acting as central players. From the perspective of policy style, this article shows how Turkey's general characteristics of policy‐making processes have been reflected in its pandemic management policies.
Preclinical findings reveal the pharmacological targets of ferulic acid in the treatment of traumatic brain injury
Authors: Dong Qinghua , Yang Shenglin , Liao Huafeng , He Qi , Xiao Junxin
Published: August 2022

Traumatic brain injury (TBI) is characterized by cellular damage and inflammation in lesioned brain tissue. Ferulic acid has been shown to have a melioration effect on neurological functions. However, the active pharmacological effects and the underlying mechanisms of ferulic acid against TBI remain unclear. On the basis of network pharmacology and molecular docking methodology, this study aimed to investigate the beneficial effects of ferulic acid in treating TBI, and characterized the detailed biotargets and mechanisms of these actions. The identified core targets were validated via in silico simulation. We identified 91 overlapping targets associated with ferulic acid and TBI. In‐silico simulation analysis validated the putative core targets of tumor protein p53, mitogen‐activated protein kinase (MAPK) 1, and estrogen receptor 1. The Gene Ontology‐enriched annotations and findings were largely associated with cell proliferation, apoptosis, and inflammation in nerve cells. Additional Kyoto Encyclopedia of Genes and Genomes enrichment analysis unmasked the pharmacological pathways of ferulic acid in treating TBI, including the MAPK signaling pathway and hypoxia‐inducible factor‐1 signaling pathway. Bioinformatic analyses and findings provide a new preclinical strategy for revealing the core targets and network pathways of ferulic acid in treating TBI. Moreover, some bioinformatic findings were computationally validated in silico for exhibiting the neuroprotective action of ferulic acid against TBI.
Reusable and Antibacterial Polymer‐Based Nanocomposites for the Adsorption of Dyes and the Visible‐Light‐Driven Photocatalytic Degradation of Antibiotics
Authors: Wang Jiao , Sgarzi Massimo , Němečková Zuzana , Henych Jiří , Licciardello Nadia , Cuniberti Gianaurelio
Published: August 2022

Adsorption and advanced oxidation processes, especially photocatalysis, are amongst the most common water treatment methodologies. Unfortunately, using each of these techniques independently does not fully eliminate the pollutants of diverse nature, which are present in wastewater. Here, an avenue for multifunctional materials for water treatment is opened by reporting for the first time the preparation, characterization, and study of the properties of a novel multifunctional nanocomposite with both adsorption and visible‐light‐driven photocatalysis abilities. These multifunctional nanocomposites, namely iron (II, III) oxide/poly(N‐isopropylacrylamide‐co‐methacrylic acid)/silver‐titanium dioxide (Fe3O4/P(NIPAM‐co‐MAA)/Ag‐TiO2), are prepared by combining magnetic polymeric microspheres (Fe3O4/P(NIPAM‐co‐MAA)) with silver‐decorated titanium dioxide nanoparticles (Ag‐TiO2 NPs). Cationic dyes, such as basic fuchsin (BF), can be adsorbed by the nanocomposites thanks to the carboxylic groups of Fe3O4/P(NIPAM‐co‐MAA) microspheres. Concomitantly, the presence of Ag‐TiO2 NPs endows the system with the visible‐light‐driven photocatalytic degradation ability toward antibiotics such as ciprofloxacin (CIP) and norfloxacin (NFX). Furthermore, the proposed nanocomposites show antibacterial activity toward Escherichia coli (E. coli), thanks to the presence of silver nanoparticles (Ag NPs). Due to the superparamagnetic properties of iron (II, III) oxide nanoparticles (Fe3O4 NPs), the nanocomposites can be also recycled and reused, after the cleaning process, by using an external magnetic field.