bluuebunny/crossref_metadata_2025 huggingface dataset:
Integrated Environmental and Exergoeconomic Analysis of Biomass‐Derived Maleic Anhydride
Authors: Blanco Jorge , Linares Maria , López Granados Manuel , Agirre Ion , Gandarias Iñaki , Arias Pedro Luis , Iglesias Jose , Moreno Jovita , García Alicia
Published: June 2022

Life cycle analysis and exergy analysis are applied to compare the production of maleic anhydride from different feedstock, both biomass‐ and petrochemical‐derived raw materials, in order to evaluate the sustainability of alternative biorefinery processes to conventional routes. The considered processes involve two options: gas and aqueous phase furfural oxidation with oxygen (air) and hydrogen peroxide as oxidants, respectively, considered as sustainable technologies because of the use of renewable feedstock. Conventional routes, used as benchmarks, include the current production processes using benzene or butane as raw materials. The results show that the aqueous phase process is far from being viable from an energy and environmental point of view due to the high exergy destruction and the use of H2O2 as oxidant (whose production entails important environmental drawbacks). On the contrary, the gas phase oxidation of furfural shows competitive results with petrochemical technologies. Nevertheless, the major environmental drawback of the new furfural‐to‐maleic anhydride production processes is detected on the environmental profile of the starting raw material. The results suggest that a better environmental footprint for maleic anhydride production in gas phase can be obtained if environmentally friendly furfural production technologies are used at the commercial scale.
The impact of the Meals‐to‐You program on food insecurity
Authors: Anderson Theresa , Waxman Elaine , Gundersen Craig
Published: June 2022

Food insecurity among children in the United States remains a serious problem, especially during summer months. While there are summer meal programs such as the Summer Food Service Program (SFSP), participation rates are low. In response, in 2019, Meals‐to‐You (MTY) was piloted by the U.S. Department of Agriculture through the Baylor Collaborative on Hunger and Poverty where food boxes were delivered to households with a focus on rural areas. This was expanded during COVID to an Emergency Meals‐to‐You component. We find that among participating households, those receiving more boxes had larger declines in food insecurity, especially in more remote rural areas.
Contributors to SerumNfLLevels in People without Neurologic Disease
Authors: Fitzgerald Kathryn C. , Sotirchos Elias S. , Smith Matthew D. , Lord Hannah‐Noelle , DuVal Anna , Mowry Ellen M. , Calabresi Peter A.
Published: June 2022

Objective

To assess the effects of demographics, lifestyle factors, and comorbidities on serum neurofilament light chain (sNfL) levels in people without neurologic disease and establish demographic‐specific reference ranges of sNfL.

Methods

The National Health and Nutrition Examination Survey (NHANES) is a representative sample of the US population in which detailed information on demographic, lifestyle, routine laboratory tests, and overall health status are systematically collected. From stored serum samples, we measured sNfL levels using a novel high‐throughput immunoassay (Siemens Healthineers). We evaluated the predictive capacity of 52 demographic, lifestyle, comorbidity, anthropometric, or laboratory characteristics in explaining variability in sNfL levels. Predictive performance was assessed using cross‐validatedR2(R2cv) and forward selection was used to obtain a set of best predictors of sNfL levels. Adjusted reference ranges were derived incorporating characteristics using generalized additive models for location, scale, and shape.

Results

We included 1,706 NHANES participants (average age: 43.6 ± 14.8 y; 50.6% male, 35% non‐white) without neurological disorders. In univariate models, age explained the most variability in sNfL (R2cv = 26.8%). Multivariable prediction models for sNfL contained three covariates (in order of their selection): age, creatinine, and glycosylated hemoglobin (HbA1c) (standardized β—age: 0.46, 95% confidence interval [CI]: 0.43, 0.50; creatinine: 0.18, 95% CI: 0.13, 0.22; HbA1c: 0.09, 95% CI: 0.06, 0.11). Adjusted centile curves were derived incorporating identified predictors. We provide an interactive R Shiny application to translate our findings and allow other investigators to use the derived centile curves.

Interpretation

Results will help to guide interpretation of sNfL levels as they relate to neurologic conditions. ANN NEUROL 2022;92:688–698
Ein Kupfer‐Käfig‐Komplex als Nachahmung der pMMO CuC‐Seite
Authors: Bete Sarah C. , May Leander K. , Woite Philipp , Roemelt Michael , Otte Matthias
Published: June 2022

Das aktive Zentrum der partikulären Methan‐Monooxygenase (pMMO) und ihr Wirkungsmechanismus sind nicht bekannt. In den letzten Jahren trat die CuC‐Seite als potentielles aktives Zentrum auf, jedoch fehlt es bisher an biomimetischen Studien zu dieser vom Enzym bereitgestellten Koordinationssphäre. Hier wird über die Synthese eines Käfigliganden berichtet, welcher solch eine Koordinationssphäre bereitstellt. Die Koordination an Kupfer erfolgt durch die beiden Imidazol‐ und eine Carboxylatgruppe des Liganden. Abhängig von der Oxidationsstufe kann der Ligand unterschiedliche Koordinationsmodi annehmen, was durch Festkörperstrukturen und computerchemische Untersuchungen belegt wurde. Der Kupfer(I)‐Komplex reagiert leicht mit Sauerstoff und geht dadurch eine CH‐Aktivierung ein. Darüber hinaus wird die katalytische aerobe Oxidation von Hydrochinonen als Ubichinol‐Nachahmungen gezeigt. Eine saubere Ein‐Elektronen‐Oxidation findet unter milden Bedingungen statt. Die EPR‐Analyse des Kupfer(II)‐Komplexes zeigt in Gegenwart von Wasser bemerkenswerte Ähnlichkeiten zu Daten, welche von pMMO erhalten wurden.
Upconversion Luminescence‐Boosted Escape of DNAzyme from Endosomes for Enhanced Gene‐Silencing Efficacy
Authors: Chen Yaoxuan , Zhao Rupeng , Li Lele , Zhao Yuliang
Published: June 2022

Despite the enormous potential of DNAzyme for gene therapy, its efficacy is hampered by the limited endosomal escape capability. Here, we develop a near‐infrared (NIR) light‐controlled DNAzyme delivery platform to achieve enhanced gene‐silencing efficacy. The nanoplatform is composed of therapeutic DNAzyme, photosensitizers (PSs) and upconversion nanoparticles (UCNPs) that can convert NIR light to visible light. The system allows NIR light‐activatable generation of cytotoxic reactive oxygen species due to the energy transfer from the UCNPs to PSs, which boosts the endosomal escape of DNAzyme for an improved gene‐silencing efficacy. We demonstrate that the nanocomposites represent a promising platform to integrate DNAzyme‐based gene therapy with NIR light‐triggered photodynamic therapy for combinational tumor treatment. This work highlights a robust approach to combat the current limitations of DNAzyme delivery systems.
Efficient Broadband Near‐Infrared Emission from Lead‐Free Halide Double Perovskite Single Crystal
Authors: Zhang Gangyi , Wang Deyin , Lou Bibo , Ma Chong‐Geng , Meijerink Andries , Wang Yuhua
Published: June 2022

Ultra‐broadband near‐infrared (NIR) luminescent materials are the most important component of NIR light‐emitting devices (LED) and are crucial for their performance in sensing applications. A major challenge is to design novel NIR luminescent materials to replace the traditional Cr3+‐doped systems. We report an all‐inorganic bismuth halide perovskite Cs2AgBiCl6 single crystal that achieves efficient broadband NIR emission by introducing Na ions. Experiments and density functional theory (DFT) calculations show that the NIR emission originates from self‐trapped excitons (STE) emission, which can be enhanced by weakening the strong coupling between electrons and phonons. The high photoluminescence quantum efficiency (PLQY) of 51 %, the extensive full width at half maximum (FWHM) of 270 nm and the stability provide advantages as a NIR luminescent material. The single‐crystal‐based NIR LED demonstrated its potential applications in NIR spectral detection as well as night vision.
Photostability and Dynamic Helical Behavior in Chiral Poly(phenylacetylene)s with a Preferred Screw‐Sense
Authors: Rey‐Tarrío Francisco , Guisán‐Ceinos Santiago , Cuerva Juan M. , Miguel Delia , Ribagorda Maria , Quiñoá Emilio , Freire Félix
Published: June 2022

Helical polymers such as poly(phenylacetylene)s (PPAs) are interesting materials due to the possibility of tuning their helical scaffold (sense and elongation) once they have been prepared and by the presence of external stimuli. The main limitation in the application of PPAs is their poor photostability. These polymers degrade under visible light exposure through a photochemical electrocyclization process. In this work, it was demonstrated, through a selected example, how the photochemical degradation in PPAs is directly related to their dynamic helical behavior. Thus, while PPAs with dynamic helical structures show poor photostability under UV/Vis light exposure, poly‐(R)‐1, bearing an enantiopure sulfoxide group as pendant group and designed to have a quasi‐static helical behavior, shows a large photostability due to the restricted conformational composition at the polyene backbone, needed to orient the conjugated double bonds prior to the photochemical electrocyclization process and the subsequent degradation of the material.
Simulating the Structure of Carbon Dots via Crystalline π‐Aggregated Organic Nanodots Prepared by Kinetically Trapped Self‐Assembly
Authors: Yang Jianye , Guo Like , Yong Xue , Zhang Tongjin , Wang Boyang , Song Haoqiang , Zhao Yong Sheng , Hou Hongwei , Yang Bai , Ding Jie , Lu Siyu
Published: June 2022

This work reports the successful preparation of a new type of crystalline luminescent organic nanodot (<3.5 nm) by kinetically trapped self‐assembly, which is then used as a simplified π‐packing model to simulate the structure of CDs. The precise structure and J‐aggregation‐induced photoluminescence (PL) of the nanodots are revealed by investigating the structural relationship between the nanodots and the corresponding single crystals and their properties. Compared with the single crystals, crystalline organic nanodots show longer PL lifetime, higher PL quantum yield, and narrower PL peak, indicating that they are potential organic quantum nanodots. In addition, the efficient π‐stacking environment in the corresponding single crystals can promote π‐aggregation‐induced PL anisotropy. This work indicates crystalline organic nanodots with precise structures to be potentially useful for understanding the structures of CDs and to be attractive potential luminescent materials.
PEG‐Functionalized Hollow Multishelled Structures with On‐Off Switch and Rate‐Regulation for Controllable Antimicrobial Release
Authors: Zhao Decai , Wei Yanze , Jin Quan , Yang Nailiang , Yang Yang , Wang Dan
Published: June 2022

The construction of responsive antimicrobial carriers with multifunctional and controllable release is an attractive but challenging proposition. Recently developed hollow multishelled structures (HoMSs) offers structural advantages, such as easily modifiable surfaces and mutually influenced shells. Herein, we report a novel pH‐responsive antimicrobial carrier having hierarchical shells as multilevel responsive bodies using polyethylene glycol (PEG) as a gated regulator. The interaction between PEG‐functionalized shells endows them with a pH‐responsive switch and rate‐regulator capability. These features are present in the form of rapid release of molecules wrapped in the outer shell, and controlled diffusion of antimicrobials stored in the inner shell by electrostatic interaction, resulting in a long‐lasting mildew resistance for up to 71 days. The versatility of the hierarchical interactions of HoMSs will inspire the design of promising smart drug carriers.
Cu‐catalyzed synthesis of 1‐naphthols with terminal alkynes and 2‐bromoaryl ketones
Authors: Ma Peng , Wang Yuhang , Wang Jianhui
Published: June 2022

A Cu‐catalyzed straightforward synthesis of 1‐naphthols via an 6‐endo‐dig cyclization of terminal alkynes with 2‐bromoaryl ketones in water is reported. The Cu(I) catalytic system tolerates various electron‐withdrawing and electron‐donating functional groups on both substrates and exhibits unique 6‐endo‐dig selectivity to give 1‐naphthols in moderate to good yields.
Porous carbon‐supported CoPd nanoparticles: High‐performance reduction reaction of nitrophenol
Authors: Buğday Nesrin , Altin Serdar , Yaşar Sedat
Published: June 2022

Magnetic porous carbon composite was synthesized from zeolitic imidazolate framework (ZIF‐12) and used as a support material to fabricate CoPd nanoparticles decorated NPC@ZIF‐12 nanocatalyst. The structure of CoPd@NPC@ZIF‐12 has been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), Raman, Brunauer–Emmett–Teller (BET), X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and inductively coupled plasma mass spectrometry (ICP‐MS) techniques. The catalytic reduction reaction of nitrophenols (NP) to aminophenols (AP) was successfully achieved by CoPd@NPC@ZIF‐12 nanocatalyst. When the catalytic performance of the catalyst was compared with other reported catalysts, the performance of the catalyst and reusability was found much better. This better catalytic activity of the CoPd@NPC@ZIF‐12 nanocatalyst may be attributed to facilitating the mass transfer of the nitro compound and the wettability of catalyst caused by the high nitrogen content of the carbon matrix and to the synergistic effect of Co and Pd nanoparticles. The CoPd@NPC@ZIF‐12 nanocatalyst showed perfect catalytic activity in the reduction of 4‐nitrophenol (4‐NP), 3‐nitrophenol (3‐NP), and 2,4‐nitrophenol (2,4‐DNP) reactions with high turnover frequency (TOF) values of 1679, 2687, and 1014 h−1, respectively. The reusability experiments of the CoPd@NPC@ZIF‐12 nanocatalyst showed that the catalytic activity of the CoPd@NPC@ZIF‐12 nanocatalyst was almost retained after 10 consecutive reaction runs. The SEM, XRD, and FTIR analyses of the 10 times used CoPd@NPC@ZIF‐12 nanocatalyst showed that there were limited changes in the structure of the CoPd@NPC@ZIF‐12 nanocatalyst. This highly active, magnetically separable, and recyclable CoPd@NPC@ZIF‐12 catalyst exhibits better catalytic activity than commercial Pd/C catalysts.
Investigation of the gas permeation properties of a polyether sulfone asymmetric membrane via the phase inversion method
Authors: Huang Nai‐Yi , Wang Cheng‐Chien , Chen Chuh‐Yung
Published: June 2022

A defect‐free polyether sulfone (PES) asymmetric membrane was prepared by a one‐step phase inversion process and applied gas separation process in this article. The morphology of the PES asymmetric membrane formed via phase inversion that was correlated with the solvent composition, evaporation environment, coagulation bath, and so forth. The results reveal two kinds of coagulation phenomena that lead to different membrane structures and separation results. An instantaneous coagulation PES membrane formed a finger‐like structure within the membrane, and a delayed coagulation PES membrane resulted in a sponge‐like structure membrane. The selectivity of O2/N2 for membrane gas separation indicated that the asymmetric membranes prepared via a one‐step process in this study were defect‐free. Using the phase inversion method to fabricate asymmetric membranes improved the low permeability characteristic of glassy polymers. The maximum permeability of CO2 for the PES asymmetric membrane in the text can approach 30 Barrer. The results of gas separation for the sponge‐like PES membrane showed that the selectivity of O2/N2 and CO2/N2 was 7.1 and 35.6, respectively. This research showed that a PES asymmetric membrane was fabricated via a one‐step process without further defect repair and was applied effectively for CO2 membrane gas separation.
Ligand‐binding specificities of four odorant‐binding proteins in Conogethes punctiferalis
Authors: Tian Lin , Guo Hong‐Gang , Ren Zheng‐Guang , Zhang Ai‐Huan , Qin Xiao‐Chun , Zhang Min‐Zhao , Du Yan‐Li
Published: June 2022

Odorant‐binding proteins (OBPs) play essential roles in lepidopteran insects' perception of host volatiles by binding and transporting hydrophobic ligands. The yellow peach moth (YPM), Conogethes punctiferalis (Guenée), is a serious agricultural pest, with broad host range and cryptic feeding habits. However, few studies about YPM perceiving pheromones and host plant odorants have been reported. In this study, four OBP genes (CpunOBP8, CpunOBP9, CpunABP, and CpunGOBP2) were cloned from the antennae of YPM. The recombinant proteins were expressed and purified by prokaryotic expression system, with their binding affinities to 26 ligands being tested. Four CpunOBPs all had six conserved cysteine residues, which were typical structural characteristics of classical OBPs. The fluorescence competitive binding assay indicated that CpunOBP8 and CpunABP could not only exhibit high binding affinities to female sex pheromones, but also to host plant odorants. For example, CpunOBP8 bound strongly with cis‐10‐hexadecenal, hexadecanal, and so forth, whereas CpunABP bound with cis‐10‐hexadecenal, camphene, and 3‐carene. Comparatively, CpunOBP9 and CpunGOBP2 could only bind with host plant odorants, with CpunOBP9 binding strongly to 3‐methyl‐1‐butanol, hexyl acetate, and so forth, while CpunGOBP2 displaying the widest binding spectra and correlating with 3‐carene, pentyl acetate, and so forth. The results indicated that on the one hand, each of the four CpunOBPs had its specific binding spectra when binding and transporting olfactory ligands; on the other hand, the same ligand might be bound to more than one CpunOBPs, which would provide information for the potential application of semiochemicals in controlling YPM.
Strong Association of Combined Genetic Deficiencies in the Classical Complement Pathway With Risk of Systemic Lupus Erythematosus and Primary Sjögren's Syndrome
Authors: Lundtoft Christian , Sjöwall Christopher , Rantapää‐Dahlqvist Solbritt , Bengtsson Anders A. , Jönsen Andreas , Pucholt Pascal , Wu Yee Ling , Lundström Emeli , Eloranta Maija‐Leena , Gunnarsson Iva , Baecklund Eva , Jonsson Roland , Hammenfors Daniel , Forsblad‐d'Elia Helena , Eriksson Per , Mandl Thomas , Bucher Sara , Norheim Katrine B. , Auglaend Johnsen Svein Joar , Omdal Roald , Kvarnström Marika , Wahren‐Herlenius Marie , Truedsson Lennart , Nilsson Bo , Kozyrev Sergey V. , Bianchi Matteo , Lindblad‐Toh Kerstin ,   the DISSECT consortium, the ImmunoArray consortium, Yu Chack‐Yung , Nordmark Gunnel , Sandling Johanna K. , Svenungsson Elisabet , Leonard Dag , Rönnblom Lars
Published: June 2022

Objective

Complete genetic deficiency of the complement component C2 is a strong risk factor for monogenic systemic lupus erythematosus (SLE), but whether heterozygous C2 deficiency adds to the risk of SLE or primary Sjögren's syndrome (SS) has not been studied systematically. This study was undertaken to investigate potential associations of heterozygous C2 deficiency and C4 copy number variation with clinical manifestations in patients with SLE and patients with primary SS.

Methods

The presence of the common 28‐bp C2 deletion rs9332736 and C4 copy number variation was examined in Scandinavian patients who had received a diagnosis of SLE (n = 958) or primary SS (n = 911) and in 2,262 healthy controls through the use of DNA sequencing. The concentration of complement proteins in plasma and classical complement function were analyzed in a subgroup of SLE patients.

Results

Heterozygous C2 deficiency—when present in combination with a low C4A copy number—substantially increased the risk of SLE (odds ratio [OR] 10.2 [95% confidence interval (95% CI) 3.5–37.0]) and the risk of primary SS (OR 13.0 [95% CI 4.5–48.4]) when compared to individuals with 2 C4A copies and normal C2. For patients heterozygous for rs9332736 with 1 C4A copy, the median age at diagnosis was 7 years earlier in patients with SLE and 12 years earlier in patients with primary SS when compared to patients with normal C2. Reduced C2 levels in plasma (P = 2 × 10−9) and impaired function of the classical complement pathway (P = 0.03) were detected in SLE patients with heterozygous C2 deficiency. Finally, in a primary SS patient homozygous for C2 deficiency, we observed low levels of anti–Scl‐70, which suggests a risk of developing systemic sclerosis or potential overlap between primary SS and other systemic autoimmune diseases.

Conclusion

We demonstrate that a genetic pattern involving partial deficiencies of C2 and C4A in the classical complement pathway is a strong risk factor for SLE and for primary SS. Our results emphasize the central role of the complement system in the pathogenesis of both SLE and primary SS.
Semi‐supervised empirical Bayes group‐regularized factor regression
Authors: Münch Magnus M. , van de Wiel Mark A. , van der Vaart Aad W. , Peeters Carel F. W.
Published: June 2022

The features in a high‐dimensional biomedical prediction problem are often well described by low‐dimensional latent variables (or factors). We use this to include unlabeled features and additional information on the features when building a prediction model. Such additional feature information is often available in biomedical applications. Examples are annotation of genes, metabolites, or p‐values from a previous study. We employ a Bayesian factor regression model that jointly models the features and the outcome using Gaussian latent variables. We fit the model using a computationally efficient variational Bayes method, which scales to high dimensions. We use the extra information to set up a prior model for the features in terms of hyperparameters, which are then estimated through empirical Bayes. The method is demonstrated in simulations and two applications. One application considers influenza vaccine efficacy prediction based on microarray data. The second application predicts oral cancer metastasis from RNAseq data.
From carbon dependence to renewables: The European oil majors' strategies to face climate change
Authors: Vieira Leticia Canal , Longo Mariolina , Mura Matteo
Published: June 2022

International oil companies play a central role in the transition towards a low‐carbon economy. These companies have the leadership and influence to advance technological alternatives or sustain the current dependence on fossil fuels. This article aims to analyse the decarbonisation strategies that European oil companies are performing in the wake of climate change. A document analysis was integrated with carbon emission data from 10 European international oil companies and uncovered the four main strategies adopted by companies: sustained carbon dependence, carbon emissions compensation, carbon emissions mitigation and carbon independence. The results indicate that companies have adopted variable levels of action, despite their overlapping discourse on climate mitigation, with only one of the analysed firms performing a transition away from fossil fuels.
A High‐Nuclear Isopolymolybdate Cluster Assembled with an Anionic [{Mo24O48(OMe)32}]8−and Two Charge‐Neutral [{Mo24O52(OMe)28}] Cages
Authors: Wang Yingyue , Ma Xinyi , Li Guoao , Li Huafeng , Wang Quanzhong , Chen Wenjing , Ma Pengtao , Li Shuhua , Niu Jingyang , Wang Jingping
Published: June 2022

We synthesized a high‐nuclear isopolymolybdate cluster (n‐Bu4N)6H2[{Mo24O48(OMe)32}{Mo24O52(OMe)28}2] ⋅ 25H2O ⋅ 6CH3CN (1) by using [Mo6O19]2−as the base precursor. Crystallographic characterization shows the cluster is composed of an anionic [{Mo24O48(OMe)32}]8−cage and two charge‐neutral [{Mo24O52(OMe)28}] cages. Supported by the electrospray ionization mass spectrometry study, the polyoxoanion structural unit [Mo24O48(CH3O)27]3−demonstrates strong stability in acetonitrile solution. Moreover, 1 exhibits good proton conductivity of 1.79×10−3 S cm−1at 358 K and 98 % relative humidity.
In Situ Preparation of CsPbBr3@CsPb2Br5 Composite Assisted with Water as a Highly Efficient and Stable Catalyst for Photothermal CO2 Hydrogenation
Authors: Gao Peng , Cui Zihao , Liu Xiaolei , Wu Yaqiang , Zhang Qianqian , Wang Zeyan , Zheng Zhaoke , Cheng Hefeng , Liu Yuanyuan , Li Qing , Huang Baibiao , Wang Peng
Published: June 2022

Lead halide perovskite has triggered a lot of research due to its superior optical properties. However, halide perovskite materials have poor environmental stabilities and are easily affected by external factors such as water and heat, resulting in structural decomposition and performance failure. Contrary to this commonplace concept, it is found that CsPbBr3 (CPB) can convert to CsPb2Br5 (CP2B5) partially when meeting a small amount of water, and the CsPbBr3@CsPb2Br5 (CPB@CP2B5) composite is synthesized by an in situ method accordingly. The CPB@CP2B5 composite shows an enhanced catalytic performance compared with pure CPB, as well as a dramatically synergistic effect of photo and thermal for catalytic CO2 hydrogenation. The CO production rate of CPB@CP2B5 is determined as 69 μmol g−1 h−1 under light irradiation at 200 °C, which is 156.8 and 43.4 times higher than that under pure photo (0.44 μmol g−1 h −1) and pure thermal (1.59 μmol g−1 h −1) condition, respectively. Meanwhile, the CPB@CP2B5 sample is also stable, which shows no significant decline in the catalytic activity during 8 cycles of repeated experiments. The probable mechanism is explored by utilizing a series of in situ characterizations.
Direct C−H Trifluoromethylation of (Hetero)Arenes in Water Enabled by Organic Photoredox‐Active Amphiphilic Nanoparticles
Authors: Eisenreich Fabian , Palmans Anja R. A.
Published: June 2022

Photoredox‐catalyzed chemical conversions are predominantly operated in organic media to ensure good compatibility between substrates and catalysts. Yet, when conducted in aqueous media, they are an attractive, mild, and green way to introduce functional groups into organic molecules. We here show that trifluoromethyl groups can be readily installed into a broad range of organic compounds by using water as the reaction medium and light as the energy source. To bypass solubility obstacles, we developed robust water‐soluble polymeric nanoparticles that accommodate reagents and photocatalysts within their hydrophobic interior under high local concentrations. By taking advantage of the high excited state reduction potential of N‐phenylphenothiazine (PTH) through UV light illumination, the direct C−H trifluoromethylation of a wide array of small organic molecules is achieved selectively with high substrate conversion. Key to our approach is slowing down the production of CF3 radicals during the chemical process by reducing the catalyst loading as well as the light intensity, thereby improving effectiveness and selectivity of this aqueous photocatalytic method. Furthermore, the catalyst system shows excellent recyclability and can be fueled by sunlight. The method we propose here is versatile, widely applicable, energy efficient, and attractive for late‐stage introduction of trifluoromethyl groups into biologically active molecules.
Rapid Discrimination of Bacterial Drug Resistivity by Array‐Based Cross‐Validation Using 2D MoS2
Authors: Behera Pradipta , Kumar Singh Krishna , Kumar Saini Deepak , De Mrinmoy
Published: June 2022

The precise discrimination of microbes based on family, class and drug resistivity is essential for the early diagnosis of infectious diseases. Information about the type and strength of drug resistivity can help the analyst to prescribe a suitable antibiotic at the proper dosage to completely eradicate microbes without giving them a chance to gain further resistance. Herein, we propose a sensor array based on the use of cationic two‐dimensional MoS2 units and green fluorescence protein as building blocks. Cationic surfaces of receptors with various functionality were suitable for tunable interaction with anionic surfaces of microbes. The array successfully discriminates six different bacterial strains. The versatile ability of the receptors to bind with the wild‐type as well as the corresponding ampicillin‐resistant strain contributed significantly to rapid detection with high sensitivity. The optimized array was able to classify five different types and three different extents of drug‐resistant variants of Escherichia coli by using bacteria cells and lysates. Finally, we have introduced the cross identification method using both bacteria cells and lysates and we found a great enhancement of detection in sensitivity and accuracy. This is the first report of this approach, which can be extended to many other methods for better accuracy in array‐based detection.
Double‐σ‐Bonded Close‐Shell Dimers and Peroxy‐Linked Open‐Shell Dimer Derived from aC3Symmetric Trioxophenalenyl Neutral Diradical
Authors: Murata Tsuyoshi , Yoshida Kenta , Suzuki Shuichi , Ueda Akira , Nishida Shinsuke , Kawai Junya , Fukui Kozo , Sato Kazunobu , Takui Takeji , Nakasuji Kazuhiro , Morita Yasushi
Published: June 2022

A novel neutral diradical of π‐extended phenalenyl derivative having three oxo‐groups, tri‐tert‐butyl‐1,4,7‐trioxophenalenyl, and two types of the corresponding σ‐dimers were investigated. Quantum chemical calculations showed that the neutral diradical is in triplet ground state having doubly degenerate singly occupied molecular orbitals. The neutral diradical undergoes a σ‐dimerization, generating two types of σ‐dimers immediately after the preparation. One of the σ‐dimers, which was selectively generated in the crystalline state, was a close‐shell dimer linked through double‐σ‐bonds on the phenalenyl skeleton with a long C−C bond length of 1.66 Å. The other σ‐dimer, which existed only in the solution state, was a peroxy‐linked open‐shell dimer in which one σ‐bond was formed between two oxygen atoms. Furthermore, the temperature‐dependent1H NMR and ESR spectra revealed that these σ‐dimers are in equilibrium in the solution state by the reversible σ‐bond formation/cleavage via the neutral diradical as a key intermediate.
Immunofluorescent and molecular characterization of effusion tumor cells reveal cancer site‐of‐origin and disease‐driving mutations
Authors: Zhu Yili , Wang Aihui , Allard Grace M. , Nordberg Joshua J. , Nair Ramesh V. , Kunder Christian A. , Lowe Alarice C.
Published: June 2022

Background

Effective cancer treatment relies on precision diagnostics. In cytology, an accurate diagnosis facilitates the determination of proper therapeutics for patients with cancer. Previously, the authors developed a multiplexed immunofluorescent panel to detect epithelial malignancies from pleural effusion specimens. Their assay reliably distinguished effusion tumor cells (ETCs) from nonmalignant cells; however, it lacked the capacity to reveal specific cancer origin information. Furthermore, DNA profiling of ETCs revealed some, but not all, cancer‐driver mutations.

Methods

The authors developed a new multiplex immunofluorescent panel that detected both malignancy and pulmonary origin by incorporating the thyroid transcription factor‐1 (TTF‐1) biomarker. Evaluation for TTF‐1–positive ETCs (T‐ETCs) was performed on 12 patient samples. T‐ETCs and parallel ETCs from selected patients were collected and subjected to DNA profiling to identify pathogenic mutations. All samples were obtained with Institutional Review Board approval.

Results

Malignancy was detected in all samples. T‐ETCs were identified in 9 of 10 patients who had clinically reported TTF‐1 positivity (90% sensitivity and 100% specificity). Furthermore, DNA profiling of as few as five T‐ETCs identified pathogenic mutations with equal or greater sensitivity compared with profiling of ETCs, both of which showed high concordance with clinical findings.

Conclusions

The findings suggest that the immunofluorescent and molecular characterization of tumor cells from pleural effusion specimens can provide reliable diagnostic information, even with very few cells. The integration of site‐specific biomarkers like TTF‐1 into ETC analysis may facilitate better refined diagnosis and improve patient care.
Measurement of Blood‐Brain Barrier Disruption in Mice Following Ozone Exposure Using Highly Sensitive Radiotracer Assays
Authors: Erickson Michelle A. , Banks William A. , Baumann Kristen K.
Published: June 2022

Ozone is a widespread air toxicant. Although its primary target organ is the lungs, emerging evidence suggests that ozone also has harmful effects on the brain. The vascular blood‐brain barrier (BBB), an endothelial interface that regulates passage of substances between the brain and peripheral tissues, is a likely mediator of ozone's adverse effects on the brain. Ozone can cause BBB disruption, a pathological state in which the BBB becomes leaky, resulting in the unregulated entry of circulating substances into the brain. BBB disruption can be detected using many methods, which each have their strengths and limitations. Recent data suggest that BBB disruption can occur in mice following ozone exposures, albeit at a low level. Therefore, robust and highly sensitive assays for BBB disruption are needed. Assays commonly used to detect BBB disruption, however, can be time consuming, lack sensitivity, and can be vulnerable to artifacts that are typically not addressed in the experimental design. Radiochemical assays are among the most sensitive and specific for detecting subtle disruptions of the BBB and require minimal sample processing for detection. Radiochemical assays can also be multiplexed to include radiotracer conjugates of large and small molecular weights, and the uptake of each of them can provide information about the severity and mechanism of BBB disruption. Here, we describe a protocol to use two of these radiotracer conjugates, 14C‐sucrose and 99mTc‐ albumin, to measure BBB disruption following an acute exposure to ozone in mice. We provide the steps to expose mice acutely to ozone, to label albumin with 99mTc‐pertechnetate, and to measure BBB disruption by evaluating permeability to 99mTc‐albumin and 14C‐sucrose after ozone exposure. These methods can be adapted to different ozone exposure paradigms and to different rodent species/strains, allowing for the sensitive and rapid assessment of BBB disruption that is detectable in whole brains or in brain regions. © 2022 Wiley Periodicals LLC.

Basic Protocol 1: Ozone exposures in mice

Basic Protocol 2: Measurement of blood‐brain barrier disruption by evaluating permeability to 14C‐sucrose and 99mTc‐albumin

Support Protocol: Labeling of bovine serum albumin with 99mTc
Bridging the gap between emerging models and humans by learning from polio animal studies: A systematic review
Authors: Moreni Giulia , Aknouch Ikrame , Ras Morris , Brouwer Lieke , Spijker René , Calitz Carlemi , Stittelaar Koert J. , Sridhar Adithya , Wolthers Katja C. , Pajkrt Dasja
Published: June 2022

Disease modelling plays a fundamental role in biomedical research, even more in virology where the virus depends strictly on its host for replication. Although animal models are extensively used in virology, there is an increasing demand for animal‐free research. Therefore, during this transition, it is crucial to learn and take advantage of animal research to better implement new emerging models. In this study, we aim to systematically review the translation from animal models to humans for the well‐characterized viral disease polio, as a reference for novel in vitro models in virology. We found a high risk of bias in the included studies and a large diversity of animal models. Moreover, we showed that animal models for studying poliovirus pathogenesis are mainly discrimination models focusing on specific aspects of the disease allowing an insightful understanding of the complex poliovirus infection. Our review underlines the importance of proper standardization of new emerging models and a careful interpretation of the results from discrimination models.
Indigenous microbial communities as catalysts for early marine cements: An in vitro study
Authors: Diaz Mara R. , Eberli Gregor P. , Weger Ralf J.
Published: June 2022

Early marine cementation is a fundamental process for many characteristics of carbonates, like the stabilisation of steep slopes. The genesis of early cements is often attributed to physicochemical processes but there is evidence for microbial mediation. To elucidate the role of microbes and associated organic material, in vitro experiments were undertaken in the presence and absence of indigenous microbiota in ooids from Schooner Cays, Bahamas and compared with native grapestones from Joulter Cays, Bahamas. Microscopic examinations by stereomicroscopy, scanning electron microscopy and thin section analysis of in vitro incubations with native flora document rapid grain fusion, resulting in the formation of grapestones within 30–60 days. The initial binding of the grains is primarily facilitated by exudates of extracellular polymeric substances and microbial communities acting as catalysts in the formation of micritic bridges, cements and encrusted aggregates. In vitro grapestones are similar to native grapestones from Joulter Cays with intergranular areas infested with extracellular polymeric substances, microbes, micritic cements, amorphous calcium carbonate nanograins and micritised outer surfaces. These similarities suggest that incubations with native flora follow similar mineralisation mechanisms as in the natural environment. In contrast, sterilised grains remain loose with little crystal formation after 60 days and are devoid of microbes and organic exudates. Owing to the near absence of precipitates, abiotic precipitation is not the driving force promoting early cements. In contrast, grain fusion is microbially mediated via both a passive mechanism, where extracellular polymeric substances and cell surfaces function as templates for crystal nucleation and generation of micritic cements, and through an active mechanism by which biofilm heterotrophs and autotrophs induce chemical alterations of a local environment, facilitating precipitation. This study underscores that microbially mediated cementation can occur at fast rates and that firmground to hardgrounds and slope stabilisation take place shortly after deposition of carbonate grains.
The athletic characteristics of Olympic sports to assist anti‐doping strategies
Authors: Hayward Gregory , Gaborini Lorenzo , Sims David , Schumacher Yorck Olaf , Millet Grégoire P. , Rhumorbarbe Damien , Coquet Ronan , Robinson Neil
Published: June 2022

The determinants of success in Olympic Games competition are specific to the athletic demands of the sporting event. A global evaluation to quantify the athletic demands across the spectrum of the Olympic Games sport events has not previously been conducted. Thus far, the interpretation and the comparison of sport physiological characteristics within anti‐doping organisations (ADOs) risk assessments remains subjective without a standardised framework. Despite its subjective assessment, this information is a key component of any anti‐doping programme. Sport characteristics inevitably influence the type of substances and/or methods used for doping purposes and should be captured through a comprehensive analysis. Seven applied sport scientists independently conducted an assessment to quantify the athletic demands across six preselected athletic variables. A principal component analysis was performed on the results of the panel's quantitative assessment for 160 Olympic sport events. Sport events were clustered using the Hierarchical Density Based Spatial Clustering of Applications with Noise (HDBSCAN) algorithm. The HDBSCAN identified 19 independent cluster groups; 36 sport events remained statistically unassigned to a cluster group representing unique and event‐specific athletic demands. This investigation provides guidance to the anti‐doping community to assist in the development of the sport specific physiology component of the risk assessment for Olympic Games disciplines. The dominant athletic characteristics to excel in each of these individual events will highlight areas of how athletes may strive to gain a competitive advantage through doping strategies, and inform the development of an effective and proportionate allocation of testing resources.
Species richness is a strong driver of forest biomass along broad bioclimatic gradients in the Himalayas
Authors: Dyola Nita , Sigdel Shalik Ram , Liang Eryuan , Babst Flurin , Camarero J. Julio , Aryal Sugam , Chettri Nakul , Gao Shan , Lu Xiaoming , Sun Jian , Wang Tao , Zhang Gengxin , Zhu Haifeng , Piao Shilong , Peñuelas Josep
Published: June 2022

Forest biomass is an important component of terrestrial carbon pools. However, how climate, biodiversity, and structural attributes co‐determine spatiotemporal variation in forest biomass remains not well known. We aimed to shed light on these drivers of forest biomass by measuring diversity and structural attributes of tree species in 400‐m2 plots located every 100 m along a 4200‐m elevational gradient in the eastern Himalayas. We applied structural equation models to test how climate, species richness, structural attributes, and their interactions influence forest biomass. Importantly, species richness was a stronger driver of biomass than environmental and structural attributes such as annual air temperature or stem density. Integrating the availability of energy and the demand for water, potential evapotranspiration was more strongly correlated with biomass than water availability, likely due to the strong influence of the Indian summer monsoon. Thus, interactions between climate and tree community composition ultimately control how much carbon is stored in woody biomass across bioclimatic gradients. This fundamental understanding will support predictive efforts of the forest carbon sink in this hydroclimatically important region and help preserving regional forests as a potent natural solution for climate change mitigation.
The Use of Sustainable Transition Metals for the Cycloaddition of Epoxides and CO2 under Mild Reaction Conditions
Authors: Al‐Qaisi Feda'a M. , Qaroush Abdussalam K. , Okashah Ibrahim K. , Eftaiha Ala'a F. , Vasko Petra , Alsoubani Fatima , Repo Timo
Published: June 2022

Following green chemistry principles, we present a one pot synthesis of zinc curcumin complex as a homogeneous, sustainable catalyst for cyclic carbonate (CC) synthesis from CO2 and a variety of terminal and internal epoxides under 1 bar CO2 at 60 °C using DMSO as a solvent. Zinc curcumin (Zn‐Cur) complex was identified via 1H/13C NMR and ATR‐FTIR spectroscopies, elemental analysis, ionic conductivity, and quantitative silver nitrate test to confirm a 1 : 1 molar ratio of metal to the ligand. Interestingly, Zn‐Cur showed an outstanding performance in catalysing the synthesis of renewable CCs including dimeric pinene and limonene carbonates. In this context, other metal complexes, including magnesium (MgII), calcium (CaII), and nickel (NiII) complexes showed good to excellent catalytic activity. Furthermore, a plausible reaction mechanism was investigated by density functional theory (DFT) calculations. The reaction was found to be overall exergonic by 39 kJ/mol and the rate determining step was CO2 insertion, which is in good agreement with the experimental findings.
Access to Sulfocoumarins by Three‐Component Reaction of β‐Keto Sulfonyl Fluorides, Arynes, and DMF
Authors: Huang Yuan , Zhao Xueyan , Chen Dengfeng , Zheng Yu , Luo Jinyue , Huang Shenlin
Published: June 2022

Sulfonyl fluorides have found diverse applications in multiple disciplines due to their reactivity and stability. Thus, exploiting the new reactivity of sulfonyl fluorides is of high importance to Sulfur (VI) Fluoride Exchange (SuFEx) chemistry. Reported herein is a three‐component reaction of β‐keto sulfonyl fluorides, arynes and DMF for the streamline synthesis of sulfocoumarins. The reaction proceeds by trapping of the in situ generated o‐quinone methides with β‐keto sulfonyl fluorides, followed by selective cyclization with sulfonyl fluorides. This strategy provides a new avenue to access diverse sulfocoumarins with under mild conditions.
The State of Israel: Toward a Renewable Low‐Carbon Energy Production
Authors: Kraytsberg Alexander , Ein-Eli Yair
Published: June 2022

Israel is located within the global solar belt, having high population density, a small share of rural population, while industry makes up a great part of the gross domestic product. As such, Israel is an excellent practice test site for identifying the best approaches to increase photovoltaic (PV) power penetration into the economies of developed countries. The core of the new distributed renewable power friendly paradigm is local prosumer‐to‐prosumer microgrids, which are aggregated into secondary supergrids, which may be, in turn, aggregated into ternary supergrids. Besides, the approach is also promising from the social point of view, transferring the power management to the people. The comment dwells into the challenges and possible solutions, which Israel is facing toward zero carbon energy production. Resolving these issues will affect the way of future sustainable energy supply growth and management. The comment written here refers also to the paradigm of battery technology for storing the PV energy, pointing on a possible misunderstanding within the battery community, which addresses the number of cycles a battery system can provide, rather than the expected service life of the system itself. In this aspect, it is proposed to focus the efforts of the researchers and developers into an alternative battery system.
Carbon Nanofiber Decorated Ternary Transition Metal Oxide Anodes for Fast Charging Lithium‐Ion Batteries
Authors: Park Mihee , Park Minjoon
Published: June 2022

Fast charging rate capability of electrochemically active ternary transition metal Ni–Co–Mn oxides (NCMO) anode incorporated with the carbon nanofibers (CNF‐NCMO) is prepared by a simple thermal decomposition of acetylene gas on spherical Ni–Co–Mn oxide particles, and the tap density of the particles is around 1.3 g cm−3. The CNF‐NCMO showed the reversible capacity of 447 mAh g−1 at 10C rate (10 A g−1) in lithium metal half‐cells at room temperature (loading level was 1.4 mg cm−2). However, pristine NCMO only shows a reversible capacity of 124 mAh g−1 at 10C rate. The improved lithium storage and rate capability are mainly ascribed to the conductive CNF networks, reducing the contact and charge transfer resistance between the NCMO samples. Also, these results suggest that the carbon nanofibers act as a buffer layer for preventing the volume expansion during the lithium conversion reactions with the improved structural integrity.