bluuebunny/crossref_metadata_2025 huggingface dataset:
Cobalt‐Catalyzed Cross‐Coupling Reactions
Authors: Capdevila Lorena , Ribas Xavi
Published: January 2022

This chapter covers all types of cobalt‐catalyzed cross‐coupling reactions reported so far, focusing on the mainstream CC cross‐coupling methodologies with organometallic nucleophilic reagents (organomagnesium, organozinc, and organoboron). A dedicated section on the mechanistic aspects of these catalysis is then included. Finally, the more recent cobalt‐catalyzed C–heteroatom bond‐forming reactions (CN, CO, CS, and CP) are covered. All these examples exemplify the potential and adaptability of cobalt to a variety of experimental conditions to effectively perform the desired transformations and the long‐run future lying ahead for cobalt catalysis.
Replacing gamma knife beam‐profiles on film with point‐detector scans
Authors: Rudek Benedikt , Bernstein Kenneth , Osterman Sunshine , Qu Tanxia
Published: January 2022

Purpose

Detector arrays and profile‐scans have widely replaced film‐measurements for quality assurance (QA) on linear accelerators. Film is still used for relative output factor (ROF) measurements, positioning, and dose‐profile verification for annual Leksell Gamma Knife (LGK) QA. This study shows that small‐field active detector measurements can be performed in the easily accessed clinical mode and that they are an effective replacement to time‐consuming and exacting film measurements.

Methods

Beam profiles and positioning scans for 4‐mm, 8‐mm, and 16‐mm‐collimated fields were collected along the x‐, y‐, and z‐axes. The Exradin W2‐scintillator and the PTW microdiamond‐detector were placed in custom inserts centered in the Elekta solid‐water phantom for these scans. GafChromic EBT3‐film was irradiated with single uniformly collimated exposures as the clinical‐standard reference, using the same solid‐water phantom for profile tests and the Elekta film holder for radiation focal point (RFP)/patient‐positioning system (PPS) coincidence. All experimental data were compared to the tissue‐maximum‐ratio‐based (TMR10) dose calculation.

Results

The detector‐measured beam profiles and film‐based profiles showed excellent agreement with TMR10‐predicted full‐width, half‐maximum (FWHM) values. Absolute differences between the measured FWHM and FWHM from the treatment‐planning system were on average 0.13 mm, 0.08 mm, and 0.04 mm for film, microdiamond, and scintillator, respectively. The coincidence between the RFP and the PPS was measured to be ≤0.5 mm with microdiamond, ≤0.41 mm with the W2‐1 × 1 scintillator, and ≤0.22 mm using the film‐technique.

Conclusions

Small‐volume field detectors, used in conjunction with a clinically available phantom, an electrometer with data‐logging, and treatment plans created in clinical mode offer an efficient and viable alternative for film‐based profile tests. Position verification can be accurately performed when CBCT‐imaging is available to correct for residual detector‐position uncertainty. Scans are easily set up within the treatment‐planning‐system and, when coupled with an automated analysis, can provide accurate measurements within minutes.
Mineral Modulated Single Atom Catalyst for Effective Water Treatment
Authors: Dong Xiongbo , Chen Zitong , Tang Aidong , Dionysiou Dionysios D. , Yang Huaming
Published: January 2022

Single atom catalysts (SACs) have been growing as an emerging “hot” topic in environmental remediation. Their performance can be rationally optimized via modulating spatial coordination configuration and the porous structure of SACs, which is still challenging. Herein, a novel Si, N co‐coordinated cobalt SAC (p‐CoSi1N3@D) with 3D free standing architecture is tailored via employing natural mineral (diatomite) as a Si source and porous template. Theoretical calculations and experimental analysis reveal that the substitution of N by Si dramatically accelerates the interaction and electron transfer between peroxymonosulfate and the Co single atom center. Moreover, p‐CoSi1N3@D inherits the hierarchically porous architecture of diatomite, providing more accessible cobalt sites and open diffusion channels for peroxymonosulfate and contaminants in water treatment applications. Thanks to optimal coordination structure and porous architecture, p‐CoSi1N3@D can serve as a highly active catalyst for peroxymonosulfate activation, with a turnover frequency of 299.8 min−1 for bisphenol A degradation, surpassing those of catalysts with transition metal SACs or oxides in the disclosed literature. This work provides a novel strategy for the development of SACs for wastewater reclamation, and deepens the understanding of the significant role of templates in spatial coordination configuration of SACs.
Promoting Homogeneous Interfacial Li+ Migration by Using a Facile N2 Plasma Strategy for All‐Solid‐State Lithium‐Metal Batteries
Authors: Yao Zhengyin , Kang Yao , Hou Minjie , Huang Jian , Zhang Jiaqing , Yang Bin , Dai Yongnian , Liang Feng
Published: January 2022

Hybrid solid electrolytes (HSEs) with satisfactory ionic conductivities, good flexibilities, and ideal interface compatibilities are crucial for the development of all‐solid‐state lithium‐metal batteries. However, Li dendrites and sluggish interfacial Li+ transfer dynamics between the Li metal and HSEs restrict practical applications. Herein, a facile strategy is proposed to promote homogeneous interfacial Li+ migration by modifying HSEs by using nitrogen plasma. N2 plasma not only decreases the crystallinity and glass transition temperature of HSE but also in‐situ generates an ultra‐stable and conductive Li3N layer on the HSE surface. This conductive layer promotes interfacial Li+ migration and favorable wettability, thus effectively improving Li+ transfer dynamics and homogeneous deposition. Therefore, a HSE modified by N2 plasma for 10 s exhibits a low interfacial impedance of 26.5 Ω cm−2 and a high Li+ conductivity of 7.35 × 10−5 S cm−1 at 30 °C. Moreover, a symmetric Li|HSE|Li battery exhibits a stable plating/stripping capability without Li dendrite growth at a current density of 0.1 mA cm−2 during continuous operation over 1000 h. In addition, an all‐solid‐state Li|HSE|LiFePO4 battery exhibits an initial specific capacity of 145.0 mAh g−1 at 1 C with a high capacity retention of 92.4% (134.0 mAh g−1) after 140 cycles.
Targeting the Meningeal Compartment to Resolve Chemobrain and Neuropathy via Nasal Delivery of Functionalized Mitochondria
Authors: Alexander Jenolyn F. , Mahalingam Rajasekaran , Seua Alexandre V. , Wu Suhong , Arroyo Luis D. , Hörbelt Tina , Schedlowski Manfred , Blanco Elvin , Kavelaars Annemieke , Heijnen Cobi J.
Published: January 2022

Cognitive deficits (chemobrain) and peripheral neuropathy occur in ∼75% of patients treated for cancer with chemotherapy and persist long‐term in >30% of survivors. Without preventive or curative interventions and with increasing survivorship rates, the population debilitated by these neurotoxicities is rising. Platinum‐based chemotherapeutics, including cisplatin, induce neuronal mitochondrial defects leading to chemobrain and neuropathic pain. This study investigates the capacity of nasally administered mesenchymal stem cell‐derived mitochondria coated with dextran‐triphenylphosphonium polymer (coated mitochondria) to reverse these neurotoxicities. Nasally administered coated mitochondria are rapidly detectable in macrophages in the brain meninges but do not reach the brain parenchyma. The coated mitochondria change expression of >2400 genes regulating immune, neuronal, endocrine and vascular pathways in the meninges of mice treated with cisplatin. Nasal administration of coated mitochondria reverses cisplatin‐induced cognitive deficits and resolves neuropathic pain at a >55‐times lower dose compared to uncoated mitochondria. Reversal of these neuropathologies is associated with resolution of cisplatin‐induced deficits in myelination, synaptosomal mitochondrial integrity and neurogenesis. These findings demonstrate that nasally administered coated mitochondria promote resolution of chemobrain and peripheral neuropathy, thereby identifying a novel facile strategy for clinical application of mitochondrial donation and treating central and peripheral nervous system pathologies by targeting the brain meninges.
Unraveling Crystallization Mechanisms and Electronic Structure of Phase‐Change Materials by Large‐Scale Ab Initio Simulations
Authors: Xu Yazhi , Zhou Yuxing , Wang Xu‐Dong , Zhang Wei , Ma En , Deringer Volker L. , Mazzarello Riccardo
Published: January 2022

Ge–Sb–Te (“GST”) alloys are leading phase‐change materials for digital memories and neuro‐inspired computing. Upon fast crystallization, these materials form rocksalt‐like phases with large structural and vacancy disorder, leading to an insulating phase at low temperature. Here, a comprehensive description of crystallization, structural disorder, and electronic properties of GeSb2Te4 based on realistic, quantum‐mechanically based (“ab initio”) computer simulations with system sizes of more than 1000 atoms is provided. It is shown how an analysis of the crystallization mechanism based on the smooth overlap of atomic positions kernel reveals the evolution of both geometrical and chemical order. The connection between structural and electronic properties of the disordered, as‐crystallized models, which are relevant to the transport properties of GST, is then studied. Furthermore, it is shown how antisite defects and extended Sb‐rich motifs can lead to Anderson localization in the conduction band. Beyond memory applications, these findings are therefore more generally relevant to disordered rocksalt‐like chalcogenides that exhibit self‐doping, since they can explain the origin of Anderson insulating behavior in both p‐ and n‐doped chalcogenide materials.
Recent Progress and Future Prospects for Light Management of All‐Perovskite Tandem Solar Cells
Authors: Islam Md. Rasidul , Wu Yulin , Liu Kong , Wang Zhijie , Qu Shengchun , Wang Zhanguo
Published: January 2022

Developing tandem solar cells is an excellent strategy to break through the Shockley–Queisser limit for single‐junction solar cells. All‐perovskite tandem solar cells (all‐PTSCs) are considered to have great potential by virtue of their advantages of low‐cost and low‐temperature fabrication. However, complicated light distribution and potential loss of incident light are two issues that hinder the development of all‐PTSCs. In this review, the recent progress in light management of two‐terminal (2T) and four‐terminal (4T) all‐PTSCs is summarized. The authors discuss the problems with wide‐bandgap and narrow‐bandgap sub‐cells and optimization strategies for efficient light management of tandem solar cells. Then, main light losses are analyzed, such as parasitic absorption, reflection, and thermal relaxation. Current mismatching is a critical condition that can affect the practical application of 2T tandem solar cells. The authors discuss how the thickness and bandgap of the absorber layer, interference, back reflections, and light distribution influence on light losses in devices and ultimately impact current matching. Also, the impact of light management on the performance of all‐PTSCs is comprehensively reviewed. Finally, key issues and the prospects for the future development of all‐PTSCs are outlined.
3D Microstructured Inorganic Perovskite Materials for Thermal Neutron Detection
Authors: Caraveo‐Frescas Jesus A. , Reyes‐Banda Martin G. , Fernandez‐Izquierdo Leunam , Quevedo‐Lopez Manuel A.
Published: January 2022

A combination of novel techniques such as a solvent‐free thin‐film deposition, perovskite patterning, and 10B back‐fill technique enables the high neutron detection efficiency in a perovskite‐based microstructured thermal neutron detector. High‐efficiency cesium lead bromide (CsPbBr3) perovskite‐based microstructured detectors are demonstrated here. Trenches up to 10 µm deep are etched into the CsPbBr3 thin films using a novel dry etching process involving a combination of HBr and Ar plasma. The microstructured diodes are then backfilled with isotopically enriched boron as neutron conversion material via a sedimentation process to preserve the perovskite integrity. The fabricated microstructured CsPbBr3 thermal neutron detectors show an efficiency of 4.3%. This represents >1.2x efficiency improvement over planar silicon (3.5%) and >2x efficiency improvement over planar CsPbBr3 (2.1%) detectors, respectively. More importantly, gamma‐ray discrimination of 107 is measured in CsPbBr3‐based microstructured neutron detectors.
Transparent, P‐channel CuISn Thin‐film Transistor with Field Effect Mobility of 45 cm2 V–1 s–1 and Excellent Bias Stability
Authors: Mude Narendra Naik , Bukke Ravindra Naik , Jang Jin
Published: January 2022

The p‐type semiconducting materials are essential building blocks for high performance complementary metal‐oxide semiconductor (CMOS) thin‐film transistor (TFT) circuits. Here, the development of the transparent and high performance of p‐channel copper‐iodide‐tin (CuISn) TFTs is reported. Sn alloy in CuI exhibits remarkable changes in structural and physical properties, which are studied by scanning electron microscopy, high‐resolution transmission electron microscopy, and X‐ray photoelectron spectroscopy, and Hall effect measurements. It is confirmed that 25% Sn‐alloyed CuI has p‐type conductivity with carrier concentration of 2.1 × 1017 cm–3 and Hall mobility of 63.8 cm2 V–1 s–1. The TFT made with 25% CuISn exhibits the high field‐effect mobility (μFE) of 45.5 cm2 V–1 s–1, which is 10‐fold higher than that of the pristine CuI TFT. The CuISn TFT on polyimide substrate exhibits the μFE of 42.5 cm2 V–1 s–1 and ON/OFF current ratio of ≈107. In addition, the CuISn TFT shows excellent stability with the threshold voltage shift of 0.6 V under negative gate bias stress. In addition, the hetrojunction with Li doped ZnO, CuISn/LZO p‐n junction exhibit excellent rectifying characteristics with the diode ideality factor of 1.3 and forward to reverse current ratio of ≈107, which is three order higher than that of CuI/LZO diode. Therefore, the p‐channel CuISn TFTs can be widely used to open up cost‐effective transparent CMOS TFT circuits, displays, and flexible electronics.
Pathways of Exciton Triggered Hot‐Carrier Injection at Plasmonic Metal−Transition Metal Dichalcogenide Interface
Authors: Wen Xiewen , Wang Weipeng , Zhang Xiang , Chen Hailong , Jia Shuai , Gong Yongji , Chen Weibing , Wang Yanfeng , Zhu Hanyu , Zheng Junrong , Ajayan P. M. , Lou Jun
Published: January 2022

Surface plasmon induced hot‐carrier injection to semiconducting transition metal dichalcogenide (TMD) monolayers has been extensively studied. However, comprehensive understanding of the injection kinetics by fully considering the weak metal−TMD interaction and the TMDs’ exciton formation kinetics is missing. Here, a hot‐carrier injection pathway is elucidated by systematically investigating the interfacial interaction kinetics among different plasmonic metals and TMDs. The pathway highlights the exciton formation timescale as a threshold for interfacial carrier injection, before which plasmonic hot carriers and free electron−hole pairs are relaxed incoherently across the interface. The injected hot carriers will interact with excitons to form charged quasiparticles as trions, which have extended lifetime. The pathway reveals the fundamental mechanism of the plasmonic hot‐carrier−TMD interactions, opens the possibility of controllable manipulation of hot‐carrier injection process, and allows future research toward opto‐electrical guidance of trions in metal−TMD systems.
Efficient and Stable Self‐Trapped Blue Emission from a 1D Organolead Chloride Crystalline Material
Authors: Jiang Yilin , Fei Honghan
Published: January 2022

Intrinsic blue emission with high stability and high efficiency remains to be a great challenge for metal halide hybrids. In this study, a single‐crystalline, ultrastable self‐trapped blue‐light emitter based on 1D cationic [Pb2Cl2]2+ haloplumbate chains is discovered, which affords a Stokes shift of 78 nm and Commission Internationale de l'Eclairage chromaticity coordinates of (0.156, 0.080), very close to blue standard (0.140, 0.080). The Stokes shift is the lowest reported value among the intrinsic self‐trapped emission from the vast majority of organometal halide hybrids. Moreover, the presence of out‐of‐plane chloride results in highly localized self‐trapped excitons in 1D cationic chains and high photoluminescence quantum yield of 72%, which exceeds many intrinsic blue‐light‐emitting metal halide materials. Analogous to the previously reported organocarboxylate‐based lead halide hybrids, the material exhibits ultrastable continuous photoemission in air for at least 24 h and maintains the efficient emission after a variety of thermal or chemical treatments. The excellent blue‐light‐emitting performance of the material enables its promising applications in high‐definition lighting and display fields.
Photo‐Controlled Reversible Multicolor Room‐Temperature Phosphorescent Solid Supramolecular Pseudopolyrotaxane
Authors: Zhang Yi , Zhang Cong , Chen Yong , Yu Jie , Chen Lei , Zhang Hui , Xu Xiufang , Liu Yu
Published: January 2022

The photoreversible switch persistent room‐temperature phosphorescent (p‐RTP) system is attractive but challenging in the field of smart luminescent materials. In particular, those p‐RTPs with the excitation‐wavelength‐responsive and time‐dependent multicolor emission are very important but underexplored. Herein an excitation‐wavelength‐responsive and time‐dependent multicolor p‐RTP emission pseudopolyrotaxanes supramolecular system based on host–guest interaction between α‐cyclodextrin (α‐CD) and two luminophores (benzene and naphthalene) modified polyethylene glycol (PEG) derivatives is reported. The excitation‐wavelength‐responsive and time‐dependent multicolor afterglows of the supramolecular system are derived from the diverse p‐RTP emission species with different lifetimes. More importantly, the p‐RTP can be reversibly adjusted by photoisomerization of diarylethylene (DAE), that is, it could be erased under ultraviolet light and recovered under visible‐light for several cycles. Taking advantage of the reversible photoencryption property, this intelligent luminescence supramolecular system has broad application prospects in information storage and treatment.
Identification of mung bean germplasm for resistance against Cercospora canescens and to study the association of biochemical parameters with defense mechanisms
Authors: Mahapatra Sushree Suparna , Swain Dhaneswar , Beura Surjya Kanta , Rout Gyana Ranjan
Published: January 2022

Sizable loss in crop yields resulting from Cercospora leaf spot (CLS), caused by Cercospora canescens and is a major disease in mung bean [Vigna radiata (L.) R. Wilczek] crops, demands a thorough evaluation of various parameters dealing with the infection. Determination of components for CLS resistance is associated with leaf spot intensity in the field, which is estimated from the area under the disease progress curve (AUDPC). The present study showed that out of 261 genotypes screened in the field for CLS, 88, 89, 51 and, 33 genotypes were found to be resistant, moderately resistant, moderately susceptible, and susceptible, respectively, on the basis of the AUDPC values. Further, five resistant and five susceptible genotypes were selected from the screened genotypes for bioassay analysis and were subjected to artificial inoculation with three different isolates of Cercospora canescens to study the effectiveness in polyhouse. The morphological data along with disease incidence, chlorophyll content, proline content, phenol content and enzymatic activities of phenylalanine ammonia‐lyase (PAL), peroxidase (POX), and superoxide dismutase (SOD) were estimated. The findings showed that there was a significant increase in the enzymatic activities, total phenol, and proline contents in inoculated resistant and susceptible genotypes vs. control (without inoculation). However, the total chlorophyll content reduced in both resistant and susceptible genotypes after inoculation. Moreover, higher enzyme activities were marked in the resistant genotypes than the susceptible genotypes. This study will help to identify the resistant and susceptible mung bean genotypes against Cercospora canescens for further agronomic study as well as breeding programs.
Diminishing returns among lamina fresh and dry mass, surface area, and petiole fresh mass among nine Lauraceae species
Authors: Li Yirong , Shi Peijian , Niinemets Ülo , Song Yu , Yu Kexin , Schrader Julian , Niklas Karl J.
Published: January 2022

Premise

The phenomenon called “diminishing returns” refers to a scaling relationship between lamina mass (M) vs. lamina area (A) in many species, i.e., M ∝ Aα>1, where α is the scaling exponent exceeding unity. Prior studies have focused on the scaling relationships between lamina dry mass (DM) and A, or between fresh mass (FM) and A. However, the scaling between petiole mass and M and A has seldom been investigated. Here, we examine the scaling relationships among FM, DM, A, and petiole fresh mass (PFM).

Methods

For each of 3268 leaves from nine Lauraceae species, FM, DM, A, and PFM were measured, and their scaling relationships were fitted using reduced major axis regression protocols. The bootstrap percentile method was used to test the significance of the difference in α‐values between any two species.

Results

The phenomenon of diminishing returns was verified between FM vs. A and DM vs. A. The FM vs. A scaling relationship was statistically more robust than the DM vs. A scaling relationship based on bivariate regression r2‐values. Diminishing returns were also observed for the PFM vs. FM and PFM vs. A scaling relationships. The PFM vs. FM scaling relationship was statistically more robust than the PFM vs. A scaling relationship.

Conclusions

“Diminishing returns” was confirmed among the FM, DM, A, and PFM scaling relationships. The data collectively indicate that the petiole scales mechanically more strongly with lamina mass than with area, suggesting that static (self) loading takes precedence over dynamic (wind) loading.
Pathogenic variant in NFIA associated with subdural hematomas mimicking nonaccidental trauma
Authors: Wongkittichote Parith , Kondis Jamie S. , Peglar Lindsay M. , Strahle Jennifer M. , Miller‐Thomas Michelle , Abell Katherine B.
Published: January 2022

Subdural hematoma (SDH) in infants raises the concern for nonaccidental trauma (NAT), especially when presenting with associated injuries. However, isolated SDH could be caused by multiple etiologies. NFIA (MIM# 600727) encodes nuclear factor I A protein (NFI‐A), a transcription factor which plays important roles in gliogenesis. Loss‐of‐function variants in NFIA are associated with autosomal dominant brain malformations with or without urinary tract defects (MIM# 613735). Intracranial hemorrhage of various types besides SDH has been reported in patients with this condition. Here, we report a patient with a heterozygous novel NFIA pathogenic variant affecting splicing who initially presented with SDH concerning for NAT. We also review previous NFIA‐related disorder cases with intracranial hemorrhage. This report emphasizes the importance of genetic evaluation in infants presenting with isolated SDH.
Carbamoylated Guanidine‐Containing Polymers for Non‐Covalent Functional Protein Delivery in Serum‐Containing Media
Authors: Barrios Alfonso , Estrada Marilen , Moon Joong Ho
Published: January 2022

Despite the high potential of controlling cellular processes and treating various diseases by intracellularly delivered proteins, current delivery systems exhibit poor efficiency due to poor serum stability, cellular entry, and cytosolic availability of proteins. Here, we report a novel functional group, phenyl carbamoylated guanidine (Ph‐CG), that greatly enhances the delivery efficiency to various types of cells. Owing to the substantially lowered pKa, the hydrophobic Ph‐CG offers optimized inter‐macromolecular interactions via enhanced hydrogen‐bonding and hydrophobic interactions. The coplanarity of Ph‐CG also leads to the better intracellular entry of protein complexes. Intracellularly delivered apoptosis‐inducing enzymes and antibodies significantly induce cell viability inhibitions in a serum‐containing medium. The newly developed Ph‐CG can be introduced to various existing carriers, leading to the realization of future therapeutic protein delivery.
Generic Rules for Distinguishing Autophoretic Colloidal Motors
Authors: Peng Yixin , Xu Pengzhao , Duan Shifang , Liu Jiayu , Moran Jeffrey Lawrence , Wang Wei
Published: January 2022

Distinguishing the operating mechanisms of nano‐ and micromotors powered by chemical gradients, i.e. “autophoresis”, holds the key for fundamental and applied reasons. In this article, we propose and experimentally confirm that the speeds of a self‐diffusiophoretic colloidal motor scale inversely to its population density but not for self‐electrophoretic motors, because the former is an ion source and thus increases the solution ionic strength over time while the latter does not. They also form clusters in visually distinguishable and quantifiable ways. This pair of rules is simple, powerful, and insensitive to the specific material composition, shape or size of a colloidal motor, and does not require any measurement beyond typical microscopy. These rules are not only useful in clarifying the operating mechanisms of typical autophoretic micromotors, but also in predicting the dynamics of unconventional ones that are yet to be experimentally realized, even those involving enzymes.
Raman spectroscopy is a powerful tool in molecular paleobiology: An analytical response to Alleon et al. (https://doi.org/10.1002/bies.202000295)
Authors: Wiemann Jasmina , Briggs Derek E. G.
Published: January 2022

A recent article argued that signals from conventional Raman spectroscopy of organic materials are overwhelmed by edge filter and fluorescence artefacts. The article targeted a subset of Raman spectroscopic investigations of fossil and modern organisms and has implications for the utility of conventional Raman spectroscopy in comparative tissue analytics. The inferences were based on circular reasoning centered around the unconventional analysis of spectra from just two samples, one modern, and one fossil. We validated the disputed signals with in situ Fourier‐Transform Infrared (FT‐IR) Spectroscopy and through replication with different lasers, filters, and operators in independent laboratories. Our Raman system employs a holographic notch filter which is not affected by edge filter or other artefacts. Multiple lines of evidence confirm that conventional Raman spectra of fossils contain biologically and geologically meaningful information. Statistical analyses of large Raman and FT‐IR spectral data sets reveal patterns in fossil composition and yield valuable insights into the history of life.
Development and validation of liquid chromatography–tandem mass spectrometry method for the estimation of a potential genotoxic impurity 2‐(2‐chloroethoxy)ethanol in hydroxyzine
Authors: Lakka Narasimha S. , Kuppan Chandrasekar , Ravinathan Poornima , Palakurthi Ashok Kumar
Published: January 2022

2‐(2‐Chloroethoxy)ethanol (CEE) belongs to the so‐called cohort of concerns which were classified as highly potent mutagenic carcinogens by the World Health Organization. It is widely used in the synthesis of the essential anti‐histamine drug hydroxyzine. In addition, it is used as a primary solvent in dyes, nitrocellulose, paints, inks and resins. Owing to its potential genotoxicity, an efficient liquid chromatography–tandem mass spectrometry method was developed for the quantitative estimation of CEE traces in an active pharmaceutical ingredients and in tablet dosage forms of hydroxyzine‐free base. The chromatographic separation was achieved on a C18column using a gradient elution mode with a binary solvent system (ammonium formate and methanol). Mass detection was performed for CEE using a positive mode with selected ion monitoring technique atm/zvalue of [M + NH4]+. The developed method was validated as per the International Conference on Harmonizaiton guidelines. The quantitation limit, linearity and recoveries were found to be 0.56 ppm, 0.56–7.49 ppm (r2 > 0.9985) and 93.6–99.3%, respectively. The proposed method was highly compatible and was used effectively to estimate CEE traces in different stages of drug synthesis and in tablet dosage forms of hydroxyzine for routine and stability testing.
Nocardia rubra cell‐wall skeleton influences the development of cervical carcinoma by promoting the antitumor effect of macrophages and dendritic cells
Authors: Zhang Siyang , Wang Han , Liu Yisi , Tao Tao , Zeng Zhi , Zhou Yingying , Wang Min
Published: January 2022

Background

As an immune enhancer, Nocardia rubra cell‐wall skeleton (Nr‐CWS) has been used to treat persistent human papillomavirus infection and cervical precancerous lesions. However, it is still unclear whether it can be used to treat cervical carcinoma.

Methods

In our study, the aim was to determine whether Nr‐CWS affects the apoptosis of cervical carcinoma cells by enhancing the antitumor effect of dendritic cells and macrophages in vivo and in vitro.

Results

The experimental results showed that Nr‐CWS can promote the activity of dendritic cells and macrophages and reduce their apoptosis. It also increased the cytokines IL‐6, IL‐12, TNF‐ɑ, and IL‐1β secreted by dendritic cells and macrophages and reduced their PD‐L1 expression. In vitro, Nr‐CWS inhibited the proliferation, colony forming ability of HeLa and SiHa cervical carcinoma cell lines cultured with macrophages, and more cells were blocked in G2/M phase. Nr‐CWS promoted TNF‐ɑ/TNFR1/caspase‐8‐mediated apoptosis by increasing macrophages secretion of TNF‐ɑ and inhibited cell migration and invasion regulated by the WNT/β‐catenin‐EMT pathway. Nr‐CWS also reduced the expression of the cervical carcinoma genes E6 and E7 thereby increasing expression of p53 gene and decreasing expression of PD‐L1 gene. In vivo, Nr‐CWS inhibited tumor growth and decreased the expression of E6, E7, PD‐L1, P16, Ki67, and PCNA in tumors.

Conclusions

Therefore, our results suggest that Nr‐CWS can promote apoptosis of cervical carcinoma cells by enhancing the antitumor effect of dendritic cells and macrophages.
Structure Analysis and Anti‐Inflammatory Effect of a Polysaccharide from Hippocampus mohnikei
Authors: Cui Mingxiao , Wang Yu , Liu Kehai
Published: January 2022

The purpose of this study was to analyze the structure of a polysaccharide (HMP‐1) from Hippocampus mohnikei, and to explore its anti‐inflammatory effect. HMP‐1 was obtained from Hippocampus mohnikei by ethanol sedimentation and secondary column chromatography purification. Its structural characteristics were analyzed by gel permeation chromatography (GPC), Fourier transform infrared (FT‐IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and scanning electron micrograph (SEM). Results showed its molecular weight (Mw) was 7296 Da, and it mainly consisted of six residues: 1,3‐β‐Glcp, 1,4‐α‐Manp, 1,4‐α‐GalpA, 1,4‐β‐GlcpA2S, 1,4‐α‐Galp3S, and 1,4‐β‐GlcNAc. HMP‐1 could protect RAW246.7 cells from the cytotoxic effect induced by LPS. HMP‐1 also could reduce the levels of nitric oxide and reactive oxygen species produced by LPS stimulation, suggesting that HMP‐1 has anti‐inflammatory activities within a certain concentration range.
Promoting digitalization‐related competencies of prospective chemistry teachers – comparison of the effectiveness of a university seminar in a face‐to‐face and online format
Authors: Zimmermann Franziska , Melle Insa
Published: January 2022

Durch die fortschreitende Digitalisierung muss sich auch die Lehrkräftebildung den veränderten Anforderungen der schulischen Bildung anpassen, indem Professionalisierungsmaßnahmen entwickelt werden, welche explizit digitalisierungsbezogene Kompetenzen von (angehenden) Lehrkräften fördern. Deshalb wurde ein Hochschulseminar zur Förderung digitalisierungsbezogener Kompetenzen angehender Chemielehrkräfte entwickelt und evaluiert. Aufgrund der Corona‐Pandemie musste dieses zu Beginn des Sommersemesters 2020 in ein Online‐Format übertragen werden. Damit stellte sich die Frage, ob die Förderung digitalisierungsbezogener Kompetenzen angehender Chemielehrkräfte in einem online durchgeführten Seminar gleichermaßen effektiv ist. Dazu wurden die Studierendengruppen des Präsenz‐ und Online‐Formats hinsichtlich ihrer Veränderungen der Fähigkeiten, digitale Werkzeuge in die Unterrichtsplanung zu integrieren und hinsichtlich ihrer TPACK‐Selbstwirksamkeit und Einstellung zum Einsatz digitaler Werkzeuge im Chemieunterricht miteinander verglichen. Insgesamt stellte sich dabei heraus, dass das in ein Online‐Format übertragene Seminar effektiv zur Förderung digitalisierungsbezogener Kompetenzen angehender Chemielehrkräfte ist. Auch wenn im Vergleich zu Präsenz‐Veranstaltungen kein expliziter Nachteil für die Studierenden der Online‐Veranstaltung festgestellt werden konnte, deuten die Ergebnisse an, dass der Lernzuwachs im Präsenz‐Format größer ist, weshalb dieses zu bevorzugen bleibt.
Rational Design and Identification of Harmine‐Inspired,N‐Heterocyclic DYRK1A Inhibitors Employing a Functional Genomic In VivoDrosophilaModel System**
Authors: Huizar Francisco J. , Hill Harrison M. , Bacher Emily P. , Eckert Kaitlyn E. , Gulotty Eva M. , Rodriguez Kevin X. , Tucker Zachary D. , Banerjee Monimoy , Liu Haining , Wiest Olaf , Zartman Jeremiah , Ashfeld Brandon L.
Published: January 2022

Deregulation of dual‐specificity tyrosine phosphorylation‐regulated kinase 1A (DYRK1A) plays a significant role in developmental brain defects, early‐onset neurodegeneration, neuronal cell loss, dementia, and several types of cancer. Herein, we report the discovery of three new classes ofN‐heterocyclic DYRK1A inhibitors based on the potent, yet toxic kinase inhibitors, harmine and harmol. An initial in vitro evaluation of the small molecule library assembled revealed that the core heterocyclic motifs benzofuranones, oxindoles, and pyrrolones, showed statistically significant DYRK1A inhibition. Further, the utilization of a low cost, high‐throughput functional genomic in vivo model system to identify small molecule inhibitors that normalizeDYRK1Aoverexpression phenotypes is described. This in vivo assay substantiated the in vitro results, and the resulting correspondence validates generated classes as architectural motifs that serve as potential DYRK1A inhibitors. Further expansion and analysis of these core compound structures will allow discovery of safe, more effective chemical inhibitors of DYRK1A to ameliorate phenotypes caused by DYRK1A overexpression.
Psychophysiological treatment of chronic tinnitus: A review
Authors: Czornik Manuel , Malekshahi Azim , Mahmoud Wala , Wolpert Stephan , Birbaumer Niels
Published: January 2022

Subjective chronic tinnitus consists of a more or less continuous perception of sound in the absence of a corresponding acoustic source, which can lead to various psychological problems like depression, anxiety, attentional deficits and sleep disturbances. The prevalence is 10%–15% of the general population. Various therapy and management options have been proposed, but outcomes vary, and no generally accepted cure exists. In this review, the coherence of the most frequently used aetiological models shall be evaluated, and the efficacy of several treatment options will be discussed. With respect to tinnitus treatments, we focus on controlled studies and meta‐analyses. Although there are some therapies that outweigh placebo effects such as cognitive behavioural therapy, neurofeedback or neuromodulation techniques, they mainly target secondary symptoms and not the tinnitus tone itself. Furthermore, positive treatment effects only seem to last for a limited period of time. We conclude that long‐lasting combination therapies such as neurofeedback of auditory cortex inhibitory EEG signatures, cognitive therapy and sound‐tactile stimulation may provide more efficient outcomes if they target the intensity of the tinnitus tone itself and not only secondary psychological symptoms.
Generation of Human Pluripotent Stem Cell‐Derived Polarized Hepatocytes
Authors: Bushweller Leila , Zhao Yuanyuan , Zhang Fan , Wu Xianfang
Published: January 2022

Human pluripotent stem cell (hPSC)–derived hepatocyte‐like cells (HLCs) are valuable tools to study liver biology. HLCs, however, lack certain key in vivo characteristics relevant to their physiological function. One such characteristic is cellular polarity, which is critical to hepatocyte counter‐current flow systems involving canalicular bile secretion and sinusoidal secretion of large quantities of serum proteins into blood. Model systems using non‐polarized hepatocytes, therefore, cannot recapitulate this physiological function of hepatocytes. Here, we describe a stepwise protocol to generate hPSC‐derived polarized HLCs (pol‐HLCs), which feature clearly defined basolateral and apical membranes separated by tight junctions. Pol‐HLCs not only display many hepatic functions but are also capable of directional cargo secretion, mimicking the counter‐current flow systems. We describe protocols for stem cell culture maintenance and for differentiating hPSCs into pol‐HLCs. In addition, we describe protocols to assay the pol‐HLCs for basic hepatic functions and polarized hepatic characteristics. Once successfully differentiated, these pol‐HLCs can be used as an in vitro model system to study hepatocyte biology, disease mechanisms, genetic variation, and drug metabolism. The establishment of hepatic polarity from non‐polarized hPSCs also provides a useful tool to study the development and maintenance of hepatic polarity. © 2022 Wiley Periodicals LLC.

Basic Protocol 1: Maintenance of hPSCs

Basic Protocol 2: Differentiation of hPSCs to pol‐HLCs

Basic Protocol 3: Assaying pol‐HLCs for basic hepatic functions

Support Protocol 1: Assessment of pol‐HLC monolayer tightness

Support Protocol 2: Assessment of pol‐HLC polarity
Nitrogen fertilizer and clover inclusion effects on the establishment of fine fescue taxa
Authors: Braun Ross C. , Braithwaite Emily T. , Kowalewski Alexander R. , Watkins Eric , Hollman Andrew B. , Patton Aaron J.
Published: January 2022

Little information exists on establishment vigor differences among fine fescue taxa (Festuca L. spp.) and on the effects N fertilizer levels or clover (Trifolium L. spp.)‐inclusion during establishment. Five replicated field experiments in Indiana, Minnesota, and Oregon were conducted from 2019 to 2021. Data collection continued for 9 mo after planting to investigate differences among four fine fescue taxa and determine optimal N fertility or clover‐inclusion programs for the establishment of fine fescue taxa. Six N fertilizer levels ranged from 0 to 122.5 kg N ha−1 during the 8 wk after planting, and two treatments included clover‐inclusion + 0 kg N ha−1 at seeding. The three taxa of the Festuca rubra complex—strong creeping red fescue (F. rubra L. ssp. rubra Gaudin), slender creeping red fescue [F. rubra ssp. littoralis (G. Mey.) Auquier], and Chewings fescue (F. rubra ssp. commutata Gaudin)—were similar to one another and required the shortest amount of time until 90% establishment (i.e., faster establishment) compared with hard fescue (Festuca brevipila Tracey). Providing 24.5 kg N ha−1 at seeding hastened establishment of all fine fescues compared with no N fertilizer (0 kg N ha−1). Applying 49 kg N ha−1 at establishment provided faster establishment than the 24.5 kg N ha−1 treatment; however, treatments receiving 73.5–122.5 kg N ha−1 during the first 8 wk after planting provided a similar rate of establishment as 49 kg N ha−1. Inclusion of clover with fine fescue resulted in slower establishment than fertilizer levels of ≥24.5 kg N ha−1.
Angiosarcoma arising in the capsule of a mammary silicone implant
Authors: Rajan Sreekumar Sundara , Haider Asma , Burrell Helen , Whisker Lisa , Tamimy Muhammad , McCulloch Tom , Lee Andrew H. S.
Published: January 2022

A 40‐year‐old woman with silicone implants inserted 21 years before presented with sudden onset of painful right breast swelling. Clinical examination revealed a firm swollen breast with appearance of old bruising. Ultrasound showed fluid around the implant. Cytology of the fluid showed cells with large pleomorphic nuclei with prominent nucleoli including elongated forms and very occasional vacuoles. The cell block also contained small fragments with atypical spindle cells around slit‐like spaces that were positive for CD31 and CD34. MRI showed a 25 mm serpiginous area of enhancement on the inner aspect of the fibrous capsule with haematoma between the capsule and the implant. The capsule and adjacent area were excised. Histology showed angiosarcoma extending from the inner aspect of the capsule into the cavity around the implant. The location of the tumour on the inner aspect of the capsule is the same site that breast implant associated anaplastic large cell lymphomas arise and suggests a possible causal link between the implant and the angiosarcoma. This case emphasises the value of cytological assessment of fluid around breast implants and the role of cell blocks and immunohistochemistry.
Removal of the influence of plasma volume fluctuations for the athlete biological passport and stability of haematological variables in active women taking oral contraception
Authors: Moreillon Basile , Equey Tristan , Astolfi Tiffany , Salamin Olivier , Faiss Raphael
Published: January 2022

The haematological module of the athlete biological passport (ABP) monitors longitudinal haematological variations that could be indicative of blood manipulation. This study applied a multi‐parametric model previously validated in elite cyclists to compare inferred and actual PV variations, whereas the potential influence of the oral contraceptive pill (OCP) cycle on the ABP blood biomarkers and plasma volume (PV) in 14 physically active women taking OCPs was also investigated. Blood and serum samples were collected each week for 8 weeks, and the ABP haematological variables were determined according to the World Anti‐Doping Agency guidelines. Transferrin (sTFN), ferritin (FERR), albumin (ALB), calcium (Ca), creatinine (CRE), total protein (TP) and low‐density lipoprotein (LDL) were additionally computed as ‘volume‐sensitive’ variables in a multivariate analysis to determine individual estimations of PV variations. Actual PV variations were indirectly measured using a validated carbon monoxide rebreathing method. We hypothesised ABP markers to be stable during a standard OCP cycle and estimated PV variations similar to measured PV variations. Measured PV variations were in good agreement with the predictions and allowed to explain an atypical passport finding (ATPF). The ABP biomarkers, Hbmass and PV were stable over 8 weeks. Significant differences occurred only between Week 7 and Week 1, with lower levels of haemoglobin concentration ([Hb]), haematocrit (HCT) and red blood cell count (RBC)(−4.4%, p < 0.01; −5.1%, p < 0.01; −5.2%, p < 0.01) and higher levels of PV at week 7 (+9%, p = 0.05). We thus concluded that estimating PV variations may help interpret individual ABP haematological profiles in women.
Simulation‐based guidance for improving CO2${\rm CO}_{2}$ reduction on silver gas diffusion electrodes
Authors: Heßelmann Matthias , Bräsel Berinike Clara , Keller Robert Gregor , Wessling Matthias
Published: January 2022

The reduction of in an electrochemical reactor using electrical energy is a promising approach to implement a more sustainable carbon economy and to replace fossil fuels with renewable carbon sources. Conventionally used solid plate electrodes are limited by poor mass transport of the reactants. Gas diffusion electrodes (GDEs) can overcome this limitation and have gained industrial relevance during the last decades. A comprehensive understanding of transport and conversion phenomena within such porous electrodes is not yet well developed. Here, we report a one‐dimensional steady state model of the GDE to investigate the influence of relevant operational parameters and GDE properties on reduction. The results indicate the importance of controlling the local reaction environment, that is, the reactant concentration and the pH value, by tuning the electrolyte and gas composition, and flow rate as well as the catalyst layer properties.
Root morphological‐physiological traits for japonica/indica hybrid rice with better yield performance under low N conditions
Authors: Chu Guang , Xu Ran , Chen Song , Xu Chunmei , Liu Yuanhui , Abliz Buhailiqem , Zhang Xiufu , Wang Danying
Published: January 2022

Newly bred japonica/indica hybrid rice (JIHR) cultivars might produce more grain yield and have better nitrogen‐use efficiency (NUE) under low N conditions. This study determined whether an improved root system in JIHR cultivars could benefit shoot growth, physiological processes, and thereby grain yield and NUE. Four rice cultivars, including two JIHR cultivars and two local high‐yielding japonica hybrid rice (JHR) cultivars were field‐grown under two N application levels: 120 kg ha−1 (low application of N, LN) and 180 kg ha−1 (normal application of N, NN). Grain yield and the amount of N taken up from the soil were higher in JIHR cultivars than in JHR cultivars by 12.1% and 18.1% under NN and 12.5% and 14.0% under LN, respectively. Compared with JHR cultivars, JIHR cultivars had higher N partial factor productivity (PFPN) under both N treatments and higher internal N‐use efficiency (IEN) and N harvest index only under LN treatment. Under LN treatment, JIHR cultivars had several improved root morphological and physiological traits, for instance, greater root dry weight (DW), root length density and root volume, longer root length, larger specific root length, deeper root distribution, larger root total and active absorption area, higher root oxidation activity (ROA), and concentration of zeatin (Z) plus zeatin riboside (ZR) in root‐bleeding sap, than JHR cultivars. Generally, the results suggest that improved root morphological and physiological traits might benefit shoot growth, physiological processes, and thereby grain yield and NUE for JIHR cultivars under low N conditions.
Disrupted BRCA1‐PALB2 interaction induces tumor immunosuppression and T‐lymphocyte infiltration in HCC through cGAS‐STING pathway
Authors: Ma Hui , Kang Zhihua , Foo Tzeh Keong , Shen Zhiyuan , Xia Bing
Published: January 2022

Background and Aims:

BRCA1 (BRCA1 DNA repair associated) and PALB2 (partner and localizer of BRCA2) interact with each other to promote homologous recombination and DNA double‐strand breaks repair. The disruption of this interaction has been reported to play a role in tumorigenesis. However, its precise function in HCC remains poorly understood.

Approach and Results:

We demonstrated that mice with disrupted BRCA1‐PALB2 interaction were more susceptible to HCC than wild‐type mice. HCC tumors arising from these mice showed plenty of T‐lymphocyte infiltration and a better response to programmed cell death 1 (PD‐1) antibody treatment. Mechanistically, disruption of the BRCA1‐PALB2 interaction causes persistent high level of DNA damage in HCC cells, leading to activation of the cyclic GMP‐AMP synthase (cGAS)–stimulator of interferon genes (STING) signaling pathway in both malignant hepatocytes and M1 macrophages in the tumor microenvironment. The activated cGAS‐STING pathway induces programmed cell death 1 ligand 1 expression via the STING–interferon regulatory factor 3 (IRF3)–signal transducer and activator of transcription 1 pathway, causing immunosuppression to facilitate tumorigenesis and tumor progression. Meanwhile, M1 macrophages with an activated cGAS‐STING pathway could recruit T lymphocytes through the STING‐IRF3 pathway, leading to T‐lymphocyte infiltration in tumors. After normalizing immune responses by PD‐1 antibody treatment, the infiltrating T lymphocytes attack tumor cells rapidly and effectively.

Conclusions:

This study reveals that persistent DNA damage caused by a defective BRCA pathway induces tumor immunosuppression and T‐lymphocyte infiltration in HCC through the cGAS‐STING pathway, providing insight into tumor immune microenvironment remodeling that may help improve HCC response to PD‐1 antibody treatment.