bluuebunny/crossref_metadata_2025 huggingface dataset:
Frequency of Anemia in Patients Admitted with Acute Decompensated Heart Failure in Tertiary Care Cardiac Hospital
Authors: Bhuromal Sharwan , Memon Faraz Farooq , Shaikh Muhammad Asim , Kumar Suresh
Published: June 2022

Introduction: Anemia is one of the potential comorbid condition in patients with acute decompensated heart failure (ADHF) which is linked to higher morbidity and mortality rates. Worldwide, its prevalence ranges from 4% to >70% in hospitalized patients with ADHF. Unfortunately data is lacking from our region and hence we aimed to conduct this study to scientifically fill the present gap by evaluating the actual burden of anemia in patients hospitalized with ADHF in a tertiary care hospital of Karachi, Pakistan.

Patients and Methods: This was a hospital based study conducted in the Department of Cardiology, Tabba Heart Institute, Karachi From 1st November 2019 to 30th April 2020. A total of 203 patients with ADHF with age >35 years and <80 years were selected. A blood sample was taken to determine the hemoglobin levels and hemoglobin (Hb) levels <12.0 g/dL in women and <13.0 g/dL in men were taken as cut-off for anemia.

Results: Overall mean and SD of age was 63.70±10.53 years and among them most of were males (n = 116, 57.1%). The overall prevalence of anemia in patients with ADHF was quite high and 63.5% (n = 129). Only three condition, hypertension, diabetes mellitus, and current smoking habits had significant association with the occurrence of anemia in patients with ADHF, p value <0.05.

Conclusion: In conclusion, the results showed that anemia is an independent risk for HF. Anemia was observed in one-third of the study population. More prevalent in male gender, elderly patients of age above 60 years, and associated with other comorbids.
The Effect of REACT Strategy Enriched with Reflective Thinking Activities on Students' Reflective Thinking
Authors: ASLANGİRAY Hilal , USTA GEZER Seda
Published: June 2022

The aim of this study is to examine the effect of teaching carried out using the REACT strategy enriched with reflective thinking activities on students' Reflective Thinking. The research was carried out in the first semester of the 2019 – 2020 academic year with students studying at a public school in Istanbul. A quasi-experimental design with control and experimental groups was used in the research. The application was designed by the researcher in the form of 28 lesson hours in total, eight weeks for the "Systems in Our Body" unit. The reflective Thinking Scale was used as a data collection tool in the study. Obtained quantitative data were analyzed with IBM SPSS v22. According to the results of the analysis, a significant difference was found after the application in the pretest and posttest scores of the experimental group students. As a result of the research, it was determined that the students in the experimental group also increased their Reflective Thinking Scale total scores. There was no increase between the Reflective Thinking Scale pretest and posttest scores of the control group students.
The Role of Schwann Cells in Cancer
Authors: Deborde Sylvie , Wong Richard J.
Published: June 2022

Schwann cells (SCs) are the most abundant cell type in the nerves in the peripheral nervous system and compose a family of subtypes that are endowed with a variety of different functions. SCs facilitate the transmission of neural impulses, provide nutrients and protection for neurons, guide axons in nerve repair, and regulate immune functions. In the context of cancer, recent studies have revealed an active role of SCs in promoting cancer cell invasion, modulating immune responses, and transmitting pain sensation.
Benzimidazole Based Hole‐Transporting Materials for High‐performance Inverted Perovskite Solar Cells
Authors: Tingare Yogesh S. , Su Chaochin , Lin Ja‐Hon , Hsieh Yi‐Chun , Lin Hong‐Jia , Hsu Ya‐Chun , Li Meng‐Che , Chen Guan‐Lin , Tseng Kai‐Wei , Yang Yi‐Hsuan , Wang Leeyih , Tsai Hsinhan , Nie Wanyi , Li Wen‐Ren
Published: June 2022

Interfaces play a decisive role in perovskite solar cells’ power conversion efficiency and their long‐term durability. Small‐molecule hole‐transporting materials (HTMs) have grabbed enormous attention due to their structural flexibility, material properties, and stabilities, allowing for improved operational durability in perovskite photovoltaics. This study synthesizes and investigates a new class of benzimidazole‐based small molecules, named YJS001 and YJS003, serving as the HTMs to enable high‐efficiency mixed‐cation mixed‐halide perovskite solar cells. The benzimidazole‐based materials are dopant‐free HTMs composed of donor and acceptor building blocks that are designed to engineer the energy level alignment near the HTM/perovskite interface. Mixed‐cation mixed‐halide perovskites can be grown uniformly on both HTMs with large crystalline grains. It is discovered that the donor‐rich YJS003‐based solar cell exhibits a high open‐circuit voltage of 1.09 V with a champion power conversion efficiency of over 20%. Power‐dependent current–voltage characteristics of the solar cells are analyzed, from which the high performance of YJS003's excellent hole mobility and well‐aligned energy level is attributed. This work introduces a new class of benzimidazole‐based small molecules as HTMs, that paves the path for dopant free interface material development for commercialization of perovskite solar cells.
Laser‐Based Growth and Treatment of Graphene for Advanced Photo‐ and Electro‐Related Device Applications
Authors: Wang Ying , Zhao Yang , Li Xin , Jiang Lan , Qu Liangti
Published: June 2022

Graphene is considered as a competitive material for the development of photo‐ and electrodevices because of its superior electrical and optical properties. Meanwhile, laser processing technologies with high precision, fast reaction speed, and high maneuverability are widely used for the fast and facile fabrication of functionalized graphene and relevant devices. In particular, it enables desired performance tuning, programmable structural designing, micro‐ or nanoscale processing, and large‐scale integration for advanced graphene‐based photo‐ and electro‐related devices, which has greatly promoted the development of multiscale and multidimensional device manufacturing technology. In this review, the interaction principle and processing strategies of functional graphene prepared and treated by laser, especially for the regulation of optical and electrical properties, will be fully understood and introduced. The latest progress and reports of advanced photoelectro devices, including electric energy storage devices, generators, sensors, actuators, photodetectors, photothermal devices, and photovoltaic devices, are classified and summarized. In general, this review may provide positive and meaningful guidance for flourishing graphene‐based photo‐ and electroindustries.
Kinetics‐Controlled Interfacial Synthesis of Janus and Patchy Heterostructures Based on Perovskite Nanocrystals
Authors: Chen Shuhua , Mao Xinnan , Zhong Qixuan , Pan Qi , Liu Jun , Fu Jie , Yang Di , Chen Jinxing , Wang Lu , Zhang Qiao , Cao Muhan
Published: June 2022

Heterostructures integrated by diverse material featuring nanocrystals (NCs) tunable properties and functions are of great interest. However, to rationally design and precisely control the heterostructures in multiple shapes still remains a tremendous challenge. In this work, the nucleation of SiO2 nanoparticles is manipulated via a kinetics‐controlled water–hexane interfacial reaction system to construct Cs3Cu2I5/SiO2 heterostructures, which can be well controlled in Janus and patchy morphology. In this interfacial reaction, the evolution of Cs3Cu2I5 NCs and the intrinsic formation mechanism of the heterostructures are investigated. It is observed that the Cs3Cu2I5 NCs on the interface undergo a morphology transformation driven by ligand loss and exposed facets evolution. Increased wettability between Cs3Cu2I5 and SiO2 favors the formation of Cs3Cu2I5/SiO2 heterostructures. The key to this strategy is to break the rule of thermodynamic domination in reaction by kinetics manipulation when constructing the patchy heterostructure. To be noted, an increased stability is conferred on the resultant heterostructure product compared to naked perovskite NCs. This work enables to better control the complicated heterostructure configurations and understand their formation mechanism.
Silver‐Catalyzed Asymmetric Aldol Reaction of Isocyanoacetic Acid Derivatives Enabled by Cooperative Participation of Classical and Nonclassical Hydrogen Bonds
Authors: Sakai Satoshi , Fujioka Akane , Imai Koji , Uchiyama Kei , Shimizu Yohei , Higashida Kosuke , Sawamura Masaya
Published: June 2022

The silver‐catalyzed asymmetric aldol reaction of isocyanoacetic acid derivatives with aldehydes has been developed by employing a chiral prolinol‐phosphine as a hydrogen‐bond‐donating P,N,O ligand. DFT calculations indicated that the reaction proceeds in a stepwise manner, involving C−C bond forming carbonyl addition and subsequent enantioselectivity‐determining oxazoline ring formation. An O−H⋅⋅⋅O/sp3‐C−H⋅⋅⋅O two‐point hydrogen bond donated by the prolinol moiety of the ligand activates the aldehyde in the C−C bond formation step and facilitates the subsequent cyclization under stereocontrol by the catalyst. The calculations further suggest that additional nonclassical C−H⋅⋅⋅O hydrogen bonds as well as London dispersion interactions may also participate synergistically in the stereocontrol.

magnified image
Low‐Voltage‐Driven Electrochemical Aerobic Oxygenation with Flavin Catalysis: Chemoselective Synthesis of Sulfoxides from Sulfides
Authors: Mizushima Taiga , Oka Marina , Imada Yasushi , Iida Hiroki
Published: June 2022

The chemoselective electrochemical oxygenation of sulfides to sulfoxides is performed using a biomimetic flavin catalyst that enables the activation of molecular oxygen under a low cathode potential. Diverse functional groups, including alcohols, ketones, aldehydes, cyclopropane, carboxylic acids, pyridine, alkenes, and alkynes, are well tolerated under low‐voltage electrolytic conditions.

magnified image
High‐Resolution Mapping of Strain Partitioning and Relaxation in InGaN/GaN Nanowire Heterostructures
Authors: Park Bumsu , Lee Ja Kyung , Koch Christoph T. , Wölz Martin , Geelhaar Lutz , Oh Sang Ho
Published: June 2022

Growing an InxGa1−xN/GaN (InGaN/GaN) multi‐quantum well (MQW) heterostructure in nanowire (NW) form is expected to overcome limitations inherent in light‐emitting diodes (LEDs) based on the conventional planar heterostructure. The epitaxial strain induced in InGaN/GaN MQW heterostructure can be relaxed through the sidewalls of NW, which is beneficial to LEDs because a much larger misfit strain with higher indium concentration can be accommodated with reduced piezoelectric polarization fields. The strain relaxation, however, renders highly complex strain distribution within the NW heterostructure. Here the authors show that complementary strain mapping using scanning transmission electron microscopy and dark‐field inline holography can comprehend the strain distribution within the axial In0.3Ga0.7N/GaN MQW heterostructure embedded in GaN NW by providing the strain maps which can cover the entire NW and fine details near the sidewalls. With the quantitative evaluation by 3D finite element modelling, it is confirmed that the observed complex strain distribution is induced by the strain relaxation leading to the strain partitioning between InGaN quantum disk, GaN quantum well, and the surrounding epitaxial GaN shell. The authors further show that the strain maps provide the strain tensor components which are crucial for accurate assessment of the strain‐induced piezoelectric fields in NW LEDs.
High‐Temperature and Dynamic RGB (Red‐Green‐Blue) Long‐Persistent Luminescence in an Anti‐Kasha Organic Compound
Authors: Zhang Qiang‐Sheng , Wang Shi‐Cheng , Xiong Xiao‐Hong , Fu Peng‐Yan , Zhang Xiao‐Dong , Fan Ya‐Nan , Pan Mei
Published: June 2022

Organic LPL (long‐persistent luminescence) materials have sparked extensive research interest due to the ultralong‐lived triplet states. Although numerous organic LPL materials have been reported, most of the triplet emission was static and monotonous. Therefore, LPL materials with dynamic triplet emission are urgently required. A triamino‐s‐triazine derivative 1 with dynamic LPL was fabricated. The single‐crystal structure shows that the abundant intermolecular interactions and small free volume restrict the molecular motion and avoid the quenchers. Spectral and theoretical calculations upheld the existence of multiple excited states in 1, and the migration of electrons between multiple excited states is very sensitive to external stimuli. By modulating the stimulus, the residence of electrons in different triplet states can be manipulated to achieve RGB LPL. Importantly, blue LPL was achieved by manipulating the anti‐Kasha emission. And the red LPL can still be observed at high temperature.
Influence of carbon nanotubes/polyetherketone‐cardo interlayer structure on mode II interlaminar fracture toughness of the interleaved carbon fiber reinforced epoxy composites
Authors: Ma Tianyi , Sun Yuekun , Yao Jiawei
Published: June 2022

Delamination is always considered as a threat to the resin matrix composite laminates due to the nonvisibility from the outside. Much effort on the interleaving toughening has been made to improve the interlaminar fracture toughness. The synergistic toughening effect of thermoplastic resin and carbon nanotubes (CNTs) has been the topic in the interleaving toughening. In this study, the influence of the hybrid structure between thermoplastic polyetherketone‐cardo (PEK‐C) and CNTs on the toughening efficiency was investigated. The mode II interlaminar fracture toughness was tested and the fracture surface was examined by scanning electron microscope. The results showed that the interlaminar structure was closely related with the interlayer structure and the synergistic toughening effect depended greatly on the hybrid structure.
A pan‐chelydrid, Chelydropsis aubasi sp. nov., from the Middle Eocene (MP 15, early Bartonian) of Chéry‐Chartreuve, France
Authors: Joyce Walter G. , Landréat Jean‐Luc , Rollot Yann
Published: June 2022

Snapping turtles (Pan‐Chelydridae) play an important role in modern ecosystems throughout North America, but their fossil record is notably poor. We here describe a new species of fossil pan‐chelydrid, Chelydropsis aubasi, from the Middle Eocene (MP15, Bartonian) of Chéry‐Chartreuve, Department of Aisne, France, based on a series of fragments that document most of the shell. The new species not only bridges the morphological gap between earlier pan‐chelydrids from North America and later pan‐chelydrids from Europe but also advances the arrival of the group from North America to Europe by at least 10 million years. Although pan‐chelydrids are notably absent from Early and Middle Eocene localities throughout Europe, the new fossil gives credence to the idea that pan‐chelydrids may have dispersed from North America to Europe in concert with other turtles during the Paleocene–Eocene Thermal Maximum, but remain undetected to date.
Effect of moxa smoke on sperm parameters and oxidative stress in rats with asthenozoospermia
Authors: Liu Yajie , An Yu , Xing Guogang , Jin Zirun , Xi Ke , Huo Yongwei , He Rui , Wang Hao , Ouyang Xiali , Huang Yueping , Huang Chang , Han Li , Zhao Baixiao
Published: June 2022

Asthenozoospermia is a leading cause of male infertility, characterized by reduced sperm motility. In this study, we determined sperm motility and the activities of antioxidant enzymes and oxidation products in the testis of rats with ornidazole (ORN)‐induced asthenozoospermia and further examined and compared the differential effects of moxa smoke (MS) and cigarette smoke (CS) on sperm motility and oxidative stress (OS) of asthenozoospermic rats. The smoke intervention was initiated 11 days after intragastric administration of ORN, followed by the examination of testis index, sperm parameters, OS‐related gene levels, and testicular histopathology. Sperm motility and antioxidant enzyme activities, as well as oxidation products significantly decreased in ORN‐induced rats compared with MS‐treated rats (p < .05–.001). MS treatment restored the reduced sperm motility and activities of glutathione peroxidase, superoxide dismutase, and catalase, but increased the malondialdehyde and nitric oxide synthetase levels in ORN‐induced rats (p < .05–.001). Also, the histopathological changes in the testis of ORN‐induced rats were improved by MS treatment. The study highlighted that MS was an effective factor in moxibustion therapy, which notably improved the sperm motility of asthenozoospermic rats by inhibiting OS in the reproductive system.
Optimization of the hongqu starter preparation process for the manufacturing of red mold rice with high gamma‐aminobutyric acid production by solid‐state fermentation
Authors: Wu Anqi , Li Liangyi , Zhang Song , Lin Qinlu , Liu Jun
Published: June 2022

Red mold rice (RMR) generally contains gamma‐aminobutyric acid (GABA), which has several physiological functions. Monascus purpureus M162, with a high GABA production of 15.10 mg/g was generated by atmospheric and room temperature plasma mutation. Furthermore, we conducted a response surface methodology to produce a premium hongqu starter. The results revealed that under optimal conditions, that is, a substrate containing brown rice and bran in a brown rice: bran ratio of 9:1 (wt/wt), an inoculation size of 21.50 mL/100 g, a mixing frequency of one time/9 h, and a cultivation time of 7.20 days, the number of active spores, α‐amylase activity, and saccharification power activity was 4.15 × 107 spores/g, 155 U/g, and 3260 U/g in the high‐quality starter, respectively. These values were 224.32‐fold, 139.64%, and 141.74% higher than those obtained with M. purpureus M162 inoculated into steamed indica rice, respectively, and 153.70‐fold, 267.24%, and 151.63% higher than those obtained with the parent strain M. purpureus M1, respectively. The premium hongqu starter of M. purpureus M162 was inoculated into steamed indica rice to produce RMR with 15.93 mg/g of GABA. In conclusion, we proposed a novel strategy for functional RMR production with high GABA concentrations by solid‐state fermentation with Monascus spp.
Media engineering in marine diatom Phaeodactylum tricornutum employing cost‐effective substrates for sustainable production of high‐value renewables
Authors: Rehmanji Mohammed , Nesamma Asha Arumugam , Khan Nida Jamil , Fatma Tasneem , Jutur Pannaga Pavan
Published: June 2022

Phaeodactylum tricornutum is a marine diatom, rich in omega‐3 polyunsaturated fatty acids especially eicosapentaenoic acid (EPA) and brown pigment, that is, fucoxanthin. These high‐value renewables (HVRs) have a high commercial and nutritional relevance. In this study, our focus was to enhance the productivities of such renewables by employing media engineering strategy via., photoautotrophic (P1, P2, P3) and mixotrophic (M1, M2, M3, M4) modes of cultivation with varying substrate combinations of carbon (glycerol: 0.1 m) and nitrogen (urea: 441 mm and/or sodium nitrate: 882 mm). Our results demonstrate that mixotrophic [M4] condition supplemented with glycerol (0.1 m) and urea (441 mm) feed enhanced productivities (mg L−1 day−1) as follows: biomass (770.0), total proteins (36.0), total lipids (22.0), total carbohydrates (23.0) with fatty acid methyl esters (9.6), EPA (2.7), and fucoxanthin (1.1), respectively. The overall yield of EPA represents 28% of total fatty acids in the mixotrophic [M4] condition. In conclusion, our improved strategy of feeding urea to a glycerol‐supplemented medium defines a new efficient biomass valorization paradigm with cost‐effective substrates for the production of HVRs in oleaginous diatoms P. tricornutum.
Rapid regulations of metabolic reactions in Escherichia coli via light‐responsive enzyme redistribution
Authors: Huang Zikang , Sun Lize , Lu Genzhe , Liu Hongrui , Zhai Zihan , Feng Site , Gao Ji , Chen Chunyu , Qing Chuheng , Fang Meng , Chen Bowen , Fu Jiale , Wang Xuan , Chen Guo‐Qiang
Published: June 2022

Protein‐based condensates have been proposed to accelerate biochemical reactions by enriching reactants and enzymes simultaneously. Here, we engineered those condensates into a photo‐activated switch in Escherichia coli (PhASE) to regulate enzymatic reactions via tuning the spatial correlation of enzymes and substrates. In this system, scaffold proteins undergo liquid–liquid phase separation (LLPS) to form light‐responsive compartments. Tethered with a light‐responsive protein, enzymes of interest (EOIs) can be recruited by those compartments from cytosol within only a few seconds after a pulse of light induction and fully released in 15 min. Furthermore, we managed to enrich small molecular substrates simultaneously with enzymes in the compartments and achieved the acceleration of luciferin and catechol oxidation by 2.3‐ and 1.6‐folds, respectively. We also developed a quantitative model to guide the further optimization of this demixed regulatory system. Our tool can thus be used to study the rapid redistribution of proteins, and reversibly regulate enzymatic reactions in E. coli.
Real‐world implications of nonbiological factors with staging, clinical management, and prognostic prediction in pancreatic ductal adenocarcinoma
Authors: Wang Chao , Chen Haoda , Deng Xiaxing , Xu Wei , Shen Baiyong
Published: June 2022

Background

The American Joint Committee on Cancer (AJCC) tumor‐node‐metastasis (TNM) staging system focuses on traditional biological factors (BFs). The present study incorporates nonbiological factors (NBFs) into the AJCC‐TNM staging system in terms of the advanced clinical management and prognostic‐prediction accuracy of pancreatic ductal adenocarcinoma (PDAC).

Methods

Eight thousand three hundred and thirty eligible patients with PDAC were obtained from Surveillance, Epidemiology, and End Results database between January 1, 2011, and December 31, 2015. Multivariate Cox proportional hazards regression analysis and Kaplan–Meier curves were used to testify the feasibility of cancer‐specific survival (CSS) prediction based on TNM‐NBF stages.

Results

The large population‐based study demonstrated that NBFs (insurance status, marital status, county‐level median household income, and unemployment) were significant prognostic indicators (p < 0.005), and multivariate Cox regression analysis demonstrated that the NBF1 stage carried a 29.4% increased risk of cancer‐specific mortality than NBF0 stage (p < 0.001). The concordance index of TNM‐NBF stage was 0.755 (95% confidence interval: 0.740–0.769).

Conclusions

The novel NBF stage was independently associated with CSS of PDAC. In addition, combining TNM with the NBF stage could provide better clinical management and prognostic‐prediction accuracy.
Seismic evacuation simulation in a dynamic indoor environment
Authors: Chu Yifan , Liu Zhen , Liu Tingting , Zhao Yumeng , Chai Yanjie
Published: June 2022

During an earthquake, interior nonstructural components of a building will be damaged. The damaged objects will obstruct pedestrians' evacuation routes and increase casualties. But this issue has received scant attention in evacuation simulation research. This paper focuses on this issue and proposes an indoor seismic evacuation model to simulate crowd evacuation in a dynamic environment. A physical model of nonstructural components is presented to simulate the dynamics of the indoor scenario. The flow field algorithm is constructed to guide pedestrian's avoidance behaviors globally to reflect the impact of environmental changes on indoor crowd path selection, and a modified social force model is built to simulate the joint influence of seismic forces and the environment on pedestrian motion states. The results of the experiments shows that the proposed model can generate realistic  evacuation scene and rational evacuation routes in the earthquake.
Vision sensor‐based SLAM problem for small UAVs in dynamic indoor environments
Authors: Zhou Lanfeng , Kong Mingyue , Liu Ziwei , Li Ling
Published: June 2022

In recent years, with the rapid development of artificial intelligence, machine vision and other related technologies, there has been a demand for higher levels of intelligence in UAVs. There are many excellent SLAM systems available, but most of them assume that their working environment is static. When there are dynamic objects in the environment the localization and mapping accuracy of the SLAM system is reduced, and it can even cause its tracking to fail. To solve this problem. In this paper, we propose a target detection‐based SLAM algorithm for real‐time operation in crowded dynamic environments. The algorithm removes feature points of dynamic objects from key frames and then constructs a point cloud map of based on the state‐of‐the‐art SLAM system ORB‐SLAM3. Finally, the proposed method is validated and evaluated on multiple dynamic datasets and real environments. The results show that the algorithm in this paper outperforms other visual SLAM algorithms in terms of localization and map building accuracy in more highly dynamic datasets, while guaranteeing performance.
Physical and microstructural quality of extruded snacks made from blends of barley and green lentil flours
Authors: Li Xiang , Guillermic Reine‐Marie , Nadimi Mohammad , Paliwal Jitendra , Koksel Filiz
Published: June 2022

Background and objectives

Most puffed snacks in the market are made from refined cereal flours which allow greater expansion and better texture but are nutritionally inferior as they lack protein and dietary fiber. Whole barley and green lentil flours at several blending ratios were extruded as a function of temperature and moisture content to optimize the physical and microstructural quality of fiber and protein‐enriched snacks.

Findings

High extrusion temperature significantly improved overall expansion and texture. The effects of feed moisture depended on the blending ratio, parallel with the total protein and dietary fiber content of extrudates. Barley:green lentil of 45:55 showed the highest extrudate expansion (~1.9 mm/mm on average) and lowest hardness (~29 N on average), followed by the blend 60:40. X‐ray microtomography showed that this blending ratio also produced a larger mean cell size (~1.6 mm), lower mean wall thickness (~0.3 mm), and higher overall connectivity between cells.

Conclusion

Barley and green lentil when blended at the ratios of 45:55 and 60:40, and extruded at higher temperature resulted in optimal extrudate physical and microstructural properties including higher expansion and crispness, thinner cell walls, reduced hardness, and crunchiness.

Significance and novelty

Blending cereal and pulse flours in snack food applications will allow development of fiber and protein‐enriched options that are also texturally and structurally appealing.
Bioinspired Photocatalyzed Organic Synthetic Transformations. The Use of Natural Pigments and Vitamins in Photocatalysis
Authors: Barata‐Vallejo Sebastián , Yerien Damian E. , Postigo Al
Published: June 2022

Due to the necessity for more environmentally benign processes in synthetic organic chemistry, and in particular in photocatalysis, a recourse to photocatalysts that are also found in nature and mimic natural processes to accomplish organic transformations is very appealing. Synthetic useful reactions such as oxidations, reductions, carbon‐oxygen, carbon‐carbon and carbon‐sulfur bond formation reactions, and E‐to‐Z geometrical isomerization reactions photocatalyzed by biological natural pigments, vitamins, cofactors, and compounds with antiviral activity will be discussed in this account. Interestingly, due to the remarkable redox properties and triplet energies of some of these catalysts that are found in nature, both electron transfer (ET)‐ and energy transfer (EnT)‐driven photocatalytic processes can be accomplished.
Desorption of Hydrogen from Graphene Induced by Charge Injection
Authors: Schmickler Wolfgang , Santos Elizabeth
Published: June 2022

Hydrogen adsorbed on a graphene electrode in contact with an aqueous solution is in a metastable state. Here, its desorption induced by a small positive charge pulse was studied by molecular dynamics with a tight binding method based on density functional theory. The efficiency of the code allowed to follow the trajectory of the desorbed particle in detail. Desorption was triggered by an oxygen atom of water, which was attracted to the surface and approached the adsorbed hydrogen. Charge transfer occured, and the hydrogen was attached to the water molecule to form a hydronium ion, which drifted into the solution, changed its solvation and underwent Grotthus steps. The reverse process, adsorption of a proton from the solution, required a pulse with a high negative charge. The reaction was governed by the field right in front of the electrode, and not by the electrode potential. The time that the proton transfer takes is much shorter than the relaxation time of the double layer, so that simulations performed with a constant electrode potential may not be realistic.
Structural and ITC Characterization of Peptide‐Protein Binding: Thermodynamic Consequences of Cyclization Constraints, a Case Study on Vascular Endothelial Growth Factor Ligands
Authors: Gaucher Jean‐François , Reille‐Seroussi Marie , Broussy Sylvain
Published: June 2022

Macrocyclization constraints are widely used in the design of protein ligands to stabilize their bioactive conformation and increase their affinities. However, the resulting changes in binding entropy can be puzzling and uncorrelated to affinity gains. Here, the thermodynamic (Isothermal Titration Calorimetry) and structural (X‐ray, NMR and CD) analysis of a complete series of lactam‐bridged peptide ligands of the vascular endothelial growth factor, and their unconstrained analogs are reported. It is shown that differences in thermodynamics arise mainly from the folding energy of the peptide upon binding. The systematic reduction in conformational entropy penalty due to helix pre‐organization can be counterbalanced by an unfavorable vibrational entropy change if the constraints are too rigid. The gain in configurational entropy partially escapes the enthalpy/entropy compensation and leads to an improvement in affinity. The precision of the analytical ITC method makes this study a possible benchmark for constrained peptides optimization.
Synthesis and Characterization of A Stable Extra‐Large‐Pore Zeolite with 15×12×12 Member‐Ring Channels
Authors: Cai Xianshu , Zhao Yue , Zi Wenwen , Jiao Feng , Du Hongbin
Published: June 2022

Extra‐large‐pore zeolites have great application potential in various industrial fields, such as oil refinery, fine chemicals and biomass processing. Herein, we report the synthesis of an extra‐large‐pore germanosilicate zeolite (named NUD‐13) by using an easily obtained aromatic organic cation 1,2‐dimethyl‐3‐propyl‐benzimidazolium as organic structure‐directing agents. NUD‐13 possesses a rare 15‐member ring extra‐large‐pore channel intersecting with two elliptical 12‐member ring channels, which is isostructural to germanosilicate zeolite GeZA synthesized by using triphenylsulfonium. The germanium in NUD‐13 can be partially substituted by acid treatment to obtain stable high silica zeolite. In addition, aluminium is added into the framework of NUD‐13 during the post‐synthesis treatment process, which provides a foundation for catalytic application.
A Highly Water‐ and Air‐Stable Iron‐Containing MRI Contrast Agent Sensor for H2O2
Authors: Karbalaei Sana , Franke Alicja , Jordan Aubree , Rose Cayla , Pokkuluri P. Raj , Beyers Ronald J. , Zahl Achim , Ivanović‐Burmazović Ivana , Goldsmith Christian R.
Published: June 2022

A highly water‐ and air‐stable Fe(II) complex with the quinol‐containing macrocyclic ligand H4qp4 reacts with H2O2 to yield Fe(III) complexes with less highly chelating forms of the ligand that have either one or two para‐quinones. The reaction increases the T1‐weighted relaxivity over four‐fold, enabling the complex to detect H2O2 using clinical MRI technology. The iron‐containing sensor differs from its recently characterized manganese analog, which also detects H2O2, in that it is the oxidation of the metal center, rather than the ligand, that primarily enhances the relaxivity.
Synthesis of New Morphinan Opioids by TBADT‐Catalyzed Photochemical Functionalization at the Carbon Skeleton**
Authors: Gorbachev Dmitry , Smith Elliot , Argent Stephen P. , Newton Graham N. , Lam Hon Wai
Published: June 2022

The synthesis of new morphinan opioids by the addition of photochemically generated carbon‐centered radicals to substrates containing an enone in the morphinan C‐ring, is described. Using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer photocatalyst, diverse radical donors can be used to prepare a variety of C8‐functionalized morphinan opioids. This work demonstrates the late‐stage modification of complex, highly functionalized substrates.
A multimodel fire detection and alarm system for automobiles using internet of things and machine learning
Authors: Uma S. , Eswari R.
Published: June 2022

Fire accidents in vehicles lead to the loss of human lives. The fire detection and alarm systems are often error‐prone and respond to nonactual indications of fire presence, known as false alarms. The proposed model detects the fire at the smoldering stage and buzzes an alarm if an actual fire or smoke is detected. This system can achieve this real alarm using multiple internet of things‐based sensors, namely smoke/gas, flame, temperature, and a visualization camera. The visualization camera continuously captures images of the vehicle to check the existence of fire. Machine learning algorithms are executed on the sensor and image dataset to reduce false alarms and achieve high accuracy of results by using various performance metrics.
Exploiting Phase Transitions in Catalysis: Adsorption of CO on doped VO2‐Polymorphs
Authors: Stahl Berenike , Bredow Thomas
Published: June 2022

VO2 is well known for its low‐temperature metal‐insulator transition between two phases with tetragonal rutile and monoclinic structure. The adsorption of CO on the two polymorphs of Mo‐doped VO2 is calculated to investigate the effect of a substrate phase change on the adsorption energy. The system is investigated theoretically at density‐functional theory level using a hybrid functional with London dispersion correction. We establish a computational protocol applicable for the study of physisorption on open‐shell transition metal oxides. The main task is to control the spin state of open‐shell slab models used to model adsorption of closed‐shell molecules in order to obtain numerically stable adsorption energies and to reduce spin contamination within the broken‐symmetry unrestricted Kohn‐Sham approximation. Applying this procedure, it is possible to identify the most stable adsorption positions of CO on both phases of VO2. CO adsorbs vertically with the C atom on a surface V atom in the monoclinic phase with an adsorption energy of −56 kJ/mol. The same adsorption position has an adsorption energy of only −46 kJ/mol on the rutile phase. Similar differences were obtained with multireference methods using an embedded cluster model. This effect may inspire experimental strategies exploiting the rutile
monoclinic VO2 phase transition in catalytic processes where CO is formed as product or as an intermediate.
Reliable data communication using post‐quantum encryption in Internet of Everything
Authors: Balaji Ashwin , Dhurandher Sanjay Kumar
Published: June 2022

Internet of Everything (IoE) is one of the emerging technologies in the advancement of digital life and innovation. But the major issue that is to be addressed is the security concerns over such an environment, especially in end‐to‐end device communication. The proposed approach primarily focuses on reliable end‐to‐end device communication using post‐quantum location‐aware encryption, aiming to achieve confidentiality and integrity in an Internet of Everything environment. Even though the post‐quantum techniques have shown to be one of the evolving solutions for reliable data communication, but its robustness against the Man‐In‐The‐Middle and Sybil attacks is still a wide‐open subject and undiscovered. Numerous traditional encryption algorithms are now in use, while post‐quantum encryption is being studied and considered as a quantum‐safe substitute. The proposed approach also demonstrates a robust attack model which focuses on communication network threats like namely, Man‐In‐The‐Middle and Sybil attacks intending to evaluate the overall performance of the network by analyzing the performance parameters like, number of nodes in the network, message size, execution time, and memory consumption by the nodes and aiming to achieve an appreciable accuracy in an IoE environment.
Successful treatment of mediastinal pancreatic pseudocyst and pancreatic pleural effusion with endoscopic pancreatic duct drainage: A case report
Authors: Watanabe Shunsuke , Toki Masao , Kambayashi Komei , Kitada Shuichi , Nosaka Takeshi , Ochiai Kazushige , Gondo Koichi , Shibahara Junji , Hisamatsu Tadakazu
Published: June 2022

An 81‐year‐old man with chronic pancreatitis was being treated with a protease inhibitor. He developed an acute exacerbation of chronic pancreatitis and dyspnea. Contrast‐enhanced computed tomography showed disruption of the main pancreatic duct, a cystic lesion connecting the mediastinum to the main pancreatic duct, and left pleural effusion. We diagnosed a pancreatic pseudocyst, mediastinal pancreatic pseudocyst, and pancreatic pleural effusion. Endoscopic retrograde pancreatography showed leakage of contrast medium from the pancreatic body; furthermore, a cystic cavity extending to the mediastinum through a pancreatic duct fistula was visualized. An endoscopic transpapillary nasopancreatic drainage tube was placed in the cystic cavity. Computed tomography showed that the mediastinal pseudocyst and pleural effusion had disappeared. Endoscopic transpapillary pancreatic duct drainage may be useful when a connection between the main pancreatic duct and a mediastinal pseudocyst is confirmed by imaging.
Temporal and spatial changes in benthic invertebrate trophic networks along a taxonomic richness gradient
Authors: Garrison Julie A. , Nordström Marie C. , Albertsson Jan , Nascimento Francisco J. A.
Published: June 2022

Species interactions underlie most ecosystem functions and are important for understanding ecosystem changes. Representing one type of species interaction, trophic networks were constructed from biodiversity monitoring data and known trophic links to assess how ecosystems have changed over time. The Baltic Sea is subject to many anthropogenic pressures, and low species diversity makes it an ideal candidate for determining how pressures change food webs. In this study, we used benthic monitoring data for 20 years (1980–1989 and 2010–2019) from the Swedish coast of the Baltic Sea and Skagerrak to investigate changes in benthic invertebrate trophic interactions. We constructed food webs and calculated fundamental food web metrics evaluating network horizontal and vertical diversity, as well as stability that were compared over space and time. Our results show that the west coast of Sweden (Skagerrak) suffered a reduction in benthic invertebrate biodiversity by 32% between the 1980s and 2010s, and that the number of links, generality of predators, and vulnerability of prey have been significantly reduced. The other basins (Bothnian Sea, Baltic Proper, and Bornholm Basin) do not show any significant changes in species richness or consistent significant trends in any food web metrics investigated, demonstrating resilience at a lower species diversity. The decreased complexity of the Skagerrak food webs indicates vulnerability to further perturbations and pressures should be limited as much as possible to ensure continued ecosystem functions.
Cystatin C in risk prediction after transcatheter aortic valve replacement: a retrospective analysis
Authors: Kuwabara Kensuke , Zen Kan , Yashige Masaki , Takamatsu Kazuaki , Ito Nobuyasu , Kadoya Yoshito , Yamano Michiyo , Yamano Tetsuhiro , Nakamura Takeshi , Yaku Hitoshi , Matoba Satoaki
Published: June 2022

Aims

No study has evaluated the prognostic value of the chronic kidney disease (CKD) classification by cystatin C‐based estimated glomerular filtration rate (eGFR) (CKDCys classification) in patients undergoing transcatheter aortic valve replacement (TAVR). This study aimed to compare the prognostic value of CKDCys classification and CKD classification by creatinine‐based eGFR (CKDCr classification) in risk prediction after TAVR.

Methods and results

We retrospectively analysed consecutive 219 patients with symptomatic severe aortic stenosis who underwent TAVR at our institute between December 2016 and June 2019. Pre‐operative CKDCr and CKDCys classifications were evaluated for their prognostic value of 2‐year major adverse cardiovascular and cerebrovascular events (MACCE) after TAVR. MACCE was defined as the composite of all‐cause mortality, non‐fatal myocardial infarction, stroke, and rehospitalization for worsening congestive heart failure. Participants had a median age of 86.0 years and were predominantly female (76.9%). In 96.6% of the cases, TAVR was performed using transfemoral access. The median creatinine‐based eGFR (52.85 mL/min/1.73 m2) was higher than the cystatin C‐based eGFR (41.50 mL/min/1.73 m2). Downward reclassification in CKD stages based on eGFRCys was observed in 49.0% of patients. During a median follow‐up period of 575.5 (interquartile range: 367.0–730.0) days, 58 patients presented with MACCE. CKDCys classification, but not CKDCr classification, significantly stratified the risk of 2‐year MACCE in patients after TAVR by log‐rank test (P = 0.003). In multivariate Cox regression analysis, only CKDCys stage 3b [hazard ratio (HR) = 4.37; 95% confidence interval (CI): 1.28–14.91; P = 0.019] and CKDCys stage 4 + 5 (HR = 3.72; 95% CI: 1.06–12.99; P = 0.040) were significant predictors of MACCE after adjustment for potential confounders.

Conclusions

The CKDCys classification could better assess the risk than the CKDCr classification in patients undergoing TAVR. CKDCys stage 3b and stage 4 + 5 correlated with adverse outcomes.
Acute Toxicity of Major Geochemical Ions to Fathead Minnows (Pimephales promelas): Part B—Modeling Ion Toxicity
Authors: Erickson Russell J. , Mount David R. , Highland Terry L. , Hockett J. Russell , Hoff Dale J. , Jenson Correne T. , Norberg-King Teresa J. , Forsman Brandy
Published: June 2022

Mathematical models are presented for the acute median lethal concentrations of major geochemical ions (Na+, K+, Ca2+, Mg2+, Cl−, SO42−, HCO3−/CO32−) to fathead minnows (Pimephales promelas), based on an extensive series of experiments presented in a companion article. Toxicity relationships across different dilution waters, individual salts, and salt mixtures suggest six independent mechanisms of toxicity to consider in modeling efforts, including Mg/Ca-specific toxicity, osmolarity-related toxicity, SO4-specific toxicity, K-specific toxicity, effects of high pH/alkalinity, and a multiple ion-related toxicity at low Ca distinct from the other mechanisms. Models are evaluated using chemical activity-based exposure metrics pertinent to each mechanism, but concentration-based alternative models that are simpler to apply are also addressed. These models are compared to those previously provided for Ceriodaphnia dubia, and various issues regarding their application to risk assessments are discussed. Environ Toxicol Chem 2022;41:2095–2106. © 2022 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Abstract
Indocyanine green potentiated paclitaxel nanoprodrugs for imaging and chemotherapy
Authors: Xiang Xiujuan , Feng Xuan , Lu Shaojin , Jiang Bowen , Hao Dengyuan , Pei Qing , Xie Zhigang , Jing Xiabin
Published: June 2022

Self‐assembled prodrug nanoparticles with tumor‐responsive capacity have great potential in tumor visualization and treatment. However, the nanoparticle formulas usually contain multiple components, especially polymeric materials, which result in various potential issues. Herein, we report an indocyanine green (ICG)‐driven assembly of paclitaxel prodrugs integrating near‐infrared fluorescence imaging and tumor‐specific chemotherapy. By feat of the hydrophilic merit of ICG, paclitaxel dimer could form more uniformly monodispersed nanoparticles. This two‐in‐one strategy reinforces the complementary advantages, resulting in superior assembly behavior, robust colloidal stability, enhanced tumor accumulation as well as desirable near‐infrared imaging and in vivo feedback of chemotherapy. The in vivo experiments validated the prodrug activation at tumor sites as evidenced by enhanced fluorescence intensity, potent tumor growth suppression, and reduced systemic toxicity compared with commercial Taxol. The universality of ICG potentiated strategy toward photosensitizers and fluorescence dyes was confirmed. This presentation provides deep insight into the feasibility of constructing clinical‐close alternatives for improving antitumor efficacy.
Consumer choice and public‐private providers: The role of perceived prices
Authors: Lim Kai Shen , Yap Wei Aun , Yip Winnie
Published: June 2022

Governments often encourage health service providers to improve quality of care and reduce prices through competition. The efficacy of competition hinges on the assumption that consumers demand high quality care at low prices for any given health condition. In this paper, we examine this assumption by investigating the role of perceived price and quality on consumer choice for four different health conditions across public and private providers. We use a nationally representative survey in Malaysia to elicit respondents' perception on prices and quality, and their preferred choice of provider. We estimate a mixed logit model and show that consumers value different dimensions of quality depending on the health condition. Furthermore, increasing perceived prices for private providers reduces demand for minor, more frequent health conditions such as flu fever or cough, but increases demand for more complex, severe conditions such as coronary artery bypass graft. These findings provide empirical support for price regulation which differentiates the severity of underlying health conditions.