bluuebunny/crossref_metadata_2025 huggingface dataset:
Boron Imidazolate Framework‐Derived Porous Carbon Nanospheres for Dual‐Mode Bioimaging‐Guided Photothermal/Sonodynamic Synergistic Cancer Therapy
Authors: Du Linyao , Ren Shuangsong , Qi Ye , Wen Ru , Feng Yue , Tong Mengying , Liu Xiaohui , Li Yachen , Che Ying
Published: April 2022

Development of efficient nanotherapeutic agents to enhance anticancer therapeutic effects is challenging. In this study, photo/sono‐dual‐responsive boron imidazolate framework‐derived single‐component porous carbon nanospheres (PCNSs) are successfully developed for dual‐mode bioimaging‐guided photothermal/sonodynamic (PTT/SDT) synergistic therapy for triple‐negative breast cancer. The PCNS not only exhibits satisfactory and excellent photothermal conversion ability under near‐infrared laser irradiation but also demonstrates a promising capability as an efficient sonosensitizer to generate cytotoxic reactive oxygen species through inertial cavitation in response to low‐intensity ultrasound stimulation. The outstanding photothermal effect enhances the blood flow in tumor tissues and thus improves the oxygen supply, helping to achieve a remarkable synergistic therapeutic effect in the PTT/SDT synergistic therapy without any tumor recurrence or systemic toxicity. Interestingly, the PCNS enables the precise visualization of solid tumors using contrast‐enhanced ultrasound and photothermal dual‐modal bioimaging techniques. Overall, this study provides valuable insights in developing all‐in‐one theranostic nanoplatforms for the clinical treatment of triple‐negative breast cancer.
2D Heterostructure of Bi2O2Se/Bi2SeOx Nanosheet for Resistive Random Access Memory
Authors: Xia Yan , Wang Jing , Chen Rui , Wang Hongbo , Xu Hang , Jiang Changzhong , Li Wenqing , Xiao Xiangheng
Published: April 2022

2D materials have shown great potential in the application of resistive random access memory (RRAM) for information storage. Much attention has been attracted from 2D semiconducting bismuth oxyselenide (Bi2O2Se) for excellent properties in multi‐performance nanoelectronics. By using a chemical vapor deposition (CVD) method, Bi2O2Se nanosheets with high quality are grown. Combining with the oxygen plasma method, 2D heterostructure of Bi2O2Se/Bi2SeOx nanosheet is realized; and the heterostructure exhibits obvious resistive switching behavior. The resistive switching mechanism is analyzed in detail, and the conductive mechanism of the fabricated device is also discussed. The resistive switching of Bi2O2Se nanosheets is endowed through the method of O2 plasma treatment, which makes it feasible for developing its application in the RRAM.
Food insecurity and time use in elderly vs. non‐elderly: An exploratory analysis
Authors: Berning Joshua , Cleary Rebecca , Bonanno Alessandro
Published: April 2022

In the US, elderly households are more food secure than younger households. A possible explanation is that increased time availability enables elderly households to adopt strategies to improve their food security. Using time use data, we find elderly households spend more time in meal preparation and eating time than younger households. Creating a matched dataset of household time use and food security, we find that meal preparation and eating time have a small contribution to differences in food insecurity between older and younger households. However, these relationships are heterogeneous depending upon marital status and age cohort of the household head.
Prescribed defoliation strategies influence soil carbon and nitrous oxide potential in pastures
Authors: Kelly Charlene N. , Koos Jordan , Griggs Thomas , Freedman Zachary B.
Published: April 2022

Cool‐season perennial grasslands are commonly used for livestock pasture. However, understanding of the belowground effects of forage defoliation (selective pressure applied by grazing) management is nascent. We investigated how defoliation management affects aboveground (forage productivity) and belowground processes (soil C/N), microbial nutrient cycling, and potential nitrous oxide [N2O] emissions). We hypothesized that rotational (moderate frequency) defoliation at low severity will increase soil organic matter (SOM) storage and microbial capacity to cycle C, N, and P, but that these changes would also lead to greater soil N2O emission potential. Data were collected from organically (OF) and conventionally managed (CF) farms with differing botanical composition in West Virginia, where three frequencies and two severities of forage defoliation were imposed. At OF, more severe defoliation decreased labile soil C content (–26%), while moderate defoliation resulted in a 39% reduction in microbial enzymatic capacity to cycle C, but not at CF. The N2O emission potential (ratio of nirK/nosZ functional gene abundance), was differentially affected by defoliation treatments at both sites. At OF, defoliation severity altered N2O emission potential, whereby low severity resulted in an 82% decrease in potential N2O emissions compared with high severity treatments. At CF, continuously defoliated plots exhibited a 71% lower N2O emission potential relative to less frequent defoliation. Belowground microbial parameters were more responsive to defoliation at OF, suggesting past management may influence how grazing management asserts belowground changes. Results suggest that defoliation management could enhance soil C storage, but potentially at the risk of increased N2O emissions.
Ausrichtung von Gastmolekülen und Defektbildung während der Porenfüllung in Metallorganischen Gerüstverbindungsdünnschichten
Authors: Baumgartner Bettina , Mashita Risa , Fukatsu Arisa , Okada Kenji , Takahashi Masahide
Published: April 2022

Der Grad der Porenfüllung definiert die Gast@MOF‐Eigenschaften in Anwendungen wie Elektronik, Optik und Gastrennung. Das Zusammenspiel von Schlüsselaspekten der Wirt‐Gast‐Wechselwirkungen, wie eine quantitative Beschreibung der Gastausrichtung oder die strukturelle Integrität des Wirts als Funktion der Porenfüllung, muss jedoch noch bestimmt werden. Polarisationsabhängige Infrarotspektroskopie in abgeschwächter Totalreflexionskonfiguration in Kombination mit Gassorption ermöglichten es, gleichzeitig die Orientierung des Gastmoleküls und strukturelle Änderungen des MOF‐Gerüsts während des Porenfüllprozesses zu untersuchen. Dabei stellten wir fest, dass sich zunächst zufällig orientierte Gastmoleküle mit zunehmender Porenfüllung während der Adsorption aus der Gasphase ausrichten. Gleichzeitig erfährt das Gerüst selbst eine reversible, vom Gastmolekül abhängige Rotation des aromatischen Liganden und einen Prozess der Ligandenablösung, wodurch Defekte induziert werden.
Highly Selective Photocatalytic CO2 Methanation with Water Vapor on Single‐Atom Platinum‐Decorated Defective Carbon Nitride
Authors: Shi Xianjin , Huang Yu , Bo Yanan , Duan Delong , Wang Zhenyu , Cao Junji , Zhu Gangqiang , Ho Wingkei , Wang Liqin , Huang Tingting , Xiong Yujie
Published: April 2022

Solar‐driven CO2 methanation with water is an important route to simultaneously address carbon neutrality and produce fuels. It is challenging to achieve high selectivity in CO2 methanation due to competing reactions. Nonetheless, aspects of the catalyst design can be controlled with meaningful effects on the catalytic outcomes. We report highly selective CO2 methanation with water vapor using a photocatalyst that integrates polymeric carbon nitride (CN) with single Pt atoms. As revealed by experimental characterization and theoretical simulations, the widely explored Pt−CN catalyst is adapted for selective CO2 methanation with our rationally designed synthetic method. The synthesis creates defects in CN along with formation of hydroxyl groups proximal to the coordinated Pt atoms. The photocatalyst exhibits high activity and carbon selectivity (99 %) for CH4 production in photocatalytic CO2 reduction with pure water. This work provides atomic scale insight into the design of photocatalysts for selective CO2 methanation.
Concise and Stereodivergent Approach to Chromanone Lactones through Copper‐Catalyzed Asymmetric Vinylogous Addition of Siloxyfurans to 2‐Ester‐Substituted Chromones
Authors: Cui Jin , Oriez Raphaël , Noda Hidetoshi , Watanabe Takumi , Shibasaki Masakatsu
Published: April 2022

Vicinal oxygen‐containing tetra‐ and tri‐substituted stereocenters exist widely in chromanone lactone and tetrahydroxanthone natural products. Their enantioselective construction in a single step remains elusive and poses a formidable challenge for chemical synthesis. Here, we report the first copper(I)‐catalyzed asymmetric vinylogous additions of siloxyfurans to 2‐ester‐substituted chromones, which enable concise and enantioselective assembly of chromanone lactones. Both syn and anti adducts can be accessed with excellent diastereo‐ and enantioselectivity by judicious choice of the chiral ligands. Our approach allowed for the efficient synthesis of (−)‐blennolide B with precise stereochemical control, which provides a formal synthesis of secalonic acid A.
Chiral Covalent Organic Framework Packed Nanochannel Membrane for Enantioseparation
Authors: Zhang Siyun , Zhou Juan , Li Haibing
Published: April 2022

A nanochannel membrane has the prospect of large‐scale separation. However, selectivity in enantioseparation is a challenge, due to the size difference between nanochannels and enantiomers. Here, we compartmented nanochannels by the in situ synthesis of a L‐tyrosine functionalized covalent organic framework (L‐Tyr‐COF). The L‐Tyr‐COF decreased the pore size of channels to match with naproxen enantiomers (S/R‐NPX) and improved the enantioselective gating. In contrast to the surface‐functionalized nanochannels (L‐Tyr channel), the L‐Tyr‐COF packed nanochannels (L‐Tyr‐COF channel) exhibited high enantioselectivity for S‐NPX and realized the enantioseparation with the enantiomer excess value up to 94.2 %. The separation flux through the highly porous L‐Tyr‐COF channel was 1.33 mmol m−2 h−1. This study provided a size‐matching strategy and the chiral covalent organic framework packed nanochannel membrane to realize enantioseparation with high selectivity and flux.
Hydroxylated Multi‐Walled Carbon Nanotubes Covalently Modified with Tris(hydroxypropyl) Phosphine as a Functional Interlayer for Advanced Lithium–Sulfur Batteries
Authors: Yang Bin , Guo Daying , Lin Peirong , Zhou Ling , Li Jun , Fang Guoyong , Wang Jinyi , Jin Huile , Chen Xi'an , Wang Shun
Published: April 2022

We have successfully constructed a new type of intercalation membrane material by covalently grafting organic tris(hydroxypropyl)phosphine (THPP) molecules onto hydroxylated multi‐walled carbon nanotubes (CNT‐OH) as a functional interlayer for the advanced LSBs. The as‐assembled interlayer has been demonstrated to be responsible for the fast conversion kinetics of polysulfides, the inhibition of polysulfide shuttle effect, as well as the formation of a stable solid electrolyte interphase(SEI) layer. By means of spectroscopic and electrochemical analysis, we further found THPP plays a key role in accelerating the conversion of polysulfides into low‐ordered lithium sulfides and suppressing the loss of polysulfides, thus rendering the as‐designed lithium–sulfur battery in this work a high capacity, excellent rate performance and long‐term stability. Even at low temperatures, the capacity decay rate was only 0.036 % per cycle for 1700 cycles.
Exploring Equilibria between Aluminium(I) and Aluminium(III): The Formation of Dihydroalanes, Masked Dialumenes and Aluminium(I) Species
Authors: Bakewell Clare , Hobson Katie , Carmalt Claire J.
Published: April 2022

The design of new reductive routes to low oxidation state aluminium (Al) compounds offers the opportunity to better understand redox processes at the metal centre and develop reactivity accordingly. Here, a monomeric AlI compound acts as a stoichiometric reducing agent towards a series of AlIII dihydrides, leading to the formation of new low oxidation state species including symmetric and asymmetric dihydrodialanes, and a masked dialumene. These compounds are formed by a series of equilibrium processes involving AlI, AlII and AlIII species and product formation can be manipulated by fine‐tuning the reaction conditions. The transient formation of monomeric AlI compounds is proposed: this is shown to be energetically viable by computational (DFT) investigations and reactivity studies show support for the formation of AlI species. Importantly, despite the potential for the equilibrium mixtures to lead to ill‐defined reactivity, controlled reactivity of these low oxidation state species is observed.
Cricoid Pressure: Contradictory Evidence Regarding a Standard Practice
Authors: Dunn Debra
Published: April 2022

The purpose of applying cricoid pressure is to prevent pulmonary aspiration of regurgitated gastric contents during airway management in mask‐ventilated patients who are at risk of aspiration. Providers may apply cricoid pressure during induction and intubation if they expect a difficult intubation or if the patient has a high risk for regurgitation. Although the application of cricoid pressure has been accepted as a standard practice worldwide, controversy persists because pulmonary aspiration can occur even when cricoid pressure is applied. The perioperative nurse should have thorough knowledge of the anatomy of the upper respiratory and gastrointestinal tracts, be able to demarcate the surface landmarks of the neck, and be skilled in applying cricoid pressure properly and safely. This article discusses cricoid pressure in the context of safe airway management as well as the perioperative nurse’s role as an assistant to the anesthesia professional when applying cricoid pressure.
Clinical Issues—May 2022
Authors: Anderson Mary Alice
Published: April 2022

THIS MONTH

Using the AORN staffing formula

Key words: safe OR staffing, direct care, indirect care, on‐call, full‐time equivalents (FTEs).

RN first assistant application prerequisites

Key words: registered nurse first assistant (RNFA), certification, curriculum, education requirements, CNOR.

Differences between preceptors and mentors

Key words: novice nurse, expert, career development, professional growth, assimilation.

Unique device identifier requirements

Key words: global unique device identification database (GUDID), automatic identification and data capture (AIDC) technology, medical device, barcode, integration.
Application of polyvinylidene fluoride membrane with demulsification property in oil–water separation
Authors: Yang Yang , Han Sheng , Yan Jincan
Published: April 2022

Membrane‐based treatment for demulsification remains a significant challenge due to membrane fouling. In this work, the demulsification and membrane separation technology were combined to design polyvinylidene fluoride (PVDF) membrane with demulsification function. The hyperbranched polyethyleneimine was prepared by the acyl chloride reaction and grafted on the PVDF membrane by dopamine. The effects of different amounts of hyperbranched polyethyleneimine on PVDF membrane were studied. The modified membrane was characterized by SEM, CA, FTIR, and XPS, and then the optimum preparation conditions were selected. The separation test shows that the modified membrane can be used to separate oil‐in‐water emulsions and the separation efficiency was more than 90%, meanwhile it showed good anti‐pollution performance owing to the water‐based protective layer on the membrane surface and the steric effect of the branches. In addition, the demulsification mechanism was analyzed and it was found that the surface tension was the key point for demulsification.
Aryl sulfonic acid catalysts: Effect of pendant group structure on activity in hydrolysis of polyethylene terephthalate
Authors: Abedsoltan Hossein , Coleman Maria R.
Published: April 2022

A series of aryl sulfonic acids were tested as catalysts for acid hydrolysis occurring at the surface of poly(ethylene) terephthalate (PET) particles. Specifically, p‐toluenesulfonic acid monohydrate (PTSA), 2‐naphthalenesulfonic acid (2‐NSA), and 1,5‐naphthalenedisulfonic acid tetrahydrate (1,5‐NDSA) were chosen to provide sulfonic acid active groups and varying hydrophobic functionality. The effect of catalyst concentration and reaction temperature on PET hydrolysis rate was studied. The aryl sulfonic acid catalysts exhibited much higher rates of PET hydrolysis than the mineral acid, H2SO4. At 150°C and 4 M catalyst, the time required to achieve more than 90% TPA yield was 3, 3, and 8 h, and 18 h for (PTSA), (2‐NSA), (1,5‐NDSA), and H2SO4, respectively. Ethyl acetate hydrolysis was performed as a model reaction to probe the activity of the catalysts in homogenous reactions to compare with the heterogenous hydrolysis reaction occurring at the PET surface. The higher catalytic activities for PET hydrolysis of the PTSA, 2‐NSA, and 1,5‐NDSA than H2SO4 was attributed to improved wetting by the reaction media and affinity of the aryl sulfonic acid catalysts for the PET surface.
Mechanically enhanced poly(lactic acid)/polyurethane blend with interfacial‐localized clay particles
Authors: Ahn Jung Hyun , Hong Joung Sook , Ahn Kyung Hyun
Published: April 2022

In this study, clays (C30B, C20A, and ) with different interlayer modifier and localization are investigated to improve mechanical properties of poly(lactic acid) (PLA)/thermoplastic polyurethane (TPU) blend based on crystallization, morphology, and rheology analyses. The mechanical properties of the PLA/TPU 70/30 blend (elongation at break: 229%, impact strength: 55 J/m) are additionally increased by the clay particles. Depending on modifiers within the particles localized at the interface, 0.1 wt% of the C30B maximizes elongation at break (289%) while 0.1 wt% of the C20A maximizes impact strength (81 J/m) due to its influence on crystal structure of PLA. Thermal analysis through differential scanning calorimeter shows that hydrophilic C30B induces ductile α' PLA crystal formation while less hydrophilic C20A induces stiff α crystal formation, which is reflected on the mechanical properties. In addition, there exists optimum degree of crystallinity for the desired mechanical properties. The excessive interfacial‐localized clay is found to interfere PLA/TPU interaction. Meanwhile, natural clay, enhances mechanical properties of blend with the reduced distance between the TPU droplets with a 0.3–3 wt% addition. In addition, rheological properties help us to design the blend and annealing condition for the desirable mechanical properties.
Flame retardancy of carboxylated polyhedral oligosilsesquioxane modified layered double hydroxide in the process of leather fatliquoring
Authors: Lyu Bin , Kou Mengnan , Gao Dangge , Luo Kang , Ma Jianzhong , Lin Yanjun
Published: April 2022

Carboxyl polyhedral oligomeric silsesquioxane(P[POSS‐MAA]) modified layered double hydroxides (LDHs) (P[POSS‐MAA]‐LDHs) was prepared by exfoliating and recombination method, which used P(POSS‐MAA) and LDHs attracted each other through electrostatic force and hydrogen bond. The structure and morphology of P(POSS‐MAA)‐LDHs were characterized by X‐ray diffraction and transmission electron microscope, which showed that LDHs was exfoliated and P(POSS‐MAA) was on the surface of LDHs. Then it was introduced into the modified zanthoxylum bungeanum seed oil(MZBMSO) to obtain MZBMSO/P(POSS‐MAA)‐LDHs and applied it in leather fatliquoring process. The effect of the introduction of P(POSS‐MAA)‐LDHs on the flame retardancy, thermal stability, thermal insulation and smoke suppression of leather was investigated. Compared to the MZBMSO treated leather, the after flame time of MZBMSO/P(POSS‐MAA)‐LDHs treated leather decreased from 84 s to 32 s, and the limiting oxygen index increased from 23.1% to 27.5%, which exhibited improvement on flame retardancy of the leather. The temperature at 50% mass loss of MZBMSO/P(POSS‐MAA)‐LDHs treated leather increased from 375.1 to 408.3°C, which showed improvement on thermal stability of the leather. And the leather treated by MZBMSO/P(POSS‐MAA)‐LDHs had reduction of the total heat release and the total smoke production around 26.8% and 65.7%, respectively, which showed that MZBMSO/P(POSS‐MAA)‐LDHs treated leather had heat insulation and smoke suppression. Flame retardant mechanism of MZBMSO/(P(POSS‐MAA)‐LDHs) treated leather involved a combination of the gaseous phase and condensed phase flame retardancy. This work provided a new material for the flame retardant field and expanded the application range of polyhedral oligomeric silsesquioxane(POSS).
Study on properties of polyurethane elastomers prepared with different hard segment structure
Authors: Zhang Shijie , Wang Kaijie , Sang Shilin , Li Yuanyuan , Tang Jialing
Published: April 2022

Four different systems of cast polyurethane elastomers were prepared through two‐step method by adjusting different isocyanates and amine chain extenders. The blocked polyurethane prepolymer synthesized by the reaction of methyl ethyl ketoxime (MEKO) and the prepolymer weakens the reactivity with the amine chain extender. The mechanical and thermal properties of cast polyurethane prepared by different combinations were analyzed through comparison. The microphase separation of hard and soft segments structure in different systems were observed by using atomic force microscope (AFM). Through dynamic mechanical analysis (DMA), the influence of various structures on the loss factor is discussed. Studying the dynamic endogenous heat of cast polyurethane (CPU) by changing the hard segment structure provides a novel idea for the construction of polyurethane with low‐damping structure.
Evaluation of Atopic Dermatitis Improvement Caused by Low‐Level, Low‐Frequency Pulsed Electromagnetic Fields
Authors: Kim Jun‐Young , Lee Ji‐Young , Lee Ja‐Woo , Lee Soo‐Kyung , Park Chang‐Soon , Yang Se‐Jung , Lee Yong‐Heum
Published: April 2022

This study aimed to evaluate the effectiveness of using low‐level, low‐frequency pulsed electromagnetic field (LLLF_PEMF) stimulation to improve atopic dermatitis induced by 2,4‐dinitrochlorobenzene (DNCB). Twenty 6‐week‐old hairless mice were randomly divided into Normal (n = 5), PEMF 15 Hz (n = 5), PEMF 75 Hz (n = 5), and Sham (n = 5) groups. Following the onset of atopic dermatitis symptoms, PEMF groups (15 and 75 Hz) were stimulated with LLLF_PEMF (15 mT) for 8 h per day for 1 week. Sensory evaluation analysis revealed a significant difference between the PEMF 15 Hz group and Sham group (P < 0.05), but these differences were not visually obvious. While both the PEMF and Sham groups had atopic dermatitis lesions, lesion size was significantly smaller in the two PEMF groups than in the Sham group (P < 0.001). Additionally, changes in epithelial thickness because of skin inflammation significantly decreased for both PEMF groups, compared with the Sham group (P < 0.001). In conclusion, these results suggest that PEMF stimulation in vivo triggers electro‐chemical reactions that affect immune response. © 2022 Bioelectromagnetics Society.
Environmental capability development in a multi‐stakeholder network setting: Dynamic learning through multi‐stakeholder interactions
Authors: Baranova Polina
Published: April 2022

The study offers a nuanced view of multi‐stakeholder networks (MSNs) as settings for capability development through learning. Unlike numerous studies of capability development in networks being framed through a resource‐based perspective, the study applies a knowledge‐based view. This approach addresses the limitations of a generic treatment of learning towards capability development in the existing literature. The paper explores the learning mechanisms and characteristics of learning towards environmental capability in an MSN where stakeholder interactions shape the learning. A qualitative case study research design is used to explore capability development experiences of 15 organisations as part of a well‐established pro‐environmental MSN with over 140 members operating in the Midlands. The study reveals a synergetic pattern in the technical, relational and sustainability skills development towards environmental capability. Capability development is also characterised by situated, collective and opportunity‐led learning features. The findings confirm the significance of a stakeholder diversity for the development of relational skills in a network setting. The study advances a knowledge‐based view of capability development by framing the MSNs as dynamic learning systems for capability development. Managerial implications are drawn including the broadening of the skills spectrum for environmental capability development, paying attention to the learning settings and patterns of learning as part of capability development and engaging with MSNs as dynamic learning systems for sustainable development.
Development of a server‐based integrated virtual laboratory for digital electronics
Authors: Ersoy Mevlüt , Kumral Cem D. , Çolak Recep , Armağan Hamit , Yiğit Tuncay
Published: April 2022

In this study, a virtual laboratory has been developed to enable the effective running of applied courses in formal and distance education. Embedded systems, field programmable gate arrays (FPGA), application programming interfaces (API), and web‐based software infrastructure are used together in the virtual laboratory. Experiments belonging to digital electronics and digital communication courses can be performed by the students in the developed experiment set. Process steps performed by the student in the experiments can be followed by the designed log circuit. Every transaction performed on the experiment set was recorded and a web environment was provided to the educators where they could evaluate the experiment process. Two groups of students were formed to evaluate the success of the virtual laboratory. The first group performed the circuit setup using the traditional method and the second group on the developed virtual laboratory. According to the survey questions directed to the students, it was revealed that the use of the virtual laboratory informal and distance education would bring positive results and provide equal opportunities for disadvantaged individuals. At the same time, it was revealed that a virtual laboratory has been developed that will provide cost benefits in educational institutions.
Anacardic Acid Derivatives Affect thein VitroReactions of Photosynthesis
Authors: de Carvalho Ana Calheiros , Severino Richele Priscila , Abubakar Mustapha Ngaski , Machado Fernando Cassas Salles , Bassicheto Milena Costa , Di Gioia Silva Giordanno , Vieira Paulo Cezar , Veiga Thiago A. M.
Published: April 2022

The dichloromethane extract of the cashew nuts fromAnacardium occidentalewas fractionated by rotation locular countercurrent chromatography aimed at discovering metabolites that could be useful as new models for photosynthesis inhibitors. The chemical fractionation afforded a complex mixture of anacardic acids, which upon catalytic hydrogenation yielded anacardic acid (1). Methylation of1via reaction with diazomethane afforded an ester2. Both compounds were evaluated using polarographic approaches and fluorescence studies of chlorophylla(ChLa). Thein vitroassays informed the decision for the classification of1and2as Hill reaction inhibitors. Besides that,1inhibited the donor side of the PSII, while2acted as an energy transfer inhibitor. Therefore, this study is important for the development of herbicides.
Influence of Ring Modifications on Nucleolar Stress Caused by Oxaliplatin‐Like Compounds**
Authors: McDevitt Christine E. , Guerrero Andres S. , Smith Haley M. , DeRose Victoria J.
Published: April 2022

Oxaliplatin, a platinum compound in broad clinical use, can induce cell death through a nucleolar stress pathway rather than the canonical DNA damage response studied for other Pt(II) compounds. Previous work has found that the oxaliplatin 1,2‐diaminocyclohexane (DACH) ring but not the oxalate leaving group is important to the ability to induce nucleolar stress. Here we study the influence of DACH ring substituents at the 4‐position on the ability of DACH−Pt(II) compounds to cause nucleolar stress. We determine that DACH−Pt(II) compounds with 4‐position methyl, ethyl, or propyl substituents induce nucleolar stress, but DACH−Pt(II) compounds with 4‐isopropyl substituents do not induce nucleolar stress. This effect is independent of whether the substituent is in the axial or equatorial position relative to the trans diamines of the ligand. These results suggest that spatially sensitive interactions could be involved in the ability of platinum compounds to cause nucleolar stress.
Synthetic Activity of Recombinant Whole Cell Biocatalysts Containing 2‐Deoxy‐D‐ribose‐5‐phosphate Aldolase from Pectobacterium atrosepticum
Authors: Varela Romina Fernández , Valino Ana Laura , Abdelraheem Eman , Médici Rosario , Sayé Melisa , Pereira Claudio A. , Hagedoorn Peter‐Leon , Hanefeld Ulf , Iribarren Adolfo , Lewkowicz Elizabeth
Published: April 2022

In nature 2‐deoxy‐D‐ribose‐5‐phosphate aldolase (DERA) catalyses the reversible formation of 2‐deoxyribose 5‐phosphate from D‐glyceraldehyde 3‐phosphate and acetaldehyde. In addition, this enzyme can use acetaldehyde as the sole substrate, resulting in a tandem aldol reaction, yielding 2,4,6‐trideoxy‐D‐erythro‐hexapyranose, which spontaneously cyclizes. This reaction is very useful for the synthesis of the side chain of statin‐type drugs used to decrease cholesterol levels in blood. One of the main challenges in the use of DERA in industrial processes, where high substrate loads are needed to achieve the desired productivity, is its inactivation by high acetaldehyde concentration. In this work, the utility of different variants of Pectobacterium atrosepticum DERA (PaDERA) as whole cell biocatalysts to synthesize 2‐deoxyribose 5‐phosphate and 2,4,6‐trideoxy‐D‐erythro‐hexapyranose was analysed. Under optimized conditions, E. coli BL21 (PaDERA C‐His AA C49M) whole cells yields 99 % of both products. Furthermore, this enzyme is able to tolerate 500 mM acetaldehyde in a whole‐cell experiment which makes it suitable for industrial applications.
Role of ferroptosis in gastrointestinal tumors: From mechanisms to therapies
Authors: Si Chenli , Zhou Xiang , Deng Jie , Ye Shijie , Kong Lingming , Zhang Baofu , Wang Weiming
Published: April 2022

Ferroptosis is an iron‐dependent nonapoptotic regulated cell death, which is mainly caused by an abnormal increase in lipid oxygen free radicals and an imbalance in redox homeostasis. Recently, ferroptosis has been shown to have implications in various gastrointestinal cancers, such as gastric carcinoma, hepatocellular carcinoma, and pancreatic cancer. This review summarises the latest research on ferroptosis, its mechanism of action, and its role in the progression of different gastrointestinal tumors to provide more information regarding the prevention and treatment of these tumors.
Silencing of YAP attenuates pericyte‐myofibroblast transition and subretinal fibrosis in experimental model of choroidal neovascularization
Authors: Xu Ya‐hui , Feng Yi‐fan , Zou Rong , Yuan Fei , Yuan Yuan‐zhi
Published: April 2022

Age‐related macular degeneration (AMD) is the main reason of irreversible vision loss in the elderly. The subretinal fibrosis subsequent to choroidal neovascularization (CNV) is an important feature in the late stage of wet AMD and is considered to be one reason for incomplete response to anti‐VEGF drugs. Recent studies have shown that pericyte‐myofibroblast transition (PMT) is an important pathological process involving fibrotic diseases of various organs. However, the specific role and mechanism of PMT in the subretinal fibrosis of CNV have not been clarified. It has been clear that the Hippo pathway along with its downstream effector Yes‐associated protein (YAP) plays an important role in both epithelial and endothelial myofibroblast development. Therefore, we speculate whether YAP participates in PMT of pericytes and promotes fibrosis of CNV. In this study, experimental CNV was induced by laser photocoagulation in C57BL/6J (B6) mice, and aberrant YAP overexpression was detected in the retinal pigment epithelial/choroid/sclera tissues of the laser‐injured eyes. YAP knockdown reduced the proliferation, migration, and differentiation of human retinal microvascular pericytes in vitro. It also reduced subretinal fibrosis of laser‐induced CNV in vivo. Moreover, by proteomics‐based analysis of pericyte conditioned medium (PC‐CM) and bioinformatic analyses, we identified that the crosstalk between Hippo/YAP and MAPK/Erk was involved in expression of filamin A in hypoxic pericytes. These findings suggest that Hippo/YAP and MAPK/Erk are linked together to mediate pericyte proliferation, migration as well as differentiation, which may embody potential implications for treatment in diseases related to CNV.
Mental illness‐related stigma among probation officers
Authors: Givens Ashley , Jacobs Leah A. , Canada Kelli E. , Edwards Daniel
Published: April 2022

Background

Probation officers tend to hold stigmatising attitudes towards individuals on their caseload with mental illnesses. This can result in poor outcomes for justice‐involved people with mental illnesses. Though anti‐stigma interventions in the general public and among other criminal–legal professionals hold promise, these interventions have not been tested among probation officers.

Aims

To measure levels of stigma towards mental illnesses among probation officers before and after a brief online training related to mental illness.

Methods

Two hundred and seventy‐five probation and parole officers in one Midwest state completed a three‐module online training programme designed to increase knowledge and skills for working with clients with mental illnesses. Officers completed a pre‐ and post‐training assessment of level of stigmatising attitudes towards individuals with mental illnesses.

Results

Officer levels of stigma statistically significantly decreased from pre‐test (8.22) to post‐test (7.37; p < 0.001, t = 6.13). Nevertheless, pre‐training stigma scores were the strongest predictor of stigma levels at post‐test (p < 0.001, b = 0.90).

Conclusions

While basic training can significantly decrease mental disorder stigmatising scores for probation officers, the practical effect of this brief online experience was very small. Nevertheless, the fact that such brief and generalised input can have impact at all is encouraging. Implementation could be a useful preliminary to improving the quality of probation supervision of clients with mental illnesses.
Sex‐based differences in patients undergoing transseptal transcatheter mitral valve replacement: Closing the sex disparity gap
Authors: Segar Matthew W. , Krajcer Zvonimir
Published: April 2022

Key Points

In a nationwide registry of more than 2000 hospitalizations, the proportion of women undergoing transseptal transcatheter mitral valve replacement increased from 50.0% in 2015 to 60.2% in 2018.

No significant differences were observed between sexes for complications, hospital length of stay, or in‐hospital mortality rate.

Women had a higher 30‐day readmission rate and were more likely than men to be discharged to a skilled nursing facility.
Reflections on the association of thrombocytopenia with adverse outcomes after PCI
Authors: Motiwala Afaq , Jneid Hani
Published: April 2022

Key Points

Moderate‐severe thrombocytopenia (platelet count < 100,000) is associated with increased rates of post‐PCI complications (pericardiocentesis, PRBC and platelet transfusions) and in‐hospital mortality.

Any degree of thrombocytopenia (platelet count < 150,000) is associated with increased risk of long‐term all‐cause mortality.

Further studies can help determine which etiologies of thrombocytopenia are at highest risk for adverse outcomes and what strategies can help mitigate the risk in those patients.
The Effects of Ring Strain on Cyclic Tetraaryl[5]cumulenes
Authors: Sun Bozheng , Oakley Meagan S. , Yoshida Kota , Yang Yanwen , Tommasini Matteo , Zanchi Chiara , Lucotti Andrea , Ferguson Michael J. , Hampel Frank , Klobukowski Mariusz , Tykwinski Rik R.
Published: April 2022

Cyclic tetraaryl[5]cumulenes (1 a–f) have been synthesized and studied as a function of increasing ring strain. The magnitude of ring strain is approximated by the extent of bending of the cumulenic core as assessed by a combination of X‐ray crystallographic analysis and DFT calculations. Trends are observed in 13C NMR, UV‐vis, and Raman spectra associated with ring strain, but the effects are small. In particular, the experimental HOMO‐LUMO gap is not appreciably affected by bending of the [5]cumulene framework from ca. 174° (λmax=504 nm) in 1 a to ca. 178° (λmax=494 nm) in 1 f.
Excited‐State Distortions Promote the Photochemical 4π‐Electrocyclizations of Fluorobenzenes via Machine Learning Accelerated Photodynamics Simulations
Authors: Li Jingbai , Lopez Steven A.
Published: April 2022

Benzene fluorination increases chemoselectivities for Dewar‐benzenes via 4π‐disrotatory electrocyclization. However, the origin of the chemo‐ and regioselectivities of fluorobenzenes remains unexplained because of the experimental limitations in resolving the excited‐state structures on ultrafast timescales. The computational cost of multiconfigurational nonadiabatic molecular dynamics simulations is also currently cost‐prohibitive. We now provide high‐fidelity structural information and reaction outcome predictions with machine‐learning‐accelerated photodynamics simulations of a series of fluorobenzenes, C6F6‐nHn, n=0–3, to study their S1→S0 decay in 4 ns. We trained neural networks with XMS‐CASPT2(6,7)/aug‐cc‐pVDZ calculations, which reproduced the S1 absorption features with mean absolute errors of 0.04 eV (<2 nm). The predicted nonradiative decay constants for C6F4H2, C6F6, C6F3H3, and C6F5H are 116, 60, 28, and 12 ps, respectively, in broad qualitative agreement with the experiments. Our calculations show that a pseudo Jahn–Teller distortion of fluorinated benzenes leads to an S1 local‐minimum region that extends the excited‐state lifetimes of fluorobenzenes. The pseudo Jahn–Teller distortions reduce when fluorination decreases. Our analysis of the S1 dynamics shows that the pseudo‐Jahn–Teller distortions promote an excited‐state cis‐trans isomerization of a πC‐C bond. We characterized the surface hopping points from our NAMD simulations and identified instantaneous nuclear momentum as a factor that promotes the electrocyclizations.
Chiral Fibers Formation Upon Assembly of Tetraphenylalanine Peptide Conjugated to a PNA Dimer
Authors: Mosseri Andrea , Sancho‐Albero Maria , Leone Marilisa , Nava Donatella , Secundo Francesco , Maggioni Daniela , De Cola Luisa , Romanelli Alessandra
Published: April 2022

Self‐assembly of biomolecules such as peptides, nucleic acids or their analogues affords supramolecular objects, exhibiting structures and physical properties dependent on the amino‐acid or nucleobase composition. Conjugation of the peptide diphenylalanine (FF) to peptide nucleic acids triggers formation of self‐assembled structures, mainly stabilized by interactions between FF. In this work we report formation of homogeneous chiral fibers upon self‐assembly of the hybrid composed of the tetraphenylalanine peptide (4F) conjugated to the PNA dimer adenine‐thymine (at). In this case nucleobases seem to play a key role in determining the morphology and chirality of the fibers. When the PNA “at” is replaced by guanine‐cytosine dimer “gc”, disordered structures are observed. Spectroscopic characterization of the self‐assembled hybrids, along with AFM and SEM studies is reported. Finally, a structural model consistent with the experimental evidence has also been obtained, showing how the building blocks of 4Fat arrange to give helical fibers.
A Series of Rare‐Earth Mesoionic Carbene Complexes
Authors: Seed John A. , Vondung Lisa , Barton Franky , Wooles Ashley J. , Lu Erli , Gregson Matthew , Adams Ralph W. , Liddle Stephen T.
Published: April 2022

We report the synthesis and characterisation of a series of rare‐earth mesoionic carbene complexes, [RE{N(SiMe3)2}3{CN(Me)C(Me)N(Me)CH}] (3RE, RE=Sc, Ce, Pr, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), greatly expanding the limited library of f‐block mesoionic carbene complexes. These complexes were prepared by treatment of the parent RE‐triamides with anN‐heterocyclic olefin (NHO), where an NHO backbone proton undergoes a formal 1,4‐proton migration to the NHO‐methylene group. For all RE(III) metals, as expected, quantum chemical calculations suggest only a σ‐component to the metal−carbene bonding, in contrast to a previously reported uranium(III) congener where the 5f3metal engages in a weak π‐back‐bond to the MIC. All complexes were characterised by static variable‐temperature magnetic measurements, and dynamic magnetic measurements reveal that3Dyand3Erare field‐induced single‐molecule magnets (SMMs), withUeffenergy barriers of 35 and 128 K, respectively. Complex3Dyis, as expected, a poorly performing SMM, but conversely3Erperforms unexpectedly well.
Significant Effect of the Flexibility of Bridging Alkyl Chains on the Proximity of Stacked Porphyrin and Phthalocyanine Conjugated with a Fourfold Rotaxane Linkage
Authors: Yamada Yasuyuki , Iida Hayato , Shibano Shinya , Mihara Nozomi , Kato Tatsuhisa , Tanaka Kentaro
Published: April 2022

Spatial distance is an important factor in controlling the functional interactions between molecular units in a conjugate; therefore, the bridging unit has been closely examined. Here, we examined the effect of the flexibility of bridging alkyl chains on the proximity of stacked porphyrin and phthalocyanine conjugated with a fourfold rotaxane linkage. We found that closely stacking two π systems requires bridging alkyl chains above a certain length, and the shorter bridges hinder stacking because of their lower flexibility. The stacking distance between porphyrin and phthalocyanine in the conjugate with decyl (C10) chains was estimated to be 4.03 Å and showed a unique physical character arising from short‐distance interactions. The longer alkyl chains minimized steric restriction inside the fourfold rotaxane and allowed efficient communication between the porphyrin and phthalocyanine units. This is due to the flexibility of the side chains.
Iridium‐Catalyzed Direct Reductive Amination of Ketones and Secondary Amines: Breaking the Aliphatic Wall
Authors: Jouffroy Matthieu , Nguyen Thi‐Mo , Cordier Marie , Blot Marielle , Roisnel Thierry , Gramage‐Doria Rafael
Published: April 2022

Direct reductive amination (DRA) is a ubiquitous reaction in organic chemistry. This transformation between a carbonyl group and an amine is most often achieved by using a super stoichiometric amount of hazardous hydride reagents, thus being incompatible with many sensitive functional groups. DRA could also be achieved by means of chemo‐ or biocatalysis, thereby attracting the interest of industry as well as academic laboratories due to the virtually perfect atom economy. Although DRAs are well‐established for substrate pairs such as aldehydes with either 1° or 2° amines as well as ketones with 1° amines, the current methodologies are limited in the case of ketones with 2° amines. Herein, we present a general DRA protocol that overcomes this major limitation by means of iridium catalysis. The applicability of the methodology is demonstrated by accessing an unprecedented range of biologically relevant tertiary amines starting from both aliphatic ketones and aliphatic amines. The choice of a disphosphane ligand (JosiphosAor Xantphos) is essential for the success of the transformation.
Direct Visualisation of the Surface Atomic Active Sites of Carbon‐Supported Co3O4 Nanocrystals via High‐Resolution Phase Restoration
Authors: Makgae Ofentse A. , Moya Arthur N. , Phaahlamohlaka Tumelo N. , Huang Chen , Coville Neil J. , Kirkland Angus I. , Liberti Emanuela
Published: April 2022

The atomic arrangement of the terminating facets on spinel Co3O4 nanocrystals is strongly linked to their catalytic performance. However, the spinel crystal structure offers multiple possible surface terminations depending on the synthesis. Thus, understanding the terminating surface atomic structure is essential in developing high‐performance Co3O4 nanocrystals. In this work, we present direct atomic‐scale observation of the surface terminations of Co3O4 nanoparticles supported on hollow carbon spheres (HCSs) using exit wavefunction reconstruction from aberration‐corrected transmission electron microscopy focal‐series. The restored high‐resolution phases show distinct resolved oxygen and cobalt atomic columns. The data show that the structure of {100}, {110}, and {111} facets of spinel Co3O4 exhibit characteristic active sites for carbon monoxide (CO) adsorption, in agreement with density functional theory calculations. Of these facets, the {100} and {110} surface terminations are better suited for CO adsorption than the {111}. However, the presence of oxygen on the {111} surface termination indicates this facet also plays an essential role in CO adsorption. Our results demonstrate direct evidence of the surface termination atomic structure beyond the assumed stoichiometry of the surface.
DNA‐Mediated Assembly of Carbon Nanomaterials
Authors: Zhu Xurong , Yan Xuehui , Yang Sichang , Wang Yong , Wang Shuang , Tian Ye
Published: April 2022

Carbon nanomaterials (CNMs) have attracted extensive attentions on account of their superior electrical, mechanical, optical, and biological properties. However, the dimensional limit and irregular arrangement have hampered their further application. It is necessary to find an easy, efficient and controllable way to assemble CNMs into well‐ordered array. DNA nanotechnology, owning to the advantages of precise programmability, highly structural predictability and spatial addressability, has been widely applied in the assembly of CNMs. Summarizing the progress and achievements in this field will be of great value to related studies. Herein, based on the different dimensions of CNMs containing 0‐dimensional (0D) carbon dots (CDs), fullerenes, 1‐dimensional (1D) carbon nanotubes (CNTs) and 2‐dimensional (2D) graphene, we introduced the conjugation strategies between DNA and CNMs, their different assembly methods and their applications. In addition, we also discuss the existing challenges and future opportunities in the field.
A simple method to control automatically the performance of three‐coil wireless power transfer systems without direct output measurement
Authors: Ricken Garcia Lucas , Abatti Paulo J.
Published: April 2022

The control and optimization of wireless power transfer (WPT) systems require the continuous monitoring of their performance or, similarly, some output parameters. The solution presented in this manuscript is based on the relationship between some figures of merit representative of the WPT systems and allows to control automatically (in a simple way, without any direct measurement at the load circuit) the performance of a three‐coil WPT system under variations on the load and/or mutual inductance between the intermediate and load coils. The qualities and limitations of the proposed method are discussed in detail. Conventional circuit analysis and practical results are included to validate the presented theory and its applicability in an automatic control scheme.