bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Photochemical Macrocyclization Route to Asymmetric Strained [3.2] Paracyclophanes
Authors: Haensch Veit G. , Görls Helmar , Hertweck Christian 
Published: September 2022

AbstractThe intricate frameworks of paracyclophanes are an important target for synthesis since they are found in various chiral auxiliaries, solar cells, high‐performance plastics, pharmaceuticals, and molecular machines. Whereas numerous methods exist for the preparation of symmetric paracyclophanes, protocols for the efficient synthesis of strained asymmetric scaffolds are limited. Here we report a remarkably simple photochemical route to strained [3.2]paracyclophanes starting from readily available educts. By way of NMR and X‐ray analyses, we discovered that UV‐irradiation of an aromatic carboxylic ester tethered to a toluene moiety leads to the intramolecular formation of a new C−C bond, with loss of an alcohol. A systematic evaluation of the reaction conditions and substituents, as well as radical starter and triplet quenching experiments, point to a reaction mechanism involving an excited triplet state and hydrogen atom transfer. The new method proved to be robust and versatile enabling the synthesis of a range of cyclophanes with different substitutions, including an unusual diastereoisomer with two planar chiral centers, and thus proved to be a valuable addition to the synthetic toolbox.
Synthesis of meso‐Free Decaphyrin(1.1.1.1.1.1.1.1.1.1) by a Hydrodebromination Protocol; Aromaticity and Solvent‐Polarity Dependent Conformational Change
Authors: Nakai Akito , Saito Hayate , Yorimitsu Hideki , Tanaka Takayuki , Osuka Atsuhiro 
Published: September 2022

AbstractA meso‐free β‐bromodecaphyrin has been constructed by [2+3+2+3] type acid‐catalyzed cross‐condensation and subsequent oxidation. Hydrodebromination of this tetrabromodecaphyrin with NaBH4 in the presence of TMEDA and palladium catalyst afforded β‐unsubstituted doubly meso‐free [46]decaphyrin(1.1.1.1.1.1.1.1.1.1) as the first example of β‐unsubstituted meso‐free regular expanded porphyrins with the number of pyrrole units larger than eight. It exhibits distinct aromaticity originating from its 46π‐conjugated electronic circuit and flexible conformational change between non‐twisted and doubly twisted forms depending on the solvent‐polarity. Their distinct conformations have been analyzed by combined experimental and theoretical investigations.
Intense Molar Circular Dichroism in Fully Conjugated All‐Carbon Macrocyclic 1,3‐Butadiyne Linked pseudo‐meta [2.2]Paracyclophanes
Authors: Sidler Eric , Zwick Patrick , Kress Charlotte , Reznikova Ksenia , Fuhr Olaf , Fenske Dieter , Mayor Marcel 
Published: September 2022

AbstractInvited for the cover of this issue is the group of Marcel Mayor at the University of Basel with co‐workers Olaf Fuhr and Dieter Fenske from Karlsruhe Institute of Technology. The image depicts the studied all‐carbon polygon shaped macrocycles along with their intense circular dichroism spectra in the background. The bright light within the macrocycles displays its efficient conjugation. Read the full text of the article at 10.1002/chem.202201764.
Photo‐triggered Intramolecular Radical Tandem Regioselective Alkylation/Cyclization of 1,6‐Dienes with Redox‐Active Esters Enabled by an EDA Complex
Authors: Sun Bin , Ling Lan , Zhuang Xiaohui , Yang Lulu , Yin Jieli , Jin Can 
Published: September 2022

Comprehensive SummaryA photocatalyst‐ and metal‐free radical tandem alkylation/cyclization between 1,6‐dienes and redox‐active esters has been developed, affording a series of N‐aryl pyrrolidine‐2‐ones in moderate to good yields. The transformation is driven by the formation of an electron‐donor‐acceptor (EDA) complex and a subsequent single electron transfer (SET) process. This photocatalyst‐free protocol features excellent regioselectivity, mild conditions and broad substrate scope, providing a facile access to 3‐alkyl‐3,4‐dimethyl‐1‐phenylpyrrolidin‐2‐one.
Drug Discovery and Development on Pma1, Where Are We Now? A Critical Review from 1995 to 2022
Authors: Tung Truong‐Thanh , Nielsen John 
Published: September 2022

AbstractPlasma membrane H+‐ATPase (Pma1) is an enzyme uniquely found in plants and fungi. The enzyme controls the nutrient uptake of plants and fungi via an electrochemical gradient processes, which is essential for their survival. Inhibiting Pma1, therefore, constitutes an alternative antifungal target void of toxicity to humans. From a medicinal chemistry point of view, this review provides a first summary of the recent drug design, synthesis, evaluation, and discovery of molecules targeting Pma1 for 25 years from 1995 to 2022.
Preparation of Au/MoS2‐CNT@CNF Composite Electrocatalyst for High‐Efficiency Hydrogen Evolution Reaction
Authors: He Miao‐miao , Wang Dan , Liu Chang‐hai , Wang Wen‐chang , Shan Xue‐ling , Chen Zhi‐dong 
Published: September 2022

AbstractBy virtue of excellent ion storage and fast ion‐diffusion rates, molybdenum disulfide (MoS2) has been regarded as a promising electrocatalyst for hydrogen evolution reaction (HER). however, it is inherently inert to HER, its electrochemical activity is usually improved by enhancing electrical conductivity or increasing exposed active sites. To improve the conductivity and adsorption of MoS2, we prepared the MoS4‐Ppy intermediate by oxidative polymerization. Taking advantage of the adsorption properties of MoS4‐Ppy to combine with Au(III), Au(III) was simultaneously reduced to Au nanoparticles(Au NPs). Combining the Au/MoS4‐Ppy with BC and converting it into a catalyst Au/MoS2‐CNT@CNF by calcination, the catalyst activity was improved by optimizing the concentration of Au(III). Combining MoS2 with Polypyrrole (Ppy) and Bacterial cellulose (BC) not only improves the conductivity of MoS2, but also increases the exposed active sites. Notably, the obtained 50 ppm Au/MoS2‐CNT@CNFs exhibited good HER catalytic performance in an acidic electrolyte (0.5 M H2SO4) with a low overpotential of only 108 mV at a current density of 10 mA ⋅ cm−2, a low Tafel slope of 52.1 mV ⋅ dec−1, and along with outstanding stability. The improvement of electrocatalytic activity is mainly attributed to the larger electrochemical specific surface area of the composites after adsorption of Au(III) and loaded BC. The low load Au NPs can provide dense active sites. Moreover, and synergistic effect among Au NPs, MoS2, and Ppy can greatly enhance the charge transfer efficiency and lead to excellent electron transfer ability, thus significantly improving the HER performance.
An efficient and secure data sharing scheme for cloud data using hash based quadraplet wavelet permuted cryptography approach
Authors: Lakshmanan Selvam , Manimozhi Braveen , Ramachandran Venkatesan 
Published: September 2022

SummaryEnsuring the reliable and secure data transmission in cloud systems is very essential and demanding task in the recent decades. For that purpose, various security frameworks have been deployed in the existing works, which are mainly focusing the improving the privacy and confidentiality of cloud data against the unauthenticated users. Yet, it facing the major problems of inefficient accessing, increased time consumption, computational complexity, storage complexity, and memory utilization rate. Hence, this research work intends to develop an advanced and efficient cryptography model, named as, hash based quadraplet wavelet permuted cryptography (HQWPC) for the secured cloud data storage and retrieval operations. Here, the bilinear mapping and group hash function generation processes are performed to generate the keys used for cryptographic operations. Also, the zig‐zag scanning, wavelet coefficients extraction, and permutation processes are accomplished for data encryption. Consequently, the inverse of these operations is performed while decrypting the data. In addition to that, an integrated signature control policy authentication mechanism is employed for validating the authenticity of the cloud data users. This kind of signature verification process could efficiently increase the security level of cloud data. For validating the performance of the proposed security framework, various evaluation metrics have been utilized during analysis. Then, the obtained results are compared with the recent state‐of‐the‐art models for proving the efficiency of the proposed technique over the other techniques.
Changes in Sertraline Plasma Concentrations Across Pregnancy and Postpartum
Authors: Stika Catherine S. , Wisner Katherine L. , George Alfred L. , Avram Michael J. , Zumpf Katelyn , Rasmussen‐Torvik Laura J. , Mesches Gabrielle A. , Caritis Steve N. , Venkataramanan Raman , Costantine Maged M. , West Holly A. , Clark Shannon , Ciolino Jody D. 
Published: September 2022

Major depressive disorder (MDD) is a common disorder in pregnancy. Although sertraline is the most frequently prescribed antidepressant for pregnant people in the United States, limited information about its pharmacokinetics in pregnancy is available. Our objectives were to characterize plasma sertraline concentration to dose (C/D) ratios across pregnancy and postpartum and investigate the effect of pharmacogenetic variability on sertraline elimination. We performed a prospective observational cohort study in people with a singleton pregnancy ≤ 18 weeks gestation and a lifetime diagnosis of MDD at the 3 Eunice Kennedy Shriver National Institute of Child Health and Human Development (NICHD)‐funded Obstetrical‐Fetal Pharmacology Research Center sites. Subjects (N = 47) were receiving maintenance sertraline therapy and chose to continue it during pregnancy. Blood samples were obtained 24‐hours postdose every 4 weeks across pregnancy and twice postpartum for measurement of plasma concentrations of sertraline and desmethylsertraline. Overall mean sertraline C/D ratios were decreased at study onset and remained consistently low until after delivery. During the last 4 weeks of pregnancy the mean sertraline C/D ratio (95% confidence interval (CI)), 0.25 (95% CI, 0.19, 0.3) ng/mL/dose (mg/day), was smaller than the mean ratio at ≥ 8 weeks after delivery, 0.32 (95% CI, 0.27, 0.37) ng/mL/dose (mg/day), a 22% difference. Mean sertraline/desmethylsertraline ratios were highest after birth, which confirmed increased sertraline elimination during pregnancy. Sertraline C/D ratios in participants with functional CYP2C19 activity did not change significantly during pregnancy, whereas ratios in participants with poor or intermediate CYP2C19 activity decreased by 51%. Exploratory pharmacogenomic analysis indicated that pregnant people with poor or intermediate CYP2C19 activity are at risk for subtherapeutic sertraline concentrations during pregnancy.
Dot‐Blotting: A Quick Method for Expression Analysis of Recombinant Proteins
Authors: Mishra Vibhor 
Published: September 2022

AbstractExpressing recombinant proteins in heterologous host cells is a prerequisite for purification and other downstream processes. Cell cultures require a protein expression test to optimize incubation time, temperature, and additives (like chemical inducers) to identify the best growth conditions with maximum recombinant protein yield. However, running SDS‐PAGE followed by western blotting is cumbersome and results are not quick. Here, I describe a simple protocol to quickly check the presence of recombinant protein in cell cultures using a dot‐blot experiment. The cells can be rapidly lysed and directly spotted on the nitrocellulose membrane. Then, the membrane is incubated with a horseradish peroxidase (HRP) conjugated antibody raised against the affinity tag present on the recombinant protein to confirm the protein expression by chemiluminescence. It takes less than an hour to get results. This method rapidly investigates recombinant protein expression in different cell lines and tests other variables. © 2022 Wiley Periodicals LLC.Basic Protocol 1: Protein expression analysis for eukaryotic systemsBasic Protocol 2: Protein expression analysis for bacterial systems
Executives' overseas background and corporate green innovation
Authors: Chen Wen , Zhu Yufeng , Wang Chenyu 
Published: September 2022

AbstractThis study examines the impact of executives' overseas background on corporate green innovation and the possible adverse selection problem in attracting overseas‐returned executives to high‐polluted cities. Based on the data from Chinese listed companies between 2002 and 2018, we empirically find that executives' overseas background has a significantly positive impact on corporate green innovation. In addition, it is found that air pollution results in the loss of overseas‐returned executives, while the effect of executives' overseas background in stimulating corporate green innovation is more prominent in high‐polluted cities, indicating that high‐polluted cities should make more efforts to attract returnees. Therefore, we further explore the policy influence of executives' excess compensation and find that excess compensation in high‐polluted cities weakens the positive impact of executives' overseas background, although it increases the effectiveness of importing overseas‐returned executives, which means that the adverse selection caused by excess compensation in high‐polluted cities is non‐negligible.
Sodium Dual‐Ion Batteries with Concentrated Electrolytes
Authors: Guo Zhenyu , Cheng Gang , Xu Zhen , Xie Fei , Hu Yong‐Sheng , Mattevi Cecilia , Titirici Maria‐Magdalena , Crespo Ribadeneyra Maria 
Published: September 2022

AbstractNa‐based dual‐ion batteries (DIBs) are a class of post‐lithium technology with advantages including extremely fast charging, cost‐effectiveness, and high natural abundance of raw materials. Operating up to high voltages (≈5.0 V), the decomposition of classic carbonate‐based electrolyte formulations and the subsequent fade of capacity continues to be a major drawback in the development of these systems. Here, the performance of a Na‐DIB was investigated in different commonly employed electrolyte system, and a highly concentrated (3 m NaPF6) and fluorine‐rich carbonate‐based formulation was optimized to achieve a good performance when compared with literature (based on energy and power density, calculated at coin cell and only using the active mass of active materials).
Assessing limits of detection in qualitative methods: A simple implementation of logistic regression in a web‐based R Shiny application environment and its potential in toxicology and doping control
Authors: Garrido Bruno Carius , de Albuquerque Cavalcanti Gustavo , Vinícius da Silva Gomes Marcio , Scofano Barrabin Juliana , Padilha Monica Costa , Gualberto Pereira Henrique Marcelo 
Published: September 2022

AbstractThe estimation of limits of detection (LOD) for solely qualitative methods in analytical chemistry may prove challenging because all the approaches with which chemists are familiar require some type of numeric data input. The best model to describe the binary response in these methods (detected/not detected) is a logistic model; however, these models are not easily handled by most of the laboratories and generally demand expensive statistical software packages. In this work, the advantages of applying this approach are discussed and its implementation using commercial spreadsheet software is demonstrated. A free online application based on the R environment using shinyapps was developed and its application was validated and discussed with a dataset of 57 different target compounds analyzed in urine according to the requirements of the World Anti‐Doping Agency (WADA). This tool allows free, extremely quick, and easy determinations of LOD in qualitative analyses as well as the determination of the probabilities of detection in any given concentration.
Divergence in digestive and metabolic strategies matches habitat differentiation in juvenile salmonids
Authors: Monnet Gauthier , Rosenfeld Jordan S. , Richards Jeffrey G. 
Published: September 2022

AbstractDivergent energy acquisition and processing strategies associated with using different microhabitats may allow phenotypes to specialize and coexist at small spatial scales. To understand how ecological specialization affects differentiation in energy acquisition and processing strategies, we examined relationships among digestive physiology, growth, and energetics by performing captive experiments on juveniles of wild coho salmon (Oncorhynchus kisutch) and steelhead trout (O. mykiss) that exploit adjacent habitats along natural low‐to‐high energy flux gradients (i.e., pools versus riffles) in coastal streams. We predicted that: (i) the specialization of steelhead trout to high‐velocity, high‐energy habitats would result in elevated food intake and growth at the cost of lower growth efficiency relative to coho salmon; (ii) the two species would differentiate along a rate‐maximizing (steelhead trout) versus efficiency‐maximizing (coho salmon) axis of digestive strategies matching their ecological lifestyle; and (iii) the higher postprandial metabolic demand (i.e., specific dynamic action, SDA) associated with elevated food intake would occupy a greater fraction of the steelhead trout aerobic budget. Relative to coho salmon, steelhead trout presented a pattern of faster growth and higher food intake but lower growth efficiency, supporting the existence of a major growth versus growth efficiency trade‐off between species. After accounting for differences in ration size between species, steelhead trout also presented higher SDA than coho salmon, but similar intestinal transit time and lower assimilation efficiency. Both species presented similar aerobic budgets since the elevated SDA of steelhead trout was largely compensated by their higher aerobic scope relative to coho salmon. Our results illustrate the key contribution of digestive physiology to the adaptive differentiation of juvenile growth, energetics, and overall performance of taxa with divergent habitat specializations along a natural productivity gradient.
Maternal testosterone affects offspring telomerase activity in a long‐lived seabird
Authors: Noguera Jose C. , Velando Alberto 
Published: September 2022

AbstractAndrogens are a group of steroid hormones that have long been proposed as a mechanism underpinning intergenerational plasticity. In birds, maternally allocated egg testosterone, one of the main androgens in vertebrates, affects a wide variety of offspring phenotypic traits but the mechanisms underlying this form of intergenerational plasticity are not yet well understood. Recent in vitro and animal model studies have shown that telomerase expression and activity are important targets of androgen signaling. The telomerase enzyme is known for its repair function on telomeres, the DNA–protein complexes at the ends of chromosomes that are involved in genomic integrity and cell aging. However, the role of maternal testosterone in influencing offspring telomerase levels in natural populations and its consequences on telomere length and potentially on offspring development is still unknown. Here, by experimentally modifying the level of egg testosterone in a natural population of yellow‐legged gull (Larus michahellis), we show that chicks hatched from testosterone‐treated eggs had higher average levels of telomerase and faster growth than controls during the first week of life. While testosterone‐treated chicks also tended to have longer telomeres than controls at hatching this difference disappeared by day 6 of age. Overall, our results suggest that maternal testosterone may have a potential adaptive value by promoting offspring growth and presumably telomerase levels, as this enzyme plays other important physiological functions (e.g., stress resistance, cell signaling, or tissue genesis) besides telomere lengthening. Nonetheless, our knowledge of the potential adaptive function of telomerase in natural populations is scarce and so the potential pathways linking maternal hormones, offspring telomerase, and fitness should be further investigated.
Predicting range shifts of the giant pandas under future climate and land use scenarios
Authors: Liu Zhenjun , Zhao Xuzhe , Wei Wei , Hong Mingsheng , Zhou Hong , Tang Junfeng , Zhang Zejun 
Published: September 2022

AbstractUnderstanding and predicting how species will respond to global environmental change (i.e., climate and land use change) is essential to efficiently inform conservation and management strategies for authorities and managers. Here, we assessed the combined effect of future climate and land use change on the potential range shifts of the giant pandas (Ailuropoda melanoleuca) in Sichuan Province, China. We used species distribution models (SDMs) to forecast range shifts of the giant pandas by the 2050s and 2070s under four combined climate and land use change scenarios. We also compared the differences in distributional changes of giant pandas among the five mountains in the study area. Our SDMs exhibited good model performance and were not overfitted, with a mean Boyce index of 0.960 0.015 and a mean omission rate of 0.002 0.003, and suggested that precipitation seasonality, annual mean temperature, the proportion of forest cover, and total annual precipitation are the most important factors in shaping the current distribution pattern of the giant pandas. Our projections of future species distribution also suggested a range expansion under an optimistic greenhouse gas emission, while suggesting a range contraction under a pessimistic greenhouse gas emission. Moreover, we found that there is considerable variation in the projected range change patterns among the five mountains in the study area. Especially, the suitable habitat of the giant panda is predicted to increase under all scenarios in the Minshan mountains, while is predicted to decrease under all scenarios in Daxiangling and Liangshan mountains, indicating the vulnerability of the giant pandas at low latitudes. Our findings highlight the importance of an integrated approach that combines climate and land use change to predict the future species distribution and the need for a spatial explicit consideration of the projected range change patterns of target species for guiding conservation and management strategies.
How to promote multifunctionality of vegetated strips in arable farming: A qualitative approach for Germany
Authors: Schütz Lukas , Wenzel Bettina , Rottstock Tanja , Dachbrodt‐Saaydeh Silke , Golla Burkhard , Kehlenbeck Hella 
Published: September 2022

AbstractVegetated strips are in the focus of many stakeholders of agroecosystems and are part of several agri‐environmental schemes in Germany. Stakeholders have different expectations and demands on the functionality and services of vegetated strips. In our review, we focused on biodiversity and the ecosystem services pollination, conservation biocontrol, landscape aesthetics, buffer function, and biomass production and their associated functions. We assessed factors that are crucial to support service provision and reviewed trade‐offs between the ecosystem (dis)services. We identified five characteristics that are important for the provision of the assessed ecosystem services: age of vegetated strips, flower cover, size or width of the strip, management, and type of adjacent habitat. We conclude that adjusting the target of subsidies with respect to the analyzed factors for biodiversity can help to promote the multifunctionality of vegetated strips in arable farming.