bluuebunny/crossref_metadata_2025 huggingface dataset:
Discovery of Two Polymorphs of TiP4N8Synthesized from Binary Nitrides
Authors: Eisenburger Lucien , Weippert Valentin , Paulmann Carsten , Johrendt Dirk , Oeckler Oliver , Schnick Wolfgang
Published: February 2022

TiP4N8was obtained from the binary nitrides TiN and P3N5upon addition of NH4F as a mineralizer at 8 GPa and 1400 °C. An intricate interplay of disorder and polymorphism was elucidated by in situ temperature‐dependent single‐crystal X‐ray diffraction, STEM‐HAADF, and the investigation of annealed samples. This revealed two polymorphs, which consist of dense networks of PN4tetrahedra (degree of condensationκ=0.5) and either augmented triangular TiN7prisms or triangular TiN6prisms for α‐ and β‐TiP4N8, respectively. The structures of TiP4N8exhibit body‐centered tetragonal (bct) framework topology. DFT calculations confirm the measured band gaps of α‐ and β‐TiP4N8(1.6–1.8 eV) and predict the thermochemistry of the polymorphs in agreement with the experiments.
Aktivierung eines biomimetischen [FeFe]‐Hydrogenase‐Komplexes für die H2‐Produktion mit sichtbarem Licht**
Authors: Buday Philipp , Kasahara Chizuru , Hofmeister Elisabeth , Kowalczyk Daniel , Farh Micheal K. , Riediger Saskia , Schulz Martin , Wächtler Maria , Furukawa Shunsuke , Saito Masaichi , Ziegenbalg Dirk , Gräfe Stefanie , Bäuerle Peter , Kupfer Stephan , Dietzek‐Ivanšić Benjamin , Weigand Wolfgang
Published: February 2022

Inspiriert von dem aktiven Zentrum der natürlichen [FeFe]‐Hydrogenasen haben wir eine kompakte und edelmetallfreie Dyade aus Photosensibilisator (PS) und Katalysator (CAT) entwickelt, die bei Bestrahlung mit sichtbarem Licht Wasserstoff generiert.PS‐CATist ein prototypischer [FeFe]‐Hydrogenase‐Modellkomplex, der π‐konjugierte Oligothiophene als Sammeleinheit für Licht nutzt.PS‐CATund seine Wechselwirkung mit dem Opferdonor 1,3‐Dimethyl‐2‐phenylbenzimidazolin wurden mittels stationärer und zeitaufgelöster Spektroskopie untersucht, verbunden mit elektrochemischen Methoden und photokatalytischen Untersuchungen mit sichtbarem Licht. Über EPR‐Spektroskopie während der Photokatalyse (operando) wurde die Bildung einer aktiven [FeIFe0]‐Spezies sichtbar, die, in Übereinstimmung mit theoretischen Berechnungen, mutmaßlich für die effektive Katalyse (TON≈210) verantwortlich ist.
A Dual pH‐ and Light‐Responsive Spiropyran‐Based Surfactant: Investigations on Its Switching Behavior and Remote Control over Emulsion Stability
Authors: Reifarth Martin , Bekir Marek , Bapolisi Alain M. , Titov Evgenii , Nußhardt Fabian , Nowaczyk Julius , Grigoriev Dmitry , Sharma Anjali , Saalfrank Peter , Santer Svetlana , Hartlieb Matthias , Böker Alexander
Published: February 2022

A cationic surfactant containing a spiropyran unit is prepared exhibiting a dual‐responsive adjustability of its surface‐active characteristics. The switching mechanism of the system relies on the reversible conversion of the non‐ionic spiropyran (SP) to a zwitterionic merocyanine (MC) and can be controlled by adjusting the pH value and via light, resulting in a pH‐dependent photoactivity: While the compound possesses a pronounced difference in surface activity between both forms under acidic conditions, this behavior is suppressed at a neutral pH level. The underlying switching processes are investigated in detail, and a thermodynamic explanation based on a combination of theoretical and experimental results is provided. This complex stimuli‐responsive behavior enables remote‐control of colloidal systems. To demonstrate its applicability, the surfactant is utilized for the pH‐dependent manipulation of oil‐in‐water emulsions.
On‐Surface Synthesis of [3]Radialenes via [1+1+1] Cycloaddition
Authors: Li Deng‐Yuan , Wang Ying , Hou Xiao‐Yu , Ren Yin‐Ti , Kang Li‐Xia , Xue Fu‐Hua , Zhu Ya‐Cheng , Liu Jian‐Wei , Liu Mengxi , Shi Xing‐Qiang , Qiu Xiaohui , Liu Pei‐Nian
Published: February 2022

[3]Radialenes are the smallest carbocyclic structures with unusual topologies and cross‐conjugated π‐electronic structures. Here, we report a novel [1+1+1] cycloaddition reaction for the synthesis of aza[3]radialenes on the Ag(111) surface, where the steric hindrance of the chlorine substituents guides the selective and orientational assembling of the isocyanide precursors. By combining scanning tunneling microscopy, non‐contact atomic force microscopy, and time‐of‐flight secondary ion mass spectrometry, we determined the atomic structure of the produced aza[3]radialenes. Furthermore, two reaction pathways including synergistic and stepwise are proposed based on density functional theory calculations, which reveal the role of the chlorine substituents in the activation of the isocyano groups via electrostatic interaction.
A Metal‐Ion‐Incorporated Mussel‐Inspired Poly(Vinyl Alcohol)‐Based Polymer Coating Offers Improved Antibacterial Activity and Cellular Mechanoresponse Manipulation
Authors: Gao Lingyan , Hou Yong , Wang Haojie , Li Mingjun , Ma Linjie , Chu Zhiqin , Donskyi Ievgen S. , Haag Rainer
Published: February 2022

Cobalt (CoII) ions have been an attractive candidate for the biomedical modification of orthopedic implants for decades. However, limited research has been performed into how immobilized CoII ions affect the physical properties of implant devices and how these changes regulate cellular behavior. In this study we modified biocompatible poly(vinyl alcohol) with terpyridine and catechol groups (PVA‐TP‐CA) to create a stable surface coating in which bioactive metal ions could be anchored, endowing the coating with improved broad‐spectrum antibacterial activity against Escherichia coli and Staphylococcus aureus, as well as enhanced surface stiffness and cellular mechanoresponse manipulation. Strengthened by the addition of these metal ions, the coating elicited enhanced mechanosensing from adjacent cells, facilitating cell adhesion, spreading, proliferation, and osteogenic differentiation on the surface coating. This dual‐functional PVA‐TP‐CA/Co surface coating offers a promising approach for improving clinical implantation outcomes.
Salt‐Stabilized Silylzinc Pivalates for Nickel‐Catalyzed Carbosilylation of Alkenes
Authors: Wang Jixin , Duan Zhili , Liu Xingchen , Dong Shoucheng , Chen Kaixin , Li Jie
Published: February 2022

We herein report the preparation of solid and salt‐stabilized silylzinc pivalates from the corresponding silyllithium reagents via transmetalation with Zn(OPiv)2. These resulting organosilylzinc pivalates show enhanced air and moisture stability and unique reactivity in the silylative difunctionalization of alkenes. Thus, a practical chelation‐assisted nickel‐catalyzed regioselective alkyl and benzylsilylation of alkenes has been developed, which provides an easy method to access alkyl silanes with broad substrate scope and wide functional group compatibility. Kinetic experiments highlight that the OPiv‐coordination is crucial to improve the reactivity of silylzinc pivalates. Furthermore, late‐stage functionalizations of druglike molecules and versatile modifications of the products illustrate the synthetical utility of this protocol.
Integrative Systemic Therapy: Integrating Individual, Couple, and Family Therapy
Authors: He Yaliu , Fisher Adam R. , Swanson Sarah E. , Lebow Jay L.
Published: February 2022

Couple and family therapy is distinguished from individual therapy due to its focus on the interactional patterns between family members. However, there is plenty of overlap because of the reciprocal relationship between individual psychopathology and its relational contexts. Many clients seeking individual therapy aim to improve their relationships, and couples and families who have relational difficulties often have at least one partner with some type of psychopathology. This article presents integrative systemic therapy (IST) as a method for integrating individual, couple, and family therapy. IST is a multitheoretical and multisystemic perspective that utilises concepts and interventions from a variety of therapies for a broad variety of presenting concerns and populations, including individuals, couples, and families. In IST, a repetitive pattern of interaction is co‐occurring at two levels – within an individuals' minds (i.e., intrapsychic) and externally in people's interactions with others in their system (i.e., interpersonal) – and they influence each other. Therefore, IST therapists utilise various interventions from individual and couple and family therapy within a case to disentangle problems occurring at various systemic levels. The paper begins with a summary of the theoretical assumptions of IST and introduces basic terms such as sequences. This is followed by specific descriptions of two critical tools, essence and blueprint, which walk therapists through the steps of how to conduct IST and integrate individual, couple, and family therapy. Finally, two case examples are used to demonstrate this process.
Study on adsorption characteristics optimization of vertical radial flow adsorber
Authors: Xu Pan , Wen Jian , Zhao Xin , Wang Simin , Li Ke , Li Yanzhong
Published: February 2022

In view of high energy consumption, poor flow uniformity, and short adsorption period in the actual work of vertical radial flow adsorber, computational fluid dynamics (CFD) technology and multiobjective genetic algorithm (MOGA) are used to optimize its structure. Through response surface analysis, it is found that the main structural parameters affecting adsorber performance are adsorption layer length and central channel diameter. The effect analysis of characteristic structural parameters and the calculation of multiobjective optimization show that the optimized structure has the ratio of horizontal to vertical of adsorption layer about 0.29 and the area ratio of central channel to annular channel about 0.67. Compared with the original structure, the optimized structure is reduced by 9.57% on pressure drop, increased by 0.86% on flow uniformity, and increased by 17.04% on breakthrough time. The data points on the response surface are used to fit the correlation of adsorber performance and the fitting degrees are 99.7% and 99.3%, respectively, which provided a theoretical reference for the optimal design of vertical radial flow adsorber.
Effects of nano‐TiO2 on the structure and properties of composite materials constructed from eggshell powder/poly(butyleneadipate‐co‐terephthalate)
Authors: Xu Dan , Xiong Zhouyi , Xia Changxing , Xiong Hanguo
Published: February 2022

In the present work, the effects of nano‐TiO2 on the properties and structure of eggshell powder/poly(butyleneadipate‐co‐terephthalate) (PBAT) composites were comprehensively explored. The results showed that nano‐TiO2 could promote the tensile strength and water resistance of the composite material, as well as reduce the light transmittance. Nano‐TiO2 reacted with PBAT to form the C‐O‐Ti bonds, resulted in enhanced structure stability of the composite material. Nano‐TiO2 served as the nanoscale filler to improve the internal compatibility of the composites through hydrogen bonds. Besides, the crystallization performance of the polymer system was also altered by nano‐TiO2 incorporation. These changes in structure promoted the thermal stability and surface hydrophobicity. Finally, the antibacterial test was performed, and the nanocomposite material containing nano‐TiO2 exhibited excellent antibacterial properties. This research provides a novel strategy for constructing an eggshell powder/PBAT/nano‐TiO2 nanocomposite biodegradable plastic that could be used for the development of antibacterial materials.
Cerebellar demyelination and neurodegeneration associated with mTORC1 hyperactivity may contribute to the developmental onset of autism‐like neurobehavioral phenotype in a rat model
Authors: Kútna Viera , O'Leary Valerie Bríd , Hoschl Cyril , Ovsepian Saak V.
Published: February 2022

The cerebellum hosts more than half of all neurons of the human brain, with their organized activity playing a key role in coordinating motor functions. Cerebellar activity has also been implicated in the control of speech, communication, and social behavior, which are compromised in autism spectrum disorders (ASD). Despite major research advances, there is a shortage of mechanistic data relating cellular and molecular changes in the cerebellum to autistic behavior. We studied the impact of tuberous sclerosis complex 2 haploinsufficiency (Tsc2+/−) with downstream mTORC1 hyperactivity on cerebellar morphology and cellular organization in 1, 9, and 18 m.o. Eker rats, to determine possible structural correlates of an autism‐like behavioural phenotype in this model. We report a greater developmental expansion of the cerebellar vermis, owing to enlarged white matter and thickened molecular layer. Histochemical and immunofluorescence data suggest age‐related demyelination of central tract of the vermis, as evident from reduced level of myelin‐basic protein in the arbora vitae. We also observed a higher number of astrocytes in Tsc2+/− rats of older age while the number of Purkinje cells (PCs) in these animals was lower than in wild‐type controls. Unlike astrocytes and PCs, Bergmann glia remained unaltered at all ages in both genotypes, while the number of microglia was higher in Tsc2+/− rats of older age. The convergent evidence for a variety of age‐dependent cellular changes in the cerebellum of rats associated with mTORC1 hyperactivity, thus, predicts an array of functional impairments, which may contribute to the developmental onset of an autism‐like behavioral phenotype in this model.

Lay Summary

This study elucidates the impact of constitutive mTORC1 hyperactivity on cerebellar morphology and cellular organization in a rat model of autism and epilepsy. It describes age‐dependent degeneration of Purkinje neurons, with demyelination of central tract as well as activation of microglia, and discusses the implications of these changes for neuro‐behavioral phenotypes. The described changes provide new indications for the putative mechanisms underlying cerebellar impairments with their age‐related onset, which may contribute to the pathobiology of autism, epilepsy, and related disorders.
Large‐Scale Synthesis of Nanostructured Carbon‐Ti4O7 Hollow Particles as Efficient Sulfur Host Materials for Multilayer Lithium‐Sulfur Pouch Cells
Authors: Mei Shilin , Siebert Andreas , Xu Yaolin , Quan Ting , Garcia‐Diez Raul , Bär Marcus , Härtel Paul , Abendroth Thomas , Dörfler Susanne , Kaskel Stefan , Lu Yan
Published: February 2022

Applications of advanced cathode materials with well‐designed chemical components and/or optimized nanostructures promoting the sulfur redox kinetics and suppressing the shuttle effect of polysulfides are highly valued. However, in the case of actual lithium‐sulfur (Li−S) batteries under practical working conditions, one long‐term obstacle still exists, which is mainly due to the difficulties in massive synthesis of such nanomaterials with low cost and ease of control on the nanostructure. Herein, we develop a facile synthesis of carbon coated Ti4O7 hollow nanoparticles (C−Ti4O7) using spherical polymer electrolyte brush as soft template, which is scalable via utilizing a minipilot reactor. The C−Ti4O7 hollow nanoparticles provide strong chemical adsorption to polysulfides through the large polar surface and additional physical confinement by rich micro‐ & mesopores and have successfully been employed as an efficient sulfur host for multilayer pouch cells. Besides, the sluggish kinetics of the sulfur and lithium sulfide redox mechanism can be improved by the highly conductive Ti4O7 via catalyzation of the conversion of polysulfides. Consequently, the C−Ti4O7 based pouch cell endows a high discharge capacity of 1003 mAh g−1 at 0.05 C, a high‐capacity retention of 83.7 % after 100 cycles at 0.1 C, and a high Coulombic efficiency of 97.5 % at the 100th cycle. This work proposes an effective approach to transfer the synthesis of hollow Ti4O7 nanoparticles from lab‐ to large‐scale production, paving the way to explore a wide range of advanced nanomaterials for multilayer Li−S pouch cells.
Comparing stimulus equivalence‐based instruction to self‐study of videos to teach examples of sign language to adults
Authors: Longo Angelina , Reeve Kenneth F. , Jennings Adrienne M. , Vladescu Jason C. , Reeve Sharon A. , Colasurdo Christopher R.
Published: February 2022

The current study compared equivalence‐based instruction (EBI) to self‐study of American Sign Language (ASL) videos to teach eight 3‐member classes of signs with 24 college students. Four of the equivalence classes consisted of verbs (i.e., throw, touch, blow, spin) and four classes were object nouns (i.e., truck, dollar, egg, ball). Each class consisted of (a) a picture corresponding to the targeted sign, (b) a video clip depicting the sign's topography, and (c) a printed corresponding word. Pretests and posttests assessed the degree to which participants (a) showed emergence of classes during match‐to‐sample (MTS) tests, (b) could sign both single words and verb‐noun pairs (i.e., speaker tasks), and (c) could comply with signed requests consisting of ASL verb‐noun pairs (i.e., listener tasks). EBI consisted of training the AB relation (picture to video clip) followed by tests of all possible derived relations. The AC relation (picture to printed word) was not trained because it was assumed to be present in the participants' repertoires. Self‐study consisted of viewing video clips of the eight ASL signs simultaneously presented with the printed word. The MTS posttest showed equivalence classes emerged for all participants from both EBI and self‐study groups. In addition, all EBI participants met passing criterion for emitting all single signs, all verb‐noun sign pairs, and they complied with all listener tasks. In contrast, only 4 of 12 participants from the self‐study group emitted the single signs. After re‐exposure to self‐study, most participants then passed all posttests. These results are important because they demonstrate recombinative generalization of ASL signs, which increases the utility of ASL skills.
Engineering Corynebacterium glutamicum for synthesis of poly(3‐hydroxybutyrate) from lignocellulose biomass
Authors: Jin Ci , Li Jing , Huang Zhen , Han Xushen , Bao Jie
Published: February 2022

Lignocellulose is the only feasible carbohydrates feedstock for commercial scale and carbon neutral production of poly(3‐hydroxybutyrate) (PHB) biopolymer by its great abundance and availability. Microbial cell factories for fermentative PHB synthesis are highly restricted by the growth suppression of inhibitors from lignocellulose pretreatment. This study targeted a potential PHB‐producing cell factory Corynebacterium glutamicum owing to its strong inhibitors tolerance. A systematic metabolic engineering was conducted starting with the stable PHB synthesis pathway construction from glucose and xylose, followed by the enhancement of PHB synthesis on PHA synthase activity and stability, cell morphology modification, and growth factors regulation. The relocation of the PHA synthase on the cell membrane guided by secrete signal peptides and cell membrane display motifs increased the PHB content by 2.4 folds. Excessive nitrogen preferentially promoted the PHB synthesis capacity and resulted in the PHB content increased by 13.3 folds. Modification of the genes responsible for cell division changed the cell morphology but the cell size was not enlarged to a PHB accumulation favorable environment. The metabolic engineering of C. glutamicum resulted in a high fermentative production of PHB using wheat straw as feedstock. This study provided an important microbial cell factory choice for PHB production using lignocellulose feedstock.
UPLC–MS/MS method for the determination of voriconazole plasma concentration from pediatric patients with hematologic tumors: An application toward personalized therapy
Authors: Wen Zhi‐peng , Zhang Hong , Li Qin , Hu Chu‐jiao , Yang Cheng‐li , Fan Xing‐hua , Zheng Zhi‐chang , Li Ming , Tan Lin , Tan Rong , Xia Bin‐yi , Ji Jing , Bai Yang , Yang Yi , Zheng Xiao‐li , Yang Ji‐hong
Published: February 2022

Untreated invasive fungal infection is one of the important risk factors affecting the prognosis of pediatric patients with hematologic tumors. Voriconazole (VOR) is the first‐line antifungal drug for the treatment of Aspergillus infections. In order to reduce the risk of adverse drug reactions while producing an ideal antifungal effect, therapeutic drug monitoring was performed to maintain the VOR plasma concentration in a range of 1,000–5,500 ng/ml. In the present study, a reliable, accurate, sensitive and quick ultra‐high performance liquid chromatograph–tandem mass spectrometry (UPLC–MS/MS) method was developed for the determination of the VOR level. Protein precipitation was performed using acetonitrile, and then the chromatographic separation was carried out by UPLC using a C18 column with the gradient mobile phases comprising 0.1% methanoic acid in acetonitrile (A) and 0.1% methanoic acid in water (B). In the selective reaction monitor mode, the mass spectrometric detection was carried out using an TSQ Endura triple quadruple mass spectrometer. The performance of this UPLC–MS/MS method was validated as per the National Medical Products Administration for Bioanalytical Method Validation. Additionally, the plasma concentrations of VOR in pediatric patients with hematologic tumors were detected using this method, and the analyzed results were used for personalized therapy.
Carcinosarcoma is an aggressive subtype of bladder cancer: A population‐based study
Authors: Liu Lin , Zhu Jinglan , Tian Yun
Published: February 2022

Background

Case reports of bladder carcinosarcoma (BCS) indicate high rates of recurrence and metastasis and poor prognosis. However, the differences in clinicopathologic characteristics and prognosis between BCS and conventional bladder cancer histologies (transitional cell carcinoma [TCC], squamous cell carcinoma [SCC] and adenocarcinoma [AC]) have not been fully clarified in a large study. Therefore, we conducted a large population‐based study to further investigate these differences.

Patients and methods

Information on patients with BCS and conventional bladder cancer (TCC, SCC or AC) was extracted from the Surveillance, Epidemiology, and End Results database. Categorical variables were compared using Pearson's chi‐squared test or Fisher's exact test. Survival analysis was carried out using the Kaplan–Meier method, and differences in survival were assessed using the log‐rank test. Propensity score matching analysis was conducted to calibrate the differences between the baseline characteristics, after which Cox regression analysis was applied to calculate the hazard ratios and 95% confidence intervals of BCS compared to other subtypes. Subgroup analysis and related interaction were tested to evaluate the consistency and heterogeneity of results.

Results

We enrolled 152 patients with BCS and 180,196 patients with TCC, SCC or AC. Our results showed that BCS was associated with poor differentiation, advanced stage and an unfavourable overall survival and cancer‐specific survival. BCS had a worse prognosis than TCC and AC, but no statistically significant difference in survival was noted between BCS and SCC.

Conclusions

BCS is a more aggressive bladder cancer than TCC and AC but is comparable to SCC. These findings broaden our understanding of BCS and may be helpful in clinical practice.
Accelerated silicosis and silico‐tuberculosis: A difficult diagnosis
Authors: Khemakhem Rim , Moussa Nedia , Kotti Amina , Feki Wiem , Mnif Zeineb , Feki Walid , Kammoun Samy
Published: February 2022

It is well established that exposure to respirable crystalline silica is associated with higher mortality. Such exposures are associated with an increased risk of silico‐tuberculosis, silicosis, and other respiratory morbidities. We report two cases of accelerated silicosis, complicated with pulmonary tuberculosis and pulmonary infection.
Iron‐Catalyzed Oxidative C−O and C−N Coupling Reactions Using Air as Sole Oxidant**
Authors: Purtsas Alexander , Rosenkranz Marco , Dmitrieva Evgenia , Kataeva Olga , Knölker Hans‐Joachim
Published: February 2022

We describe the oxygenation of tertiary arylamines, and the amination of tertiary arylamines and phenols. The key step of these coupling reactions is an iron‐catalyzed oxidative C−O or C−N bond formation which generally provides the corresponding products in high yields and with excellent regioselectivity. The transformations are accomplished using hexadecafluorophthalocyanine−iron(II) (FePcF16) as catalyst in the presence of an acid or a base additive and require only ambient air as sole oxidant.
Insights into the Electronic Structure of a U(IV) Amido and U(V) Imido Complex
Authors: Köhler Luisa , Patzschke Michael , Bauters Stephen , Vitova Tonya , Butorin Sergei M. , Kvashnina Kristina O. , Schmidt Moritz , Stumpf Thorsten , März Juliane
Published: February 2022

Reaction of the N‐heterocylic carbene ligand iPrIm (L1) and lithium bis(trimethylsilyl)amide (TMSA) as a base with UCl4 resulted in U(IV) and U(V) complexes. Uranium's +V oxidation state in (HL1)2[U(V)(TMSI)Cl5] (TMSI=trimethylsilylimido) (2) was confirmed by HERFD‐XANES measurements. Solid state characterization by SC‐XRD and geometry optimisation of [U(IV)(L1)2(TMSA)Cl3] (1) indicated a silylamido ligand mediated inverse trans influence (ITI). The ITI was examined regarding different metal oxidation states and was compared to transition metal analogues by theoretical calculations.
Retro‐Friedel–Crafts‐Type Acidic Ring‐Opening of Triptycenes: A New Synthetic Approach to Acenes
Authors: Iwata Takayuki , Kawano Ryusei , Fukami Takuto , Shindo Mitsuru
Published: February 2022

Invited for the cover of this issue is the group of Takayuki Iwata, Mitsuru Shindo, and co‐workers at Kyushu University. The image depicts ring‐opening of triptycenes to afford corresponding anthrones by acid treatment. Read the full text of the article at 10.1002/chem.202104160.
Semiclassical Trajectory Studies of Reactive and Nonreactive Scattering of OH(A2Σ+) by H2 Based on an Improved Full‐Dimensional Ab Initio Diabatic Potential Energy Matrix
Authors: Han Shanyu , de Oliveira‐Filho Antonio G. S. , Shu Yinan , Truhlar Donald G. , Guo Hua
Published: February 2022

We present a new full‐dimensional diabatic potential energy matrix (DPEM) for electronically nonadiabatic collisions of OH(A 2Σ+) with H2, and we calculate the probabilities of electronically adiabatic inelastic collisions, nonreactive quenching, and reactive quenching to form H2O+H. The DPEM was fitted using a many‐body expansion with permutationally invariant polynomials in bond‐order functions to represent the many‐body part. The dynamics calculations were carried out with the fewest‐switches with time uncertainty and stochastic decoherence (FSTU/SD) semiclassical trajectory method. We present results both for head‐on collisions (impact parameter b equal to zero) and for a full range of impact parameters. The results are compared to experiment and to earlier FSTU/SD and quantum dynamics calculations with a previously published DPEM. The various theoretical results all agree that nonreactive quenching dominates reactive quenching, but there are quantitative differences between the two DPEMs and between the b=0 results and the all‐b results, especially for the probability of reactive quenching.
The formation of “mega‐flocks” depends on vegetation structure in montane coniferous forests of Taiwan
Authors: Liao Chun‐Chieh , Ding Tzung‐Su , Chen Chao‐Chieh
Published: February 2022

A mixed‐species bird flock is a social assemblage where two or more bird species are moving together while foraging and might benefit from increased foraging efficiency and antipredator vigilance. A “mega‐flock,” which includes flocking species from different vegetation strata, often exhibits high species diversity. Mechanisms for the formation of mega‐flocks have not yet been explored. In this study, we evaluated the influence of vegetation structure and bird species diversity in driving the occurrence of mega‐flocks. We investigated the composition of mixed‐species flocks, local bird communities, and vegetation structure in five vegetation types of two high‐elevation sites in central Taiwan. Mega‐flocks occurred more frequently in pine woodland than later successional stages of coniferous forests. However, species richness/diversity of local bird communities increased along successional stages. Therefore, vegetation variables exhibit more influence on the occurrence of mega‐flocks than local bird communities. Besides foliage height diversity, understory coverage also showed positive effects on flock size of mixed‐species flocks. Our results indicated that pine woodlands with more evenly distributed vegetation layers could facilitate the interactions of canopy and understory flocks and increase the formation of mega‐flocks and thus the complexity of mixed‐species flocks.
Fabrication of Redox‐ and pH‐Sensitive Self‐Assembled Nano‐Micelles with Pegylated β‐Cyclodextrin for Codelivery of Doxorubicin and Cyclopalladated Ferrocene
Authors: Lu Xiangyu , Du Guoyuan , Zhang Zhonghui , Gong Guidong , Cai Wentao , Wu Liji , Zhao Gang
Published: February 2022

We report a dual‐responsive, self‐assembled nano micelle for co‐delivery of doxorubicin (DOX) and a previously reported cyclopalladated anti‐cancer agent (CP). In this micelle system, doxorubicin and CP were electrostatically complexed to form a hydrophobic core while a conjugation of polyethylene glycol and β‐cyclodextrin (CD) was designed to construct the hydrophilic out‐layer and stabilize the micelle. The interaction between pegylated CD and DOX‐CP composite was achieved via inclusion of ferrocene moiety by CD, which could be broken by stimulating ROS that is over‐expressed in many cancer cell lines. Moreover, the DOX‐CP adduct can be destabilized under an acidic environment that exists in most solid tumors, which can further disassemble the micelle and release the two drugs. The fabricated micelle was characterized by TEM, DLS and its stimulus‐responsive characteristic were confirmed by drug‐release profile. The in vitro cellular cytotoxicity was also evaluated, which showed improved anti‐cancer effect of drug‐loaded micelle compared to free drugs.
The Hypersilyl Substituent in Heavier Low‐Valent Group 14 Chemistry
Authors: Gour Kritika , Bisai Milan Kumar , Sen Sakya S.
Published: February 2022

The isolation of unusual compounds with low‐valent main‐group elements would not have been possible without the development of a series of sterically demanding ligands with bulky substituents. While early literature recognizes the advent of the sterically demanding tris(trimethylsilyl)silyl (SiMe3)3Si‐group, also known as hypersilyl group, to stabilize species with new coordination modes for the main group elements, it has largely been more recent studies that have utilized this group for isolating stable compounds with low‐valent main‐group elements. Such compounds are not only interesting from the structure‐bonding point of view but showcase potential for small molecule activation under ambient conditions. This review will cover the recent developments in stabilizing unusual compounds with group 14 elements using the exceptionally strong σ‐donor properties and pronounced steric effects of the hypersilyl moiety, emphasizing their synthesis, structure, and reactivity.
Recent Progress on the Mild Deprotection of Dithioketals, Dithioacetals, and Oxathiolanes
Authors: Yan Jun , Pozzo Jean‐Luc , Hamze Abdallah , Provot Olivier
Published: February 2022

Reactions for the deprotection of carbonyl derivatives have been of considerable interest to the scientific community. In recent years efforts have been made to develop mild, experimentally simple, and environmentally friendly methods. This update to previous research provides a comprehensive review of processes for the deprotection of thioacetals, thioketals and oxathiolanes to the corresponding carbonyl compounds which have been published since 2006. The main approaches used iodonium or bromonium ions, oxidants, photocatalysis, metal salts or, slightly acidic hydrolysis conditions. For each protocol, representative examples will illustrate the scope of the process and its tolerance towards functional groups.
Single metal atoms catalysts—Promising candidates for next generation energy storage and conversion devices
Authors: Lei Zhihao , Sathish CI , Liu Yanpeng , Karokoti Ajay , Wang John , Qiao Liang , Vinu Ajayan , Yi Jiabao
Published: February 2022

Single‐metal‐atom catalysts (SMACs) with the merits of maximum atom utilization, peculiar electronic structure, and adjustable coordination environment, have emerged as the rising stars. They are not only regarded as the promising electrocatalysts, but also show unconventionally excellent alkali storage, thus enabling them for energy devices. In this work, we review the up‐to‐date progress of single metal atom catalysts including the detailed synthetic strategies and all sorts of applications in energy storage and conversion. In addition, we also discuss intrinsic catalytic effects, degradation mechanism, modulation approaches, support structure design, current challenges, and potential development trends. This work may shed light on developing high‐performance SMACs using a variety of strategies for catalytic and energy applications.

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Cross‐sectional study on knowledge and attitude of telemedicine in medical students of Nepal
Authors: Kunwar Bijay , Dhungana Ayushma , Aryal Binay , Gaire Arjun , Adhikari Aramva Bikram , Ojha Rajeev
Published: February 2022

Background and Aims

Telemedicine is the delivery of healthcare services from distance using information and communication technology. It helps in overcoming the geographical physical barrier, increasing access to the healthcare services. Telemedicine has been growing in Nepal, with several hospitals and medical organizations providing services since 2006. COVID‐19 pandemic ignited significant interests in it, which previously remained unnoticed, realizing its importance for the present and future. The objective of this study was to evaluate the knowledge and attitude toward telemedicine among medical students in Nepal.

Methods

An observational study among medical students in 19 medical colleges in Nepal was performed from May to June using Google forms. The survey consisted of 27 questions including information on demography and telemedicine exposure, its status in Nepal, interest, and plans for its future utilization.

Results

Of 146 total surveyed students, 77.4% (n = 113) provided their views regarding telemedicine. Among students with knowledge of telemedicine, only 8.8% (n = 10) had attended some training. Only 6% (n = 4) of those who had previously consulted through telemedicine labeled their experience as poor. Exactly 88.5% (n = 100) were not satisfied with present telemedicine practices and coverage and 43.4% (n = 49) were optimistic about using telemedicine in future. Irrespective of location of medical colleges (Kathmandu Valley or outside) or levels of study (preclinical or clinical), students had similar knowledge and attitude regarding telemedicine.

Conclusion

The participants have good knowledge regarding the importance of telemedicine but only few of them are educated regarding its usage. Despite limited exposure to telemedicine, participants advocate for expansion and wide use of telemedicine due to economy, technological advancement, and topographic diversities. Internet, sense of reliability, privacy issue, and lack of proper curriculum seem to have raised question on their positive attitude. Formal and structured education may enable optimistic aspirants to integrate telemedicine skills with medical care delivery with ease.
Improvement of the heat transfer quality by air cooling of three‐heated obstacles in a horizontal channel using the lattice Boltzmann method
Authors: Lahmer El Bachir , Admi Youssef , Moussaoui Mohammed Amine , Mezrhab Ahmed
Published: February 2022

This study focuses on the cooling of three heated obstacles with different heights mounted on the bottom of the channel wall using different aspects that influence the enhancement of the heat exchange, as is known in the concept of cooling electronic devices. The lattice Boltzmann method associated with multiple relaxation times (LBM‐MRT) was adopted to simulate the physical configurations of the studied system. In this context, the D2Q9 and D2Q5 models are applied to describe the fluid flow behavior and conjugate heat transfer, respectively. The evaluation of heat exchange between the cold fluid and three‐heated obstacles has been accurately analyzed under the effect of several parameters such as Reynolds number, obstacle spacing, and thermal conductivity ratio. In addition, the setting of two and three fluids flow inlets were also studied. The results are presented in terms of streamlines, isotherms, and local Nusselt curves. The heat transfer increases with increasing solid‐fluid thermal conductivity. It is also more pronounced for large Reynolds numbers. Moreover, the heat transfer significantly enhances for the second and third obstacles when obstacle spacing increases. The improvement of the heat transfer is performed by the implementation of several jet flows in the studied system.
On the development of a neoantigen vaccine for the prevention of Lynch Syndrome
Authors: Solomon Adam , Alteber Zoya , Bassan David , Sharbi‐Yunger Adi , Esbit Simon , Tzehoval Esther , Eisenbach Lea
Published: February 2022

Lynch Syndrome (LS) is an autosomal dominant genetic condition that causes a high risk of colorectal cancer. The hallmark of LS is genetic instability as a result of mismatch repair (MMR) deficiency, particularly in repetitive low complexity regions called microsatellites (MS). MLH1−/− mice deficient in MMR are prone to developing tumors in the colon, upon oral administration of dextran sodium sulfate (DSS), at a rate of more than 70%. Using this LS mouse model, we found a novel tumor neo‐antigen from a deletion mutation of the coding MS in the SENP6 gene that prevented tumorigenesis or hindered tumor growth rate in immunized mice. This was accomplished via high throughput exome sequencing of DSS‐induced colorectal tumors in the MLH1−/− mice and predicting the most highly immunogenic mutant gene products processed and presented as antigens in C57BL/6 MHC‐I molecules. Throughout our study, we were able to prove the validity of the vaccine by analyzing the colorectal tumors in immunized DSS‐treated mice using either our epitope, called Sp6D1, or an unrelated peptide as a negative control. Tumors developed in this context were found to be antigenic and Sp6D1‐specific CD8+ tumor infiltrating lymphocytes were detected by flow cytometry and cytotoxic T lymphocytes (CTL) killing assays. Additionally, immunohistochemistry showed that tumor‐adjacent tertiary lymphoid organs were a potentially significant source of CD8+ lymphocytes. Altogether, our results indicate that there may be a protective effect to patients carrying LS mutations through the induction of a peptide‐specific CTL response from the use of neoepitope vaccination.
International migrants' right to sexual and reproductive health care
Authors: Chen Y. Y. Brandon
Published: February 2022

International migration puts people's sexual and reproductive health (SRH), particularly those of women and children, at increased risk. However, many international migrants are denied access to timely and adequate SRH information, goods, and services by governments and/or service providers. This article reviews relevant international human rights treaties to argue that the barriers faced by migrants in accessing SRH care constitute violations of international law. It is well established that migrants are guaranteed access to SRH care as a part of their right to health, as well as the rights enjoyed by vulnerable populations. Increasingly, hindrance of migrants' access to SRH care is also recognized as a threat to their rights to life and equality with non‐migrants. The case of Toussaint v Canada illustrates how governments may be held accountable by human rights treaty monitoring bodies when they fail to respect and fulfill migrants' right to SRH care.
ImageGP: An easy‐to‐use data visualization web server for scientific researchers
Authors: Chen Tong , Liu Yong‐Xin , Huang Luqi
Published: February 2022

Data visualization plays a crucial role in illustrating results and sharing knowledge among researchers. Though many types of visualization tools are widely used, most of them require enough coding experience or are designed for specialized usages, or are not free. Here, we present ImageGP, a specialized visualization platform designed for biology and chemistry data illustration. ImageGP could generate generalized plots like lines, bars, scatters, boxes, sets, heatmaps, and histograms with the most common input content in a user‐friendly interface. Normally plotting using ImageGP only needs a few mouse clicks. For some plots, one only needs to just paste data and click submit to get the visualization results. Additionally, ImageGP supplies up to 26 parameters to meet customizable requirements. ImageGP also contains specialized plots like volcano plot, functional enrichment plot for most omics‐data analysis, and other four specialized functions for microbiome analysis. Since 2017, ImageGP has been running for nearly 5 years and serving 336,951 visits from all over the world. Together, ImageGP (http://www.ehbio.com/ImageGP/) is an effective and efficient tool for experimental researchers to comprehensively visualize and interpret data generated from wet‐lab and dry‐lab.
Three‐dimensional knotting of W17O47@PEDOT:PSS nanowires enables high‐performance flexible cathode for dual‐functional electrochromic and electrochemical device
Authors: Zhao Qi , Wang Jinkai , Ai Xinghui , Duan Yujuan , Pan Zhenghui , Xie Shaorong , Wang John , Gao Yanfeng
Published: February 2022

An efficient integration of electrochromic and electrochemical devices into one flexible entity enables both energy storage and energy‐saving dual‐functionalities. For this purpose, achieving both high electrochromic and electrochemical performance is the key aspect. Herein, a new 3D architecture is successfully made by knotting W17O47@PEDOT (poly(3,4‐ethylenedioxythiophene)):PSS (poly(styrenesulfonate)) nanowires with NaWO3 nanoknots, and interestingly, the 3D W17O47/(NaWO3‐knots)@PEDOT:PSS cathode thus‐made simultaneously exhibits a large optical modulation (79.7% at 633 nm), an ultra‐long cycling life (76% of original optical modulation retained after 12 400 cycles), and a high areal capacitance (55.1 mF cm−2 at 0.1 mA cm−2). Our density functional theory (DFT) calculations demonstrate that the much improved dual‐functional performance is correlated to the raised electronic conductivity and ion adsorption at the W17O47/(NaWO3 nanoknots) interface, together with the ion adsorption of PEDOT:PSS in the 3D‐knotted architecture. As a proof‐of‐concept application, different‐sized flexible dual‐functional electrochromic/electrochemical devices (FDEDs) were assembled and investigated for various application scenarios, including a smart window (15 cm × 10 cm), a wearable wristband (20 cm × 2.5 cm), and a smart eyeglass. The smart window made of the FDED enables a large temperature difference of 27.6°C confirm‐tested in model houses, where the energy source also powers three light‐emitting diodes (LEDs). The understandings of the key governing principles in the electrodes and dual‐functionalities provide a timely foundation for the new generation flexible multifunctional devices.

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ThPOK Inhibits Osteoclast Formation Via NFATc1 Transcription and Function
Authors: Zou Wei , Izawa Takashi , Rohatgi Nidhi , Zou Steven Y , Li Yongjia , Teitelbaum Steven L
Published: February 2022

Both LRF (Zbtb7a) and ThPOK (Zbtb7b) belong to the POK (BTB/POZ and Kruppel) family of transcription repressors that participate in development, differentiation, and oncogenesis. Although LRF mediates osteoclast differentiation by regulating NFATc1 expression, the principal established function of ThPOK is transcriptional control of T‐cell lineage commitment. Whether ThPOK affects osteoclast formation or function is not known. We find that marrow macrophage ThPOK expression diminishes with exposure to receptor activator of NF‐kB ligand (RANKL), but ThPOK deficiency does not affect osteoclast differentiation. On the other hand, enhanced ThPOK, in macrophages, substantially impairs osteoclastogenesis. Excess ThPOK binds the NFATc1 promoter and suppresses its transcription, suggesting a mechanism for its osteoclast inhibitory effect. Despite suppression of osteoclastogenesis by excess ThPOK being associated with diminished NFATc1, osteoclast formation is not rescued by NFATc1 overexpression. Thus, ThPOK appears to inhibit NFATc1 transcription and its osteoclastogenic capacity, while its depletion has no effect on the bone‐resorptive cell. © 2022 The Authors. JBMR Plus published by Wiley Periodicals LLC on behalf of American Society for Bone and Mineral Research.
Underlying mechanisms of disruptive mood dysregulation disorder in children: A systematic review by means of research domain criteria
Authors: Brænden Astrid , Zeiner Pål , Coldevin Marit , Stubberud Jan , Melinder Annika
Published: February 2022

Background

A systematic overview of underlying mechanisms in the new disruptive mood dysregulation disorder (DMDD) diagnosis is needed. The Research Domain Criteria (RDoC) represent a system of six domains of human functioning, which aims to structure the understanding of the nature of mental illnesses. By means of the RDoC framework, the objective of this systematic review is to synthesize available data on children and youths <18 years suffering from DMDD as reported in peer reviewed papers.

Methods

A literature search guided by PRISMA was conducted using Medline, PsychInfo, and Embase, while the RDoC domains were employed to systematize research findings. Risk of bias in the included studies was examined.

Results

We identified 319 studies. After study selection, we included 29 studies. Twenty‐one of these had findings relating to >1 RDoC domain. The risk of bias assessment shows limitations in the research foundation of current knowledge on mechanisms of DMDD.

Discussion

Reviewing self‐report, behavior and neurocircuit findings by means of RDoC domains, we suggest that DMDD youths have a negative interpretation bias in social processes and valence systems. In occurrence of a negative stimuli interpretation, aberrant cognitive processing may arise. However, current knowledge of DMDD is influenced by lack of sample diversity and open science practices.

Conclusion

We found the six RDoC domains useful in structuring current evidence of the underlying mechanisms of DMDD. Important opportunities for future studies in this field of research are suggested. In clinical practice, this comprehensive summary on DMDD mechanisms can be used in psychoeducation and treatment plans.