bluuebunny/crossref_metadata_2025 huggingface dataset:
Peculiarities of formation of comfortable urban environment (on the example of Magnitogorsk)
Authors: Sal'nikova Mariya Yur'evna , Bulatova Evgeniya Konstantinovna
Published: May 2020

The subject of this research is the historical stages of creation of the beautification elements of urban environment of the city of Magnitogorsk. The object of this research is the periods of construction of recreational system objects since the XX century until the present. The authors examine such aspects of the topic as construction of recreational areas at each development period; all engineering and construction works at each historical stage pursued the key goal – quickest possible construction and bringing into service the largest metallurgical plant.  The authors propose a method of historical periodization of formation of recreational structures since the late XX century until the presents. The main conclusions lies in the results of analysis of beautification level of urban territories at different stages of its development. The elimination of such flaws would lead to a truly comprehensive beautification and creation of full-scale in functional, constructive, planning and artistic regard urban environment. The main factors of rational organization of a comfortable urban environment are determined.
Urbanization processes in the Sakha Republic (Yakutia): the dynamics of key parameters (1989-2018)
Authors: Breslavskii Anatolii Sergeevich
Published: May 2020

This article analyzes the key parameters of urbanization in the Sakha Republic (Yakutia) on the background of urbanization processes in other republics in the East of Russia during the period from 1988 to 2018. Attention is paid to the dynamics of demographic development of the cities and workers’ settlements, changes in the structure of urban localities in the republic associated to abolishment of the settlements and turning them into the rural localities. The article also demonstrates which factors affected density or urban population in Yakutia, as well as analyzes the sources and vectors of continuing urbanization. The research leans on the extensive corpus of official statistical data on 11 cities and 67 urban-type settlements acquires based on the results of All-Union Census of 1989, Russian Censuses of 2002 and 2010, and special statistical examinations of Rosstat and its regional branck in the Sakha Republic (Yakutia) conducted in 2011-2018. The conclusion is made on the overall deceleration of urbanization processes in the republic for the past 30 years. These changes were associated with restructuration of the regional industry, particularly reduction of urban-type settlement for 27 localities – from 67 to 40. At the same time, population of majority of the cities and settlements during the period from 1990 to 2018 was decreasing; however, the rapid demographic growth of Yakutsk partially compensated for these losses. It is concluded that urban population was concentrated mostly in the capital and its environs, as well as the largest cities of the republic – Neryungri, Mirny, Lensk and Aldan.
From worms to fish to mice
Authors: Benian Guy M , Choo Hyojung J
Published: May 2020

An multi-species approach can be used to identify small molecules with properties that might prove useful for the treatment of some neuromuscular diseases.
Of Legislative Waves and Case law: Effective Judicial Protection, Right to an Effective Remedy and Proceduralisation in the EU Asylum Policy
Authors: Tsourdi Evangelia (Lilian)
Published: May 2020

This article explores the multifaceted relationship between the principle of effective judicial protection, the fundamental right to an effective remedy, and secondary EU procedural rules in asylum. Proceduralisation has been an explicit goal of the EU asylum policy since its inception.
It has materialised in three legislative waves. The first resulted in the creation of a basic set of procedural guarantees, alongside a plethora of exceptional procedures. The second resulted in modest improvements in terms of harmonisation, and adherence to fundamental rights, but saw exceptional
procedural arrangements either retained or introduced. The third, forthcoming wave, aims at further harmonisation that risks, however, being heavily focused on the underlying goal of externalising protection to third countries. Case law of the Court of Justice of the European Union has further
refined procedural guarantees shaping national procedural autonomy. Drawing from the Charter rights to good administration and to an effective remedy, the Court has not shied away from adducing additional procedural requirements. It has also clarified how the principle of effective judicial
protection and the Charter right to an effective remedy relate to each other, finding that the latter reaffirms the principle of effective judicial protection and largely aligning their scope. The emerging procedural landscape is increasingly complex. The Court's nuanced assessments combined
with a plethora of exceptional arrangements at national level led to convoluted standards that are increasingly difficult to put in practice.
Diversity of cultivable protease-producing bacteria and their extracellular proteases associated to scleractinian corals
Authors: Su Hongfei , Xiao Zhenlun , Yu Kefu , Huang Qinyu , Wang Guanghua , Wang Yinghui , Liang Jiayuan , Huang Wen , Huang Xueyong , Wei Fen , Chen Biao
Published: May 2020

Protease-producing bacteria play a vital role in degrading organic nitrogen in marine environments. However, the diversity of the bacteria and extracellular proteases has seldom been addressed, especially in communities of coral reefs. In this study, 136 extracellular protease-producing bacterial strains were isolated from seven genera of scleractinian corals from Luhuitou fringing reef, and their protease types were characterized. The massive coral had more cultivable protease-producing bacteria than branching or foliose corals. The abundance of cultivable protease-producing bacteria reached 106 CFU g−1 of coral. Phylogenetic analysis of 16S rRNA gene sequences revealed that the isolates were assigned to 24 genera, from which 20 corresponded to the phyla Firmicutes and Proteobacteria. Bacillus and Fictibacillus were retrieved from all coral samples. Moreover, Vibrio and Pseudovibrio were most prevalent in massive or foliose coral Platygyra and Montipora. In contrast, 11 genera were each identified in only one isolate. Nearly all the extracellular proteases from the bacteria were serine proteases or metalloproteases; 45.83% of isolates also released cysteine or aspartic proteases. These proteases had different hydrolytic ability against different substrates. This study represents a novel insight on the diversity of cultivable protease-producing bacteria and their extracellular proteases in scleractinian corals.
A Mathematical Programming Model and Enhanced Simulated Annealing Algorithm for the School Timetabling Problem
Authors: Odeniyi O. A. , Omidiora E. O. , Olabiyisi S. O. , Oyeleye C. A.
Published: May 2020

Despite significant research efforts for School Timetabling Problem (STP) and other timetabling problems, an effective solution approach (model and algorithm) which provides boundless use and high quality solution has not been developed. Hence, this paper presents a novel solution approach for solving school timetabling problem which characterizes the problem-setting in the timetabling problem of the high school system in Nigeria. We developed a mixed integer linear programming model and meta-heuristic method - Enhanced Simulated Annealing (ESA) algorithm. Our method incorporates specific features of Simulated Annealing (SA) and Genetic Algorithms (GA) in order to solve the school timetabling problem. Both our solution approach and SA approach were implemented using Matrix Laboratory 8.6 software. In order to validate and demonstrate the performance of the developed solution approach, it was tested with the highly constrained school timetabling datasets provided by a Nigerian high school using constraints violation, simulation time and solution cost as evaluation metrics. Our developed solution approach is able to find optimal solution as it satisfied all the specified hard and soft constraints with average simulation time of 37.91 and 42.16 seconds and solution cost of 17.03 and 18.99, respectively, for JSS and SSS to the problem instance. A comparison with results obtained with SA approach shows that the developed solution approach produced optimal solution in smaller simulation time and solution cost, and has a great potential to solve school timetabling problems with satisfactory results. The developed ESA algorithm can be used for solving other related optimization problems.
Evaluation of the Liver Enzyme (AST, ALT & ALP) Levels of Adult HIV Patients on HAART in UPTH
Authors: Anyanwu Chinwe F. , Jr. Eric O. Aigbogun , Joseph Tosin O.
Published: May 2020

This study evaluated the liver enzyme levels of HIV-infected adult patients on highly active antiretroviral treatment (HAART) for not less than 1 year. The study was designed as a randomised cross-sectional study that evaluated the differences in the aspartate aminotransferase [AST], alanine transaminase [ALT] and alkaline phosphatase [ALP] of 129 (46 males and 83 females) HIV-infected adult patients. Before the study, ethical clearance (Ref: UPH/CEREMAD/REC/19) was obtained from the University of Port Harcourt Ethics Committee. Venous blood samples were obtained and the liver enzyme levels were analysed using Clinical Chemistry Analyser (VS10) manufactured by Vitro Scient. Values were further categorised into; normal or abnormal. SPSS version 21 (IBM® Armonk, USA) and Graph Pad Prism (Version 8.0.2) was used to analyse the data. T-test compared the sex differences in mean, while Chi-square analysis tested the sex differences in the categorised data. From the result, the mean AST (27.65±17.93 IU/L) and ALP (135.13±10.87 IU/L) values for males were higher than females AST (27.25±18.93 IU/L) and ALP (132.65±9.96 IU/L) values, while ALT was higher in female (34.66±22.29 IU/L) than males (33.75±18.14 IU/L); however, the differences were not significant (p>0.05). Generally, abnormal AST, ALT and ALP levels were 31%, 34% and 82% respectively; with no sex-associated differences (p>0.05). 45.7% of the patients (males: 25 [54.3%] and females: 34 [41.0%]) had cholestatic abnormality, while 8.5% (5; 10.9% males and 6; 7.2% females) had hepatocellular abnormality, 18.6% (6; 13.0% of males and 18; 21.7% of females) and mixed abnormality (AST/ALT/ALP). In conclusion, cholestatic abnormalities were observed in more than 80% of the patients as opposed to hepatocellular abnormalities, which were less than 35%. More females were associated with mixed abnormality when compared to males with independent (ALT/AST) abnormality. This study, therefore, suggests the need for a randomised case-control study to highlight the extent of deviation from normal values.
Interactions of Thymine and Uracil with Copper, Cobalt and Silver Ferrocyanides and the Implications in Chemical Evolution
Authors: Doodnauth Davendradat , Tewari Brij Bhushan
Published: May 2020

Effects on pH based adsorption of nucleic acid bases (thymine and uracil) at two different concentrations 1 x 10-4 M and 1 x 10-5 M on copper, cobalt and silver ferrocyanides were studied over a pH range (1.0 – 10.0) at temperature 30±1ºC. The progress of adsorption was followed spectrophotometrically by measuring the UV absorbance of the nucleic acid base solutions at their corresponding max. Maximum adsorptions were found at neutral pH for both thymine and uracil.  Effects of concentrations on adsorption of thymine and uracil on copper, cobalt and silver ferrocyanides were studied in a concentration range 10-4 – 10-5 M at neutral pH 7.0 ± 0.1 and at temperature 30±1°C. The interaction followed the Langmuir type of adsorption in general in the concentration range of 10-4 to 10-5 M of thymine and uracil solution. The uptake of nucleic bases on metal ferrocyanides followed the order of CuFc > AgFc > CoFc for the adsorption of thymine and CuFc > CoFc > AgFc for the adsorption of uracil. Effects of the presence of salts on the adsorption of thymine and uracil on metal ferrocyanides also had been studied. The insoluble metal ferrocyanides’ interaction with biomolecules must have either formed metal complexes or could have enhanced the formation of biopolymers in fluctuating environment.
Real‐World Outcomes Associated With Methotrexate, Sulfasalazine, and Hydroxychloroquine Triple Therapy Versus Tumor Necrosis Factor Inhibitor/Methotrexate Combination Therapy in Patients With Rheumatoid Arthritis
Authors: Curtis Jeffrey R. , Palmer J. Lynn , Reed George W. , Greenberg Jeffrey , Pappas Dimitrios A. , Harrold Leslie R. , Kremer Joel M.
Published: May 2020

Objective

Though randomized controlled trials have demonstrated relatively comparable clinical outcomes with triple therapy (methotrexate [MTX], sulfasalazine [SSZ], and hydroxychloroquine [HCQ]) compared to combination therapy (tumor necrosis factor inhibitor [TNFi] and MTX), real‐world experiences comparing these strategies have not been well studied.

Methods

We evaluated the clinical effectiveness and effects of medication discontinuation of triple therapy with MTX/SSZ/HCQ versus combination therapy with TNFi/MTX in rheumatoid arthritis (RA) patients enrolled in the Corrona RA Drug Safety & Effectiveness Registry. Propensity score matching was used to match patients up to a ratio of 1:3 to adjust for imbalances between treatment groups, with stratification performed according to biologics‐naive or biologics‐exposed status of study participants.

Results

Patients eligible for analysis in this study included biologics‐naive RA patients (3,926 who received combination therapy with TNFi/MTX and 262 who received triple therapy with MTX/SSZ/HCQ) and biologics‐exposed RA patients (3,365 who received combination therapy with TNFi/MTX and 130 patients who received triple therapy with MTX/SSZ/HCQ). Before propensity score matching, numerous factors were imbalanced between the treatment groups, with triple therapy patients generally being older, having a longer disease duration of RA and lower RA disease activity, and more likely having a history of malignancy and other comorbidities. After matching, almost all (93–98%) triple therapy patients could be matched to TNFi/MTX therapy patients, and cohort characteristics were generally well balanced. Discontinuation of medication was greater in triple therapy patients referent to TNFi/MTX therapy patients (adjusted hazard ratio [HR] of 2.17 [95% confidence interval 1.63–2.88] in the biologics‐naive group; adjusted HR of 1.51 [95% confidence interval 1.06–2.15] in the biologics‐exposed group). At 6 months, the proportion of biologics‐naive patients attaining low disease activity was significantly greater in the TNFi/MTX treatment group (49.2% in TNFi/MTX therapy patients versus 33.3% in triple therapy patients), as was the mean change in Clinical Disease Activity Index scores (–9.3 units versus –5.5 [95% confidence interval –1.5, –6.1]). Corresponding results in the biologics‐exposed patients numerically favored TNFi/MTX therapy compared to triple therapy but did not reach statistical significance.

Conclusion

Few patients receive triple therapy with MTX/SSZ/HCQ in the US. In the present study, drug persistence and clinical effectiveness outcomes were less favorable in triple therapy patients compared to TNFi/MTX therapy patients.
Progress in Auxetic Mechanical Metamaterials: Structures, Characteristics, Manufacturing Methods, and Applications
Authors: Wang Zhenwei , Luan Congcong , Liao Guangxin , Liu Jiapeng , Yao Xinhua , Fu Jianzhong
Published: May 2020

Auxetic mechanical metamaterials (AMMs), as an exciting paradigm of metamaterials, have attracted increasing attention due to their interesting mechanical properties (e.g. negative Poisson's ratio), as well as the emergence of advanced manufacturing technology (e.g. 3D printing). Although various reviews on AMMs, their structures, properties, and applications, have existed, it still lacks a comprehensive review in terms of manufacturing methods. Herein, the latest progress in AMMs is extensively reviewed, including AMMs’ structures, characteristics, manufacturing methods, and applications. In addition, the current challenges and future works of AMMs are concluded and discussed. This Review aims to serve as a collection of knowledge that supplies more comprehensive understanding and inspiration to support further developments of AMMs from the perspective of design and manufacturing.
Temperature‐ and Stress‐Dependent Electromechanical Response of Porous Pb(Zr,Ti)O3
Authors: Khansur Neamul Hayet , Biggemann Jonas , Stumpf Martin , Riess Kevin , Fey Tobias , Webber Kyle G.
Published: May 2020

The small‐signal direct piezoelectric coefficient and dielectric permittivity are characterized as a function of temperature from 25 to 450 °C and uniaxial compressive stress up to 80 MPa in porous Pb(Zr,Ti)O3 (PZT; 10, 20, 30, 40, and 50 vol% porosity). Results show retention of piezoelectric response throughout the temperature range with increasing porosity up to 30 vol%, above which a subsequent decrease is observed. Similarly, increasing porosity did not result in a significant change of the depolarization temperature, although a slight increase in the Curie point is observed with increasing porosity. Macroscopic experimental results are discussed together with microcomputed tomography, which shows the 3D pore structure. These results are important for sensing applications that operate at elevated temperatures and apply compressive stress to the electroactive element.
Interfaces Determine the Fate of Seeded α‐Synuclein Aggregation
Authors: Campioni Silvia , Bagnani Massimo , Pinotsi Dorothea , Lecinski Sarah , Rodighiero Simona , Adamcik Jozef , Mezzenga Raffaele
Published: May 2020

Amyloid fibrils formed by the α‐Synuclein (α‐Syn) protein are the pathological hallmark of multiple human disorders, generally termed α‐synucleinopathies. The aggregation process of α‐Syn into amyloids appears to be highly dependent on the presence of: i) hydrophobic–hydrophilic interfaces, and ii) pre‐formed seed fibrils. By combining Thioflavin T binding measurements with different microscopy techniques (direct stochastic optical reconstruction microscopy, atomic force microscopy, correlative super‐resolution light microscopy, and scanning electron microscopy), the effect of the air–water interface (AWI) is tested on seeded α‐Syn aggregation. The correlation of the results provided by each method reveals striking differences in the mechanism of formation, yield, length, thickness, and morphology of fibrils obtained from samples having equal initial amounts of seeds and monomers, but incubated in the presence or absence of an AWI. Overall, the results indicate that the AWI determines how amyloids grow and proliferate, the final balance between monomer and aggregates, and the morphological properties of the aggregates themselves. These observations may set the basis for amplifying and tuning the properties of specific fibril polymorphs of interest, in structural biology and cytotoxicity studies, as well as in those materials science applications featuring amyloids.
Highly Linear and Stable Flexible Temperature Sensors Based on Laser‐Induced Carbonization of Polyimide Substrates for Personal Mobile Monitoring
Authors: Gandla Srinivas , Naqi Muhammad , Lee Mingoo , Lee Jung Joon , Won Yoochan , Pujar Pavan , Kim Junchul , Lee Sunghoo , Kim Sunkook
Published: May 2020

Wearable on‐skin electronic devices that can monitor temperature in real time are of significant interest for personalized mobile health monitoring. Here, a flexible temperature sensor directly patterned by laser‐induced carbonization on Kapton polyimide films integrated with flexible printed circuit boards is reported. The proposed sensor design possessing high resistance values exhibits high‐linear and stable response to temperatures when integrated with flexible printed circuit boards (FPCBs) to enable continuous monitoring. The anisotropic conductive film bonding technique is used to obtain the stable real‐time monitoring data under various complex environments. The sensor integration with a wearable patch based FPCB establishes conformal contacts with human skin and allows wireless sensing capabilities smoothly in real time. This kind of approach can enable multifunctional sensors to be directly laser patterned on FPCBs without any additional interfacing.
Scalable Imprinting of Flexible Multiplexed Sensor Arrays with Distributed Piezoelectricity‐Enhanced Micropillars for Dynamic Tactile Sensing
Authors: Chen Xiaoliang , Shao Jinyou , Tian Hongmiao , Li Xiangming , Wang Chunhui , Luo Yongsong , Li Sheng
Published: May 2020

The ongoing revolution of human–robot interactions and electronic skins has created new requirements for tactile sensors, including good mechanical flexibility, high sensitivity, and the availability of distributed pixels for detecting force distribution. Here, a highly sensitive flexible sensor array based on piezoelectricity‐enhanced vertically aligned P(VDF‐TrFE) micropillars is developed for dynamic tactile sensing. The core piezoelectric sensing micropillars are fabricated using a straightforward and scalable nanoimprinting technology and then sandwiched between a pair of cross electrode arrays to construct multiplexed sensor arrays. Due to the proposed structural design and nanoimprinting methodology, the sensor pixels exhibit uniform output generation, robust output stability, and scalable fabrication ability. In addition, taking advantage of the high compressibility and enhanced strain of the piezoelectric micropillars compared to planar films, the microstructured sensors show an enhanced sensitivity of 228.2 mV N−1 and a highly linear response to loads. By integrating the flexible sensor with a portable signal processing circuit, a complete tactile sensing system is successfully developed to provide clear intuitive user interfaces. The good flexibility and robust stability of the sensor arrays enable them to be attached onto curved surface for real‐time tracking of dynamic force and imaging the force distribution.
Photoluminescence‐Based Characterization of Halide Perovskites for Photovoltaics
Authors: Kirchartz Thomas , Márquez José A. , Stolterfoht Martin , Unold Thomas
Published: May 2020

Photoluminescence spectroscopy is a widely applied characterization technique for semiconductor materials in general and halide perovskite solar cell materials in particular. It can give direct information on the recombination kinetics and processes as well as the internal electrochemical potential of free charge carriers in single semiconductor layers, layer stacks with transport layers, and complete solar cells. The correct evaluation and interpretation of photoluminescence requires the consideration of proper excitation conditions, calibration and application of the appropriate approximations to the rather complex theory, which includes radiative recombination, non‐radiative recombination, interface recombination, charge transfer, and photon recycling. In this article, an overview is given of the theory and application to specific halide perovskite compositions, illustrating the variables that should be considered when applying photoluminescence analysis in these materials.
Recent Advancement of p‐ and d‐Block Elements, Single Atoms, and Graphene‐Based Photoelectrochemical Electrodes for Water Splitting
Authors: Tiwari Jitendra N. , Singh Aditya Narayan , Sultan Siraj , Kim Kwang S.
Published: May 2020

Solar‐assisted photoelectrochemical (PEC) water splitting to produce hydrogen energy is considered the most promising solution for clean, green, and renewable sources of energy. For scaled production of hydrogen and oxygen, highly active, robust, and cost‐effective PEC electrodes are required. However, most of the available semiconductors as a PEC electrodes have poor light absorption, material degradation, charge separation, and transportability, which result in very low efficiency for photo‐water splitting. Generally, a promising photoelectrode is obtained when the surface of the semiconductor is modified/decorated with a suitable co‐catalyst because it increases the light absorbance spectrum and prevents electron–hole recombination during photoelectrode reactions. In this regard, numerous p‐ and d‐block elements, single atoms, and graphene‐based PEC electrodes have been widely used as semiconductor/co‐catalyst junctions to boost the performances of PEC overall water splitting. This review enumerates the recent progress and applications of p‐ and d‐block elements, single atoms, and graphene‐based PEC electrodes for water splitting. The focus is placed on fundamental mechanism, efficiency, cells design, and various aspects that contribute to the large‐scale prototype device. Finally, future perspectives, summary, challenges, and outlook for improving the activity of PEC photoelectrodes toward whole‐cell water splitting are addressed.
Single‐Step Preparation of Large Area TiO2 Photoelectrodes for Water Splitting
Authors: Franz Silvia , Arab Hamed , Chiarello Gian Luca , Bestetti Massimiliano , Selli Elena
Published: May 2020

The fast, single‐step and easily scalable production by plasma electrolytic oxidation (PEO) of large area TiO2 electrodes with excellent photoactivity in water splitting under simulated solar light is systematically investigated here. In particular, the effects that the cell voltage (100–180 V) and the processing time (0.5–15 min) have on the electrode properties are studied. The PEO‐produced oxide layers are porous, the predominant crystalline structure shifting from anatase, to an anatase‐rutile mixture, and finally to rutile by rising the cell voltage. The electrodes show a double‐layered structure, with a more compact layer at the interface with the titanium substrate and a thick porous layer on the external surface. The photocurrent density versus wavelength reflects the phase composition, with a maximum incident photon‐to‐current efficiency of 90% at 320 nm. The highest H2 production rate is attained with the mixed anatase‐rutile electrode prepared by 300 s‐long PEO at 150 V.
Challenges and Recent Progress on Key Materials for Rechargeable Magnesium Batteries
Authors: Liu Fanfan , Wang Tiantian , Liu Xiaobin , Fan Li‐Zhen
Published: May 2020

Rechargeable magnesium batteries (RMBs), which have attracted tremendous attention in large‐scale energy storage applications beyond lithium ion batteries, have many advantages such as high volumetric capacity, low cost, and environmental friendliness. However, the strong polarization effect, slow kinetic de‐intercalation of Mg2+ ions, and the incompatibility between electrodes and electrolytes limit their commercial application. Thus, developing stable and high‐efficiency electrode materials and optimization of electrolytes are key to promoting the practical application of RMBs. In this review, a summary and discussion are provided regarding the recent progress in the development of the key materials for RMBs, including cathodes, anodes, and electrolytes. The cathode materials including intercalation type cathodes and conversion type cathodes are classified and introduced in detail by the reaction mechanism, the effects of structure on the kinetics of Mg2+ ion migration are clarified; the modification and interface issues of Mg anode materials are comprehensively stated, and the potential development prospects of RMB electrolytes are systematically analyzed. In addition, the main opportunities and challenges in this field are briefly elaborated and discussed. Finally, this review will provide a framework for the key materials for RMBs as a reference for future research.
Multiscale Understanding and Architecture Design of High Energy/Power Lithium‐Ion Battery Electrodes
Authors: Zhang Xiao , Ju Zhengyu , Zhu Yue , Takeuchi Kenneth J. , Takeuchi Esther S. , Marschilok Amy C. , Yu Guihua
Published: May 2020

Among various commercially available energy storage devices, lithium‐ion batteries (LIBs) stand out as the most compact and rapidly growing technology. This multicomponent system operates on coupled dynamics to reversibly store and release electricity. With the hierarchical electrode architectures inside LIBs, versatile functionality can be realized by design, while considerable difficulties remain to be solved to fully exploit the capability of each constituent. With the rapid electrification of the transportation sector and an urgent need to overhaul electric grids in the context of renewable energy penetration, demands for concomitant high energy and high power batteries are continuously increasing. Although building an ideal battery requires effort from multiple scientific and engineering aspects, it is imperative to gain insight into multiscale transport behaviors arising in both spatial and temporal dimensions, and enable their harmonic integration inside the whole battery system. In this progress report, recent research efforts on characterizing and understanding transport kinetics in LIBs are reviewed covering a broad range of electrode materials and length scales. To demonstrate the crucial role of such information in revolutionary electrode design, examples of innovative high energy/power electrodes are provided with their unique hierarchical porous architectures highlighted. To conclude, perspectives on further approaches toward advanced thick electrode designs with fast kinetics and tailored properties are discussed.
Implanting Isolated Ru Atoms into Edge‐Rich Carbon Matrix for Efficient Electrocatalytic Hydrogen Evolution
Authors: Zhang Huabin , Zhou Wei , Lu Xue Feng , Chen Tao , Lou Xiong Wen (David)
Published: May 2020

Although the maximized dispersion of metal atoms has been realized in the single‐atom catalysts, further improving the intrinsic activity of the catalysts is of vital importance. Here, the decoration of isolated Ru atoms into an edge‐rich carbon matrix is reported for the electrocatalytic hydrogen evolution reaction. The developed catalyst displays high catalytic performance with low overpotentials of 63 and 102 mV for achieving the current densities of 10 and 50 mA cm−2, respectively. Its mass activity is about 9.6 times higher than that of the commercial Pt/C‐20% catalyst at an overpotential of 100 mV. Experimental results and density functional theory calculations suggest that the edges in the carbon matrix enhance the local electric field at the Ru site and accelerate the reaction kinetics for the hydrogen evolution. The present work may provide insights into electrocatalytic behavior and guide the design of advanced electrocatalysts.
The Impact of Atmosphere on Energetics of Lead Halide Perovskites
Authors: Hu Zhanhao , Liu Zonghao , Ono Luis K. , Jiang Maowei , He Sisi , Son Dae‐Yong , Qi Yabing
Published: May 2020

Solar cells based on metal halide perovskites have emerged as a promising low‐cost photovoltaic technology. In contrast to inert atmospheres where most of the lab‐scale devices are made to date, large‐area low‐cost production of perovskite solar cells often involves processing of perovskites in various atmospheres including ambient air, nitrogen, and/or vacuum. Herein, the impact of atmosphere on the energy levels of methylammonium lead halide perovskite films is systematically investigated. The atmosphere is varied to simulate the typical fabrication process. Through a comprehensive analysis combining the Fermi level evolution, surface photovoltage, photoluminescence properties, photovoltaic performance, and device simulation, an overall landscape of the energy diagram of the perovskite layer is able to be determined. The findings have direct implications for real‐world devices under typical atmospheres, and provide insights into the fabrication‐process design and optimization. Furthermore, a universal Fermi level shift under vacuum for lead halide‐based perovskites revealed in this study, urges a refreshed view on the energetics studies conducted without considering the atmospheric effect.
Covalent Encapsulation of Sulfur in a MOF‐Derived S, N‐Doped Porous Carbon Host Realized via the Vapor‐Infiltration Method Results in Enhanced Sodium–Sulfur Battery Performance
Authors: Xiao Fengping , Yang Xuming , Wang Hongkang , Xu Jun , Liu Yulong , Yu Denis Y. W. , Rogach Andrey L.
Published: May 2020

Practical applications of room temperature sodium–sulfur batteries are still inhibited by the poor conductivity and slow reaction kinetics of sulfur, and dissolution of intermediate polysulfides in the commonly used electrolytes. To address these issues, starting from a novel 3D Zn‐based metal–organic framework with 2,5‐thiophenedicarboxylic acid and 1,4‐bis(pyrid‐4‐yl) benzene as ligands, a S, N‐doped porous carbon host with 3D tubular holes for sulfur storage is fabricated. In contrast to the commonly used melt‐diffusion method to confine sulfur physically, a vapor‐infiltration method is utilized to achieve sulfur/carbon composite with covalent bonds, which can join electrochemical reaction without low voltage activation. A polydopamine derived N‐doped carbon layer is further coated on the composite to confine the high‐temperature‐induced gas‐phase sulfur inside the host. S and N dopants increase the polarity of the carbon host to restrict diffusion of sulfur, and its 3D porous structure provides a large storage area for sulfur. As a result, the obtained composite shows outstanding electrochemical performance with 467 mAh g−1 (1262 mAh g−1(sulfur)) at 0.1 A g−1, 270 mAh g−1 (730 mAh g−1(sulfur)) after 1000 cycles at 1 A g−1 and 201 mAh g−1 (543 mAh g−1(sulfur)) at 5.0 A g−1.
Stretch‐Safe: Magnetic Connectors for Modular Stretchable Electronics
Authors: Kettlgruber Gerald , Danninger Doris , Moser Richard , Drack Michael , Siket Christian M. , Wirthl Daniela , Hartmann Florian , Mao Guoyong , Kaltenbrunner Martin , Bauer Siegfried
Published: May 2020

Wearable healthcare devices monitor the condition of patients outside the hospital and hence increase treatment capacity and resources. At the same time, patients benefit from wireless data transmission and conformable device designs, speeding up the rehabilitation process and integration into normal daily activities. Yet, the successful implementation of personalized treatment creates an extensive engineering challenge as devices need to adapt to a vast number of different patients and treatment protocols. Herein, soft building blocks of mobile health (mHealth) devices that reversibly assemble through a magnetic click‐on mechanism are introduced. Fabrication of reliable magnetic connectors with an inherent safeguard mechanism allows the realization of personalized wearable mHealth devices, independent of the (desired) measurement technique. Stretchable elastomer‐based units combined with imperceptible electrodes are protected from overstretching by controlling the opening force of the magnetic connections. The stretchable devices retain both electrical and mechanical functionality for more than 10 000 opening cycles, on par with the standard for universal serial bus type C (USB C) connectors used in consumer electronics. A fully functional and autonomous pulse sensor wristband, assembled from the reliably connecting circuits, demonstrates the feasible implementation for mHealth devices. The plug‐and‐play modularity ensures the applicability independent of a patient's needs, without sacrificing functionality and durability.
Entwicklung molekularer Sonden für die hyperpolarisierte NMR‐Bildgebung im biologischen Bereich
Authors: Kondo Yohei , Nonaka Hiroshi , Takakusagi Yoichi , Sando Shinsuke
Published: May 2020

Die Hyperpolarisation von Atomkernen bietet einen Weg, die NMR‐Empfindlichkeit erheblich zu steigern. Durch Anwendung dieses leistungsstarken Hilfsmittels wurden niedermolekulare Verbindungen mit stabilen Isotopen für die hochempfindliche biomedizinische Bildgebung genutzt. Die jüngste Entwicklung molekularer Sonden für die hyperpolarisierte In‐vivo‐Analyse hat gezeigt, dass diese Technik in der Lage ist, einzigartige metabolische und physiologische Informationen zu liefern. Dieser Aufsatz bietet eine kurze Einführung in die Technik der Hyperpolarisation, Ansätze zum rationalen Design molekularer Sonden für die hyperpolarisierte NMR‐Bildgebung und Beispiele von Molekülen, die erfolgreich in vitro oder in vivo für diesen Zweck genutzt wurden.
A Dicopper Platform that Stabilizes the Formation of Pentanuclear Coinage Metal Hydride Complexes
Authors: Desnoyer Addison N. , Nicolay Amélie , Ziegler Micah S. , Torquato Nicole A. , Tilley T. Don
Published: May 2020

Reduction of a dicopper(II) bis(hydroxide) complex with silanes in the presence of external copper or silver cations results in the formation of multinuclear hydride clusters, which were characterized by a variety of NMR spectroscopic experiments and X‐ray crystallography. In particular, the pentanuclear complexes adopt an unusual planar “bow tie” configuration. The copper hydride complexes are efficient catalysts for the dehydrogenation of formic acid to H2 and CO2.
Tuning the Properties of Graphdiyne by Introducing Electron‐Withdrawing/Donating Groups
Authors: Xie Chipeng , Hu Xiuli , Guan Zhaoyong , Li Xiaodong , Zhao Fuhua , Song Yuwei , Li Yuan , Li Xiaofang , Wang Ning , Huang Changshui
Published: May 2020

The properties of graphdiyne (GDY), such as energy gap, morphology, and affinity to alkali metals, can be adjusted by including electron‐withdrawing/donating groups. The push–pull electron ability and size differences of groups play a key role on the partial property adjusting of GDY derivatives MeGDY, HGDY, and CNGDY. Cyano groups (electron‐withdrawing) and methyl groups (electron‐donating) decrease the band gap and increase the conductivity of the GDY network. The cyano and methyl groups affects the aggregation of GDY, providing a higher number of micropores and specific surface area. These groups also endow the original GDY additional advantages: the stronger electronegativity of cyano groups increase the affinity of GDY frameworks to lithium atoms, and the larger atomic volume of methyl groups increases the interlayer distance and provides more storage space and diffusion tunnels.
Synthesis and Localized Photoluminescence Blinking of Lead‐Free 2D Nanostructures of Cs3Bi2I6Cl3 Perovskite
Authors: Kundu Kaushik , Acharyya Paribesh , Maji Krishnendu , Sasmal Ranjan , Agasti Sarit S. , Biswas Kanishka
Published: May 2020

Two‐dimensional (2D) lead‐free halide perovskites have generated enormous perception in the field of optoelectronics due to their fascinating optical properties. However, an in‐depth understanding on their shape‐controlled charge‐carrier recombination dynamics is still lacking, which could be resolved by exploring the photoluminescence (PL) blinking behaviour at the single‐particle level. Herein, we demonstrate, for the first time, the synthesis of nanocrystals (NCs) and 2D nanosheets (NSs) of layered mixed halide, Cs3Bi2I6Cl3, by solution‐based method. We applied fluorescence microscopy and super‐resolution optical imaging at single‐particle level to investigate their morphology‐dependent PL properties. Narrow emission line widths and passivation of non‐radiative defects were evidenced for 2D layered nanostructures, whereas the activation of shallow trap states was recognized at 77 K. Interestingly, individual NCs were found to display temporal intermittency (blinking) in PL emission. On the other hand, NS showed temporal PL intensity fluctuations within localized domains of the crystal. In addition, super‐resolution optical image of the NS from localization‐based method showed spatial inhomogeneity of the PL intensity within perovskite crystal.
Protonation of CH3N3 and CF3N3 in Superacids: Isolation and Structural Characterization of Long‐Lived Methyl‐ and Trifluoromethylamino Diazonium Ions
Authors: Saal Thomas , Blastik Zsófia E. , Haiges Ralf , Nirmalchandar Archith , Baxter Amanda F. , Christe Karl O. , Vasiliu Monica , Dixon David A. , Beier Petr , Prakash G. K. Surya
Published: May 2020

The methylamino diazonium cations [CH3N(H)N2]+ and [CF3N(H)N2]+ were prepared as their low‐temperature stable [AsF6]− salts by protonation of azidomethane and azidotrifluoromethane in superacidic systems. They were characterized by NMR and Raman spectroscopy. Unequivocal proof of the protonation site was obtained by the crystal structures of both salts, confirming the formation of alkylamino diazonium ions. The Lewis adducts CH3N3⋅AsF5 and CF3N3⋅AsF5 were also prepared and characterized by low‐temperature NMR and Raman spectroscopy, and also by X‐ray structure determination for CH3N3⋅AsF5. Electronic structure calculations were performed to provide additional insights. Attempted electrophilic amination of aromatics such as benzene and toluene with methyl‐ and trifluoromethylamino diazonium ions were unsuccessful.
Homogeneous Molecular Iron Catalysts for Direct Photocatalytic Conversion of Formic Acid to Syngas (CO+H2)
Authors: Irfan Rana Muhammad , Wang Taotao , Jiang Daochuan , Yue Qiudi , Zhang Lei , Cao Hongyun , Pan Yang , Du Pingwu
Published: May 2020

The catalytic decomposition of formic acid to generate syngas (a mixture of H2 and CO) is a highly valuable strategy for energy conversion. Syngas can be used directly in internal combustion engines or can be converted to liquid fuels, meeting future energy challenges in a sustainable manner. Herein, we report the use of homogeneous molecular iron catalysts combined with a CdS nanorods (NRs) semiconductor to construct a highly efficient photocatalytic system for direct conversion of formic acid to syngas at room temperature and atmospheric pressure. Under optimal conditions, the photocatalytic system presents an activity of 150 mmol gcatalyst−1 h−1 towards H2, and an apparent quantum yield (AQY) of 16.8 %, making it among the most active noble‐metal‐free photocatalytic systems for H2 evolution from formic acid under visible light. Meanwhile, these iron‐based molecular catalysts also demonstrate remarkable enhancement in CO evolution with robust stability. The mechanistic role of the molecular catalyst is further investigated by using cyclic voltammetry, which suggests the formation of FeI species as the key step in the catalytic conversion of formic acid to syngas.
Two‐Plateau Li‐Se Chemistry for High Volumetric Capacity Se Cathodes
Authors: Qi Xiaoqun , Yang Ying , Jin Qiang , Yang Fengyi , Xie Yong , Sang Pengfei , Liu Kun , Zhao Wenbin , Xu Xiaobin , Fu Yongzhu , Zhou Jian , Qie Long , Huang Yunhui
Published: May 2020

For Li‐Se batteries, ether‐ and carbonate‐based electrolytes are commonly used. However, because of the “shuttle effect” of the highly dissoluble long‐chain lithium polyselenides (LPSes, Li2Sen, 4≤n≤8) in the ether electrolytes and the sluggish one‐step solid‐solid conversion between Se and Li2Se in the carbonate electrolytes, a large amount of porous carbon (>40 wt % in the electrode) is always needed for the Se cathodes, which seriously counteracts the advantage of Se electrodes in terms of volumetric capacity. Herein an acetonitrile‐based electrolyte is introduced for the Li‐Se system, and a two‐plateau conversion mechanism is proposed. This new Li‐Se chemistry not only avoids the shuttle effect but also facilitates the conversion between Se and Li2Se, enabling an efficient Se cathode with high Se utilization (97 %) and enhanced Coulombic efficiency. Moreover, with such a designed electrolyte, a highly compact Se electrode (2.35 gSe cm−3) with a record‐breaking Se content (80 wt %) and high Se loading (8 mg cm−2) is demonstrated to have a superhigh volumetric energy density of up to 2502 Wh L−1, surpassing that of LiCoO2.
Palladium‐Catalyzed Asymmetric [8+2] Dipolar Cycloadditions of Vinyl Carbamates and Photogenerated Ketenes
Authors: Zhang Qun‐Liang , Xiong Qin , Li Miao‐Miao , Xiong Wei , Shi Bin , Lan Yu , Lu Liang‐Qiu , Xiao Wen‐Jing
Published: May 2020

Higher‐order cycloadditions, particularly [8+2] cycloadditions, are a straightforward and efficient strategy for constructing significant medium‐sized architectures. Typically, configuration‐restrained conjugated systems are utilized as 8π‐components for higher‐order concerted cycloadditions. However, for this reason, 10‐membered monocyclic skeletons have never been constructed via catalytic asymmetric [8+2] cycloaddition with high peri‐ and stereoselectivity. Here, we accomplished an enantioselective [8+2] dipolar cycloaddition via the merger of visible‐light activation and asymmetric palladium catalysis. This protocol provides a new route to 10‐membered monocyclic architectures bearing chiral quaternary stereocenters with high chemo‐, peri‐, and enantioselectivity. The success of this strategy relied on the facile in situ generation of Pd‐containing 1,8‐dipoles and their enantioselective trapping by ketene dipolarophiles, which were formed in situ via a photo‐Wolff rearrangement.
(E)‐2‐(2‐Allylidenehydrazinyl)thiazole derivatives: Design, green synthesis, in silico and in vitro antimycobacterial and radical scavenging studies
Authors: Hublikar Mahesh , Kadu Vikas , Dublad Jitender Kumar , Raut Dattatraya , Shirame Sachin , Makam Parameshwar , Bhosale Raghunath
Published: May 2020

By understanding the rampant infections of Mycobacterium tuberculosis (Mtb) and inflammations caused due to the generation of radical species during the Mtb infection, a series of (E)‐2‐(2‐allylidenehydrazinyl)thiazole derivatives, with dual‐action properties, was designed. The molecules were designed with a considerable variation in LogP, one of the critical parameters in physicochemical properties, and analyzed for their drug‐likeness. For the synthesis, a simple, green, and multicomponent one‐pot synthesis method was developed. The in vitro inhibition potentials were evaluated against Mtb H37Rv by the microplate Alamar Blue assay. The results reveal that compound 6 was potent, with a MIC value of 6.5 µg/ml, and showed better interactions with the KasA protein with binding free energy (ΔG) of −9.4 kcal/mol. Also, the radical scavenging properties were studied to establish the dual‐action properties of the molecules. Compound 9 exhibited promising antioxidant and nitric oxide radical scavenging activities, with 81.7% and 81.0%, respectively, at 1,000‐μg/ml concentration.
Off‐target glycans encountered along the synthetic biology route toward humanizedN‐glycans inPichia pastoris
Authors: Laukens Bram , Jacobs Pieter P. , Geysens Katelijne , Martins Jose , De Wachter Charlot , Ameloot Paul , Morelle Willy , Haustraete Jurgen , Renauld Jean‐Christophe , Samyn Bart , Contreras Roland , Devos Simon , Callewaert Nico
Published: May 2020

The glycosylation pathways of several eukaryotic protein expression hosts are being engineered to enable the production of therapeutic glycoproteins with humanized application‐customized glycan structures. In several expression hosts, this has been quite successful, but one caveat is that the newN‐glycan structures inadvertently might be substrates for one or more of the multitude of endogenous glycosyltransferases in such heterologous background. This then results in the formation of novel, undesired glycan structures, which often remain insufficiently characterized. When expressing mouse interleukin‐22 in aPichia pastoris(syn.Komagataella phaffii) GlycoSwitchM5 strain, which had been optimized to produce Man5GlcNAc2N‐glycans, glycan profiling revealed two major species: Man5GlcNAc2and an unexpected, partially α‐mannosidase‐resistant structure. A detailed structural analysis using exoglycosidase sequencing, mass spectrometry, linkage analysis, and nuclear magnetic resonance revealed that this novel glycan was Man5GlcNAc2modified with a Glcα‐1,2‐Manβ‐1,2‐Manβ‐1,3‐Glcα‐1,3‐R tetrasaccharide. Expression of a Golgi‐targeted GlcNAc transferase‐I strongly inhibited the formation of this novel modification, resulting in more homogeneous modification with the targeted GlcNAcMan5GlcNAc2structure. Our findings reinforce accumulating evidence that robustly customizing theN‐glycosylation pathway inP. pastoristo produce particular human‐type structures is still an incompletely solved synthetic biology challenge, which will require further innovation to enable safe glycoprotein pharmaceutical production.