bluuebunny/crossref_metadata_2025 huggingface dataset:
Impact of Organic Templates on the Selective Formation of Zeolite Oligomers
Authors: Ciantar Marine , Trinh Thuat T. , Michel Carine , Sautet Philippe , Mellot‐Draznieks Caroline , Nieto‐Draghi Carlos
Published: November 2020

Zeolites are essential materials to industry due to their adsorption and catalytic properties. The best current approach to prepare a targeted zeolite still relies on trial and error's synthetic procedures since a rational understanding of the impact of synthesis variables on the final structures is still missing. To discern the role of a variety of organic templates, we perform simulations of the early stages of condensation of silica oligomers by combining DFT, Brønsted‐Evans‐Polanyi relationships and kinetic Monte Carlo simulations. We investigate an extended reaction path mechanism including 258 equilibrium reactions and 242 chemical species up to silica octamers, comparing the computed concentrations of Si oligomers with 29SI NMR experimental data. The effect of the templating agent is linked to the modification of the intramolecular H‐bond network in the growing oligomer, which produces higher concentration of 4‐membered ring intermediates, precursors of the key double‐four ring building blocks present on more than 39 known zeolite topologies.
Katalytische Synthese von Kaliumacyltrifluoroboraten (KATs) aus Boronsäuren und dem Thioimidat‐KAT‐Transferreagenz
Authors: Schuhmacher Anne , Ryan Sarah J. , Bode Jeffrey W.
Published: November 2020

Wir berichten über die Synthese von Kaliumacyltrifluoroboraten (KATs) mittels Palladium‐katalysierter Kreuzkupplung von Boronsäuren mit dem Thioimidat‐KAT‐Transferreagenz. Die Kombination von breit erhältlichen Aryl‐ und Vinylboronsäuren mit kommerziellem Thioimidat 1 unter Verwendung von katalytischem PdII und CuII als Additiv erlaubt die Herstellung von KATs in hohen Ausbeuten und mit guter Verträglichkeit für verschiedene funktionelle Gruppen. Das formale Einfügen von CO in Organoboronsäuren kann unter Verwendung eines geringfügig veränderten Vorgehens auch für Boronsäurepinakolester und Kaliumorganotrifluoroborate angewendet werden. Durch die einzigartige Chemie von KATs und Trifluoroboratiminiumionen (TIMs) lassen sich Kreuzkupplungen auch auf die Synthese von Amiden und α‐Aminotrifluoroboraten als Eintopfvariante ausweiten.
Improving the Overall Properties of Circularly Polarized Luminescent Materials Through Arene–Perfluoroarene Interactions
Authors: Zhang Haowen , Han Jianlei , Jin Xue , Duan Pengfei
Published: November 2020

A major trade‐off in the field of circularly polarized luminescence (CPL) of pure organic materials is that the large luminescence dissymmetry factor (glum) usually gives rise to the suppression of luminescence efficiency (ΦPL). Here, a supramolecular self‐assembled system, driven by arene–perfluoroarene (AP) interactions of chiral polycyclic aromatic hydrocarbons (PAHs) and octafluoronaphthalene (OFN), is reported to provide a solution to this problem. Two kinds of chiral PAHs based on pyrene and anthracene could co‐assemble with OFN in hybrid solvents to form long‐range‐ordered AP assemblies. The detailed process of AP interaction driving self‐assembly was verified by morphological measurements and fluorescence spectra. The AP assemblies exhibited chirality amplification not only in the excited state but also in the ground state. In addition, the AP assemblies showed an enhanced luminescence efficiency compared with the individual chiral PAHs due to the energy‐barrier effect of OFN. The present strategy based on AP interactions could be applied to boost the development of highly efficient CPL‐active materials.
Coupling of Cu(100) and (110) Facets Promotes Carbon Dioxide Conversion to Hydrocarbons and Alcohols
Authors: Zhong Dazhong , Zhao Zhi‐Jian , Zhao Qiang , Cheng Dongfang , Liu Bin , Zhang Gong , Deng Wanyu , Dong Hao , Zhang Lei , Li Jingkun , Li Jinping , Gong Jinlong
Published: November 2020

Copper can efficiently electro‐catalyze carbon dioxide reduction to C2+ products (C2H4, C2H5OH, n‐propanol). However, the correlation between the activity and active sites remains ambiguous, impeding further improvements in their performance. The facet effect of copper crystals to promote CO adsorption and C−C coupling and consequently yield a superior selectivity for C2+ products is described. We achieve a high Faradaic efficiency (FE) of 87 % and a large partial current density of 217 mA cm−2 toward C2+ products on Cu(OH)2‐D at only −0.54 V versus the reversible hydrogen electrode in a flow‐cell electrolyzer. With further coupled to a Si solar cell, record‐high solar conversion efficiencies of 4.47 % and 6.4 % are achieved for C2H4 and C2+ products, respectively. This study provides an in‐depth understanding of the selective formation of C2+ products on Cu and paves the way for the practical application of electrocatalytic or solar‐driven CO2 reduction.
A Biomimetic DNA‐Based Membrane Gate for Protein‐Controlled Transport of Cytotoxic Drugs
Authors: Lanphere Conor , Arnott Patrick M. , Jones Sioned Fôn , Korlova Katarina , Howorka Stefan
Published: November 2020

Chemistry is ideally placed to replicate biomolecular structures with tuneable building materials. Of particular interest are molecular nanopores, which transport cargo across membranes, as in DNA sequencing. Advanced nanopores control transport in response to triggers, but this cannot be easily replicated with biogenic proteins. Here we use DNA nanotechnology to build a synthetic molecular gate that opens in response to a specific protein. The gate self‐assembles from six DNA strands to form a bilayer‐spanning pore, and a lid strand comprising a protein‐binding DNA aptamer to block the channel entrance. Addition of the trigger protein, thrombin, selectively opens the gate and enables a 330‐fold increase inw the transport rate of small‐molecule cargo. The molecular gate incorporates in delivery vesicles to controllably release enclosed cytotoxic drugs and kill eukaryotic cells. The generically designed gate may be applied in biomedicine, biosensing or for building synthetic cells.
Water Mobility in the Interfacial Liquid Layer of Ice/Clay Nanocomposites
Authors: Li Hailong , Mars Julian , Lohstroh Wiebke , Koza Michael Marek , Butt Hans‐Jürgen , Mezger Markus
Published: November 2020

At solid/ice interfaces, a premelting layer is formed at temperatures below the melting point of bulk water. However, the structural and dynamic properties within the premelting layer have been a topic of intense debate. Herein, we determined the translational diffusion coefficient Dt of water in ice/clay nanocomposites serving as model systems for permafrost by quasi‐elastic neutron scattering. Below the bulk melting point, a rapid decrease of Dt is found for charged hydrophilic vermiculite, uncharged hydrophilic kaolin, and more hydrophobic talc, reaching plateau values below −4 °C. At this temperature, Dt in the premelting layer is reduced up to a factor of two compared to supercooled bulk water. Adjacent to charged vermiculite the lowest water mobility was observed, followed by kaolin and the more hydrophobic talc. Results are explained by the intermolecular water interactions with different clay surfaces and interfacial segregation of the low‐density liquid water (LDL) component.
Acceptor Engineering for Optimized ROS Generation Facilitates Reprogramming Macrophages to M1 Phenotype in Photodynamic Immunotherapy
Authors: Yang Guang , Ni Jen‐Shyang , Li Yaxi , Zha Menglei , Tu Yao , Li Kai
Published: November 2020

Reprogramming tumor‐associated macrophages to an antitumor M1 phenotype by photodynamic therapy is a promising strategy to overcome the immunosuppression of tumor microenvironment for boosted immunotherapy. However, it remains unclear how the reactive oxygen species (ROS) generated from type I and II mechanisms, relate to the macrophage polarization efficacy. Herein, we design and synthesize three donor–acceptor structured photosensitizers with varied ROS‐generating efficiencies. Surprisingly, we discovered that the extracellular ROS generated from type I mechanism are mainly responsible for reprogramming the macrophages from a pro‐tumor type (M2) to an anti‐tumor state (M1). In vivo experiments prove that the photosensitizer can trigger photodynamic immunotherapy for effective suppression of the tumor growth, while the therapeutic outcome is abolished with depleted macrophages. Overall, our strategy highlights the designing guideline of macrophage‐activatable photosensitizers.
Racemic Monomer‐Based One‐Handed Helical Polymer Recognizes Enantiomers through Auto‐Evolution of Its Helical Handedness Excess
Authors: Ikai Tomoyuki , Kurake Tomoyuki , Okuda Shogo , Maeda Katsuhiro , Yashima Eiji
Published: November 2020

A racemic monomer‐based optically inactive polyacetylene folds into a one‐handed helix assisted by a nonracemic alcohol, which can separate various enantiomers as a chiral stationary phase in chromatography. The chiral‐resolving power is virtually identical to that of the enantiopure monomer‐based one‐handed helical polyacetylene. Because of its unique static memory of the induced helicity, the original racemic polyacetylene expresses an auto‐evolution of its helical handedness over time, and at the same time, chirality of the nonracemic alcohol is discriminated accompanied by successive enhancement of its optical purity enantioselectively adsorbed on the helical polyacetylene owing to the chiral filter effect as directly monitored by NMR, which contributes to further enhancing the helix‐sense‐excess of the helical polyacetylene.
Preparation of Hierarchical Porous Activated Carbon from Banana Leaves for High‐performance Supercapacitor: Effect of Type of Electrolytes on Performance
Authors: Roy Chanchal Kumar , Shah Syed Shaheen , Reaz Akter H. , Sultana Sharmin , Chowdhury Al‐Nakib , Firoz Shakhawat H. , Zahir Md. Hasan , Ahmed Qasem Mohammed Ameen , Aziz Md. Abdul
Published: November 2020

We demonstrate a facile efficient way to fabricate activated carbon nanosheets (ACNSs) consisting of hierarchical porous carbon materials. Simply heating banana leaves with K2CO3 produce ACNSs having a unique combination of macro‐, meso‐ and micropores with a high specific surface area of ∼1459 m2 g−1. The effects of different electrolytes on the electrochemical supercapacitor performance and stability of the ACNSs are tested using a two‐electrode system. The specific capacitance (Csp) values are 55, 114, and 190 F g−1 in aqueous 0.5 M sodium sulfate, organic 1 M tetraethylammonium tetrafluoroborate in acetonitrile, and pure ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([BMIM][PF6]) electrolytes, respectively. The ACNSs also shows the largest potential window of 3.0 V, the highest specific energy (59 Wh kg−1) and specific power (750 W kg−1) in [BMIM][PF6]. A mini‐prototype device is prepared to demonstrate the practicality of the ACNSs.
Lignin valorization beyond energy use: has lignin's time finally come?
Authors: Xu Chunbao Charles , Dessbesell Luana , Zhang Yongsheng , Yuan Zhongshun
Published: November 2020

According to an old proverb, ‘you can make anything out of lignin, except money’. The complexity of lignin's structure and many inferior characteristics of lignin, such as its insolubility in organic solvent and poor reactivity related to it large molecular weight, have posed significant challenges to lignin valorization. Driven mainly by the commercial availability of large amounts of kraft lignin and hydrolysis lignin in kraft pulp mills and cellulosic ethanol plants, there is a pressing need to valorize lignin for high‐value chemical and material products for better overall profitability for the plants, and for the emerging bioeconomy. To this end, we have developed, over 10 years and in several publications, an engineering approach to lignin valorization. This perspective paper provides an overview of this process and concretizes the research achieved in support of lignin valorization. In the method presented, lignin is first de‐polymerized into de‐polymerized lignin (DL) at a high yield and with a tunable Mw (weight average molecular weight). The DL is then utilized as a mixture (no separation needed) to substitute directly petroleum‐based phenol (up to 75% substitution), polyols (up to 50% substitution), and bis‐phenol A (100 substitution) in preparation of bio‐based phenolic resins, polyurethane foams, and epoxy resins. The DL products were also used to replace petroleum‐based antioxidants resulting in enhanced thermo‐oxidative and thermal stability of polyethylene in the synthesis of bio‐based resins / plastic composites. This approach has demonstrated both technical and economic feasibility, generating a payback period of approximately 3 years for a commercial capacity of 40 000 t/y. Thus, Lignin valorization beyond energy use can be profitable, and the old proverb may prove wrong. Lignin's time might have finally come! © 2020 Society of Industrial Chemistry and John Wiley & Sons Ltd
Association Between Mobile Phone Radiation Exposure and the Secretion of Melatonin and Cortisol, Two Markers of the Circadian System: A Review
Authors: Selmaoui Brahim , Touitou Yvan
Published: November 2020

The extremely important use of mobile phones in the world, at all ages of life, including children and adolescents, leads to significant exposure of these populations to electromagnetic waves of radiofrequency. The question, therefore, arises as to whether exposure to these radiofrequencies (RFs) could lead to deleterious effects on the body's biological systems and health. In the current article, we review the effects, in laboratory animals and humans, of exposure to RF on two hormones considered as endocrine markers: melatonin, a neurohormone produced by the pineal gland and cortisol, a glucocorticosteroid synthesized by the adrenal glands. These two hormones are also considered as markers of the circadian system. The literature search was performed using PubMed, Medline, Web of Sciences (ISI Web of Knowledge), Google Scholar, and EMF Portal. From this review on RF effects on cortisol and melatonin, it appears that scientific papers in the literature are conflicting, showing effects, no effects, or inconclusive data. This implies the need for additional research on higher numbers of subjects and with protocols perfectly controlled with follow‐up studies to better determine whether the chronic effect of RF on the biological functioning and health of users exists (or not). Bioelectromagnetics. 2021;42:5–17. © 2020 Bioelectromagnetics Society
On‐Site Detection for Hazardous Materials in Chemical Accidents
Authors: Ly Nguyễn Hoàng , Kim Ho Hyun , Joo Sang‐Woo
Published: November 2020

Chemical accidents, such as fire, explosion, and leakages, not only cause damage to humans but also have a harmful impact on the environment. In modern industrialization period, researchers have been attracted by the elaboration of novel detection platforms that have been widely adopted for monitoring and the early warning of the risk of hazardous chemicals including hydrogen fluoride, hydrogen chloride, nitric acid, ammonia, hydrogen peroxide, chlorine gas, formaldehyde, aromatic compounds such as benzene‐toluene‐xylene, and heavy metals. This review explores novel sensor platforms based on novel materials including plasmonic metals, transition metal oxides, and composites. Due to the unique optical, spectroscopic, electrical, and physicochemical properties of materials, the development of functional materials‐based sensors significantly augments the current outlook on reducing the risk of hazardous chemical accidents to ensure security for humans and the environment.
Intranasal administration of perillyl alcohol–loaded nanoemulsion and pharmacokinetic study of its metabolite perillic acid in plasma and brain of rats using ultra‐performance liquid chromatography/tandem mass spectrometry
Authors: da Silva Santos Juliane , Diedrich Camila , Machado Christiane Schineider , da Fonseca Clovis Orlando , Khalil Najeh Maissar , Mainardes Rubiana Mara
Published: November 2020

Perillyl alcohol (POH) is a monocyclic terpene that has strong antitumor activity. Brain tumors are particularly difficult to treat with therapeutic agents, and clinical trials have shown their low tolerance through oral administration. We proposed the entrapment of POH into an oil‐in‐water chitosan nanoemulsion aiming its intranasal administration for brain targeting. An ultra‐performance liquid chromatography/tandem mass spectrometry (UPLC–MS/MS) method was developed and validated for the quantitation of total metabolite perillic acid (PA) in plasma and brain of rats. The rat samples containing the metabolite were treated by liquid–liquid extraction with acetonitrile. The mobile phase was 0.1% formic acid in water (solvent A) and 0.1% formic acid in methanol (solvent B), at a flow rate of 0.3 mL min−1 in gradient elution. The chromatography was run for 10 min, and analytical curves were built in acetonitrile, plasma, and brain. The PA was detected in positive ion mode with multiple reaction monitoring. The method has shown high selectivity, sensitivity, and throughput. The low quantification limits of 162, 178, and 121 ng mL−1 for acetonitrile, brain, and plasma, respectively, indicate a good detectability of the method. The repeatability and precision observed were within the limits recommended in the literature. The accuracy of the method was verified through high recovery rates (106–118%). The validated method was successfully applied to the pharmacokinetic study of the metabolite PA after the intranasal administration of free or POH‐loaded nanoemulsion in rats. The results showed that chitosan nanoemulsion improved the plasma and brain bioavailability of POH, representing a promising alternative to free POH treatment.
Minimally invasive surgery vs laparotomy for early stage cervical cancer: A propensity score‐matched cohort study
Authors: Dai Danian , Huang He , Feng Yanling , Wan Ting , Liu Zhimin , Tong Chongjie , Liu Jihong
Published: November 2020

Objective

To compare the long‐term oncologic outcomes of minimally invasive surgery (MIS) vs laparotomy for patients with stage IB (2018 FIGO) cervical cancer.

Methods

A matched retrospective study of cervical cancer patients who underwent MIS or laparotomy at Sun Yat‐sen University Cancer Center from January 2012 to December 2015 was carried out. Patients were restaged according to the 2018 FIGO staging system for cervical cancer, 700 cases with stage IB cervical cancer were enrolled. Propensity score matching (PSM) was performed by software SPSS version 22.0, and a total of 426 patients were enrolled and analyzed. Oncologic outcomes were compared between patients undergoing MIS vs laparotomy.

Results

After PSM, there were no statistical differences in other baseline characteristics between MIS and laparotomy, except for age (p = 0.008). In all stage IB patients, MIS group had significantly lower disease‐free survival (DFS) rate and overall survival (OS) rate compared with laparotomy group (5‐year DFS rate, 87.5% vs 94.1%, hazard ratio for disease recurrence, 2.403; 95% CI, 1.216‐4.744; 5‐year OS rate, 92.3% vs 98.1%, hazard ratio for death, 3.719; 95% CI, 1.370‐10.093). In stage IB1 patients population, MIS was still associated with worse DFS and OS compared to laparotomy (5‐year DFS rate: 89.5% vs 100%, p = 0.012; 5‐year OS rate: 93.4% vs 100%, p = 0.043). Even in stage IB1 patients without lymph vascular space invasion, worse oncologic outcome could be observed in MIS group (DFS: p = 0.021; OS: p = 0.076).

Conclusion

Our study suggested that laparotomy resulted in better OS and DFS compared with MIS among patients with stage IB cervical cancer. Even in stage IB1 patients without lymph vascular space invasion (2018 FIGO), laparotomy might be still an oncologically safer approach.
Biomass derived Fibers as a Substitute to Synthetic Fibers in Polymer Composites
Authors: Qasim Umair , Ali Muzaffar , Ali Touqeer , Iqbal Rameez , Jamil Farrukh
Published: November 2020

Advancement in science and technology provides the significant opportunities to utilize the plant fibers (unnoticed materials), which are cheap, abundant, sustainable, and biodegradable. A combination of polymer with the untreated and treated fibers, extracted from lignocellulosic biomass, has been getting significant attention because of their low cost, ecofriendly nature, and enhanced mechanical performance. This article delivers an explicit overview of the plant fibers, extraction and pretreatment of the plant fibers, development of the plant fibers reinforced polymeric composites, and the mechanical properties associated with these biocomposites. A special focus is concentrated on the pretreatment of hydrophilic plant fibers for better compatibility with the polymers, to obtain the enhanced composites having desirable properties. Finally, the effects of several pretreatments on the tensile and water absorption properties of the plant fibers reinforced composites has been included in detail for the better understanding of their practical applications.
A Cyanine‐Bridged Somatostatin Hybrid Probe for Multimodal SSTR2 Imaging in Vitro and in Vivo: Synthesis and Evaluation
Authors: Heing‐Becker Isabelle , Grötzinger Carsten , Beindorff Nicola , Prasad Sonal , Erdmann Sarah , Exner Samantha , Haag Rainer , Licha Kai
Published: November 2020

Multimodal imaging probes have attracted the interest of ongoing research, for example, for the surgical removal of tumors. Modular synthesis approaches allow the construction of hybrid probes consisting of a radiotracer, a fluorophore and a targeting unit. We present the synthesis of a new asymmetric bifunctional cyanine dye that can be used as a structural and functional linker for the construction of such hybrid probes. 68Ga‐DOTATATE, a well‐characterized radiopeptide targeting the overexpressed somatostatin receptor subtype 2 (SSTR2) in neuroendocrine tumors, was labeled with our cyanine dye, thus providing additional information along with the data obtained from the radiotracer. We tested the SSTR2‐targeting and imaging properties of the resulting probe 68Ga‐DOTA‐ICC‐TATE in vitro and in a tumor xenograft mouse model. Despite the close proximity between dye and pharmacophore, we observed a high binding affinity towards SSTR2 as well as elevated uptake in SSTR2‐overexpressing tumors in the positron emission tomography (PET) scan and histological examination.
Redox tolerance and metabolic reprogramming in solid tumors
Authors: Mortezaee Keywan
Published: November 2020

Tumor cells need to cope with the host environment for survival and keep growing in hard conditions. This suggests that tumors must acquire characteristics more potent than what is seen for normal tissue cells, without which they are condemned to disruption.  For example, cancer cells have more potent redox tolerance compared with normal cells, which is due to their high adaptation to an oxidative crisis. In addition, increased demand for bioenergetics and biosynthesis can cause a rise in nutrient uptake in tumors. Utilizing nutrients in low nutrient conditions suggests that tumors are also equipped with adaptive metabolic processes. Switching the metabolic demands toward glucose consumption upon exposure to the hypoxic tumor microenvironment, or changing toward using other sources when there is an overconsumption of glucose in the tumor area are examples of fitness metabolic systems in tumors. In fact, cancer cells in cooperation with their nearby stroma (in a process called metabolic coupling) can reprogram their metabolic systems in their favor. This suggests the high importance of stroma for meeting the metabolic demands of a growing tumor, an example in this context is the metabolic symbiosis between cancer‐associated fibroblasts with cancer cells. The point is that redox tolerance and metabolic reprogramming are interrelated, and that, without a doubt, disruption of redox tolerance systems by transient exposure to either oxidative or antioxidative loading, or targeting metabolic rewiring by modulation of tumor glucose availability, controlling tumor/stroma interactions, etc. can be effective from a therapeutic standpoint
Crystallographic Visualization of a Double Water Molecule Addition on a Pt1‐MOF during the Low‐temperature Water‐Gas Shift Reaction
Authors: Bilanin Cristina , Tiburcio Estefanía , Ferrando‐Soria Jesús , Armentano Donatella , Leyva‐Pérez Antonio , Pardo Emilio
Published: November 2020

The low‐temperature water‐gas shift reaction (WGSR, CO+H2O ⇔ H2+CO2) is considered a very promising reaction ‐candidate for fuel cells‐ despite an efficient and robust catalyst is still desirable. One of the more prominent catalysts for this reaction is based on single Pt atoms (Pt1) on different supports, which are supposed to manifold the reaction by the accepted mechanism for the general WGSR, i. e. by addition of one H2O molecule to CO, with generation of CO2 and H2. Here we show, experimentally, that not one but two H2O molecules are added to CO on the Pt1 catalyst, as assessed by a combination of reactivity experiments with soluble Pt catalysts, kinetic and spectroscopic measurements, and finally by in‐operando single crystal X‐ray diffraction on a Pt1‐MOF, to visualize the formation of the hemiacetal intermediate on the solid catalytic site. These results confirm our previous DFT predictions and provide a paradigmatic shift in the assumed mechanism of the WGSR, which may open the debate if two H2O molecules are recurrently added during the WGSR, not only for Pt1 catalysts but also for other metal catalysts.
A Compartmentalized‐type Bifunctional Magnetic Catalyst for One‐pot Aerobic Oxysulfonylation and Asymmetric Transfer Hydrogenation
Authors: Wang Shitong , Wang Chengyi , Lv Ning , Tan Chunxia , Cheng Tanyu , Liu Guohua
Published: November 2020

Utilization of the confined cavity of the mesoporous silica, the exploration of the synergetic catalysis process for sequential organic transformations has great significance in asymmetric catalysis. In this study, the yolk‐shell‐structured magnetic nanoparticles with the chiral Ru/diamine species within the nanochannels of the outer mesoporous silica shell and the FeCl3 species on the inner magnet core are fabricated. The electron microscopy images and the structural characterizations disclose the uniformly distributed magnetic nanoparticles with the well‐defined single‐site ruthenium/diamine active centers onto the outer silica shell. As a yolk‐shell‐structured bifunctional magnet catalyst, the FeCl3 species enables an efficient aerobic oxysulfonylation between aryl‐substituted terminal alkynes and sodium sulfinates to the β‐keto sulfones intermediates, and the ruthenium/diamine species sequentially reduces the in‐situ generated intermediate to the chiral β‐hydroxysulfones products. As we envision, this one‐pot aerobic oxysulfonylation/asymmetric transfer hydrogenation process affords various chiral β‐hydroxysulfones in high yields with excellent enantioselectivities. Furthermore, this magnetic catalyst can also be conveniently recovered via an additional outer magnet and repeatedly recycled, showing a potential application in industrial interest.
Ruthenium‐Catalyzed Secondary Amine Formation Studied by Density Functional Theory
Authors: Hückmann Lukas , Álvarez‐Barcia Sonia , Fuhrer Marina , Plietker Bernd , Kästner Johannes
Published: November 2020

Amines are a ubiquitous class of compounds found in a variety of functional organic building blocks. Within the past years, hydrogen autotransfer catalysis has evolved as a new concept for the synthesis of amines. A through understanding of the mechanism of these reactions is necessary to design optimal catalysts. We investigate secondary amine formation catalyzed by a NNNN(P)Ru‐complex and provide understanding on the three reaction steps involved. We find that the ligand has to open one coordination site in order to allow the formation of a metal hydride intermediate. In a second step, a condensation reaction, which could also happen uncatalyzed in solution, is significantly enhanced by the presence of the ruthenium complex. The back‐transfer of the hydride to the substrate in a third step regenerates the catalyst.
Bond between concrete and rigid foam in precast concrete sandwich construction
Authors: Metje Kevin , Leutbecher Torsten , Weimar Thorsten , Hammer Christian
Published: November 2020

In precast concrete sandwich construction mechanical connectors are used to transfer loads between the two concrete shells. Omitting these connectors seems economically interesting for realizing novel sandwich elements with lightweight facings made of textile‐reinforced concrete or other materials. Then, the adhesion between the isolating layer and the cover layers becomes the decisive parameter. In order to evaluate the basic influence of surface texture and type of concrete on the bond strength, an experimental study including different rigid foams and ordinary performance concrete (OPC) as well as ultra‐high performance concrete (UHPC) was carried out. The results of 120 tensile bond tests and 30 shear tests on concrete‐rigid foam composites show that technically relevant bond strengths can be achieved by pouring the concrete onto the rigid foam. For OPC, the tensile bond strength is 50% higher than the minimum value required for external thermal insulation composite systems without mechanical connectors. For UHPC significantly higher bond strengths are obtained, which can be attributed to a better micromechanical interlock. In some cases, the strength of the composite was limited by the strength of the foam. The results are valuable for identifying promising rigid foam‐concrete configurations.
Use of Crown Ether Functions as Secondary Coordination Spheres for the Manipulation of Ligand–Metal Intramolecular Electron Transfer in Copper–Guanidine Complexes
Authors: Haaf Sebastian , Kaifer Elisabeth , Wadepohl Hubert , Himmel Hans‐Jörg
Published: November 2020

Invited for the cover of this issue is the group of Hans‐Jörg Himmel at Ruprecht‐Karls‐Universität Heidelberg. The image depicts the electron transfer process using copper complexes with redox‐active guanidines. Read the full text of the article at 10.1002/chem.202003469.
Covalent Cross‐Linking of 2H‐MoS2 Nanosheets
Authors: Vázquez Sulleiro Manuel , Quirós‐Ovies Ramiro , Vera‐Hidalgo Mariano , Gómez I. Jénnifer , Sebastián Víctor , Santamaría Jesús , Pérez Emilio M.
Published: November 2020

The combination of 2D materials opens a wide range of possibilities to create new‐generation structures with multiple applications. Covalently cross‐linked approaches are a ground‐breaking strategy for the formation of homo or heterostructures made by design. However, the covalent assembly of transition metal dichalcogenides flakes is relatively underexplored. Here, a simple covalent cross‐linking method to build 2H‐MoS2–MoS2 homostructures is described, using commercially available bismaleimides. These assemblies are mainly connected vertically, basal plane to basal plane, creating specific molecular sized spaces between MoS2 sheets. Therefore, this straightforward approach gives access to the controlled connection of sulfide‐based 2D materials.
2‐ and 2,7‐Substituted para‐N‐Methylpyridinium Pyrenes: Syntheses, Molecular and Electronic Structures, Photophysical, Electrochemical, and Spectroelectrochemical Properties and Binding to Double‐Stranded (ds) DNA
Authors: Kole Goutam Kumar , Merz Julia , Amar Anissa , Fontaine Bruno , Boucekkine Abdou , Nitsch Jörn , Lorenzen Sabine , Friedrich Alexandra , Krummenacher Ivo , Košćak Marta , Braunschweig Holger , Piantanida Ivo , Halet Jean‐François , Müller‐Buschbaum Klaus , Marder Todd B.
Published: November 2020

Two N‐methylpyridinium compounds and analogous N‐protonated salts of 2‐ and 2,7‐substituted 4‐pyridyl‐pyrene compounds were synthesised and their crystal structures, photophysical properties both in solution and in the solid state, electrochemical and spectroelectrochemical properties were studied. Upon methylation or protonation, the emission maxima are significantly bathochromically shifted compared to the neutral compounds, although the absorption maxima remain almost unchanged. As a result, the cationic compounds show very large apparent Stokes shifts of up to 7200 cm−1. The N‐methylpyridinium compounds have a single reduction at ca. −1.5 V vs. Fc/Fc+ in MeCN. While the reduction process was reversible for the 2,7‐disubstituted compound, it was irreversible for the mono‐substituted one. Experimental findings are complemented by DFT and TD‐DFT calculations. Furthermore, the N‐methylpyridinium compounds show strong interactions with calf thymus (ct)‐DNA, presumably by intercalation, which paves the way for further applications of these multi‐functional compounds as potential DNA‐bioactive agents.
General Synthesis of Secondary Alkylamines by Reductive Alkylation of Nitriles by Aldehydes and Ketones
Authors: Schönauer Timon , Thomä Sabrina L. J. , Kaiser Leah , Zobel Mirijam , Kempe Rhett
Published: November 2020

The development of C−N bond formation reactions is highly desirable due to their importance in biology and chemistry. Recent progress in 3d metal catalysis is indicative of unique selectivity patterns that may permit solving challenges of chemical synthesis. We report here on a catalytic C−N bond formation reaction—the reductive alkylation of nitriles. Aldehydes or ketones and nitriles, all abundantly available and low‐cost starting materials, undergo a reductive coupling to form secondary alkylamines and inexpensive hydrogen is used as the reducing agent. The reaction has a very broad scope and many functional groups, including hydrogenation‐sensitive examples, are tolerated. We developed a novel cobalt catalyst, which is nanostructured, reusable, and easy to handle. The key seems the earth‐abundant metal in combination with a porous support material, N‐doped SiC, synthesized from acrylonitrile and a commercially available polycarbosilane.
Personal social responsibility: Scale development and validation
Authors: Davis Sylvia López , Rives Longinos Marín , Ruiz‐de‐Maya Salvador
Published: November 2020

Although the literature on consumer behavior has addressed tendencies toward responsible consumption, no research has analyzed responsible behavior as a multidimensional construct in areas not related to consumption, such as paying taxes, children's education, and recycling. It is necessary to develop the concept of personal social responsibility (PSR), which includes human behavior as a whole, beyond consumption. This research develops a reliable and valid scale to measure PSR, a concept that comprises individual behaviors from the perspective of the individual as a citizen. Study 1 (n = 138) suggests that the construct of PSR is made up of the economic, legal, ethical, philanthropic, and environmental dimensions of individual behavior. Study 2 (n = 212) demonstrates the external validity of the scale, revealing that perceived consumer effectiveness and collectivism have a positive influence on personal responsibility behaviors, and that being more responsible leads to higher levels of self‐esteem and satisfaction with life.
Porphyromonas gingivalis and Lactobacillus rhamnosus GG regulate the Th17/Treg balance in colitis via TLR4 and TLR2
Authors: Jia Lu , Wu Ruiqing , Han Nannan , Fu Jingfei , Luo Zhenhua , Guo Lijia , Su Yingying , Du Juan , Liu Yi
Published: November 2020

Objectives

CD4+ T cells are the key to many immune–inflammatory diseases mediated by microbial disorders, especially inflammatory bowel disease (IBD). The purpose of this study was to explore how pathogenic and probiotic bacteria directly affect the T helper (Th)17 and T regulatory (Treg) cell balance among CD4+ T cells to regulate inflammation.

Methods

Porphyromonas gingivalis (Pg; ATCC 33277) and Lactobacillus rhamnosus GG (LGG; CICC 6141) were selected as representative pathogenic and probiotic bacteria, respectively. Bacterial extracts were obtained via ultrasonication and ultracentrifugation. Flow cytometry, RT‐qPCR, ELISAs, immunofluorescence and a Quantibody cytokine array were used. The dextran sodium sulphate (DSS)‐induced colitis model was selected for verification.

Results

The Pg ultrasonicate induced the apoptosis of CD4+ T cells and upregulated the expression of the Th17‐associated transcription factor RoRγt and the production of the proinflammatory cytokines IL‐17 and IL‐6, but downregulated the expression of the essential Treg transcription factor Foxp3 and the production of the anti‐inflammatory factors TGF‐β and IL‐10 via the TLR4 pathway. However, LGG extract maintained Th17/Treg homeostasis by decreasing the IL‐17+ Th17 proportion and increasing the CD25+ Foxp3+ Treg proportion via the TLR2 pathway. In vivo, Pg‐stimulated CD4+ T cells aggravated DSS‐induced colitis by increasing the Th17/Treg ratio in the colon and lamina propria lymphocytes (LPLs), and Pg + LGG‐stimulated CD4+ T cells relieved colitis by decreasing the Th17/Treg ratio via the JAK‐STAT signalling pathway.

Conclusions

Our findings suggest that pathogenic Pg and probiotic LGG can directly regulate the Th17/Treg balance via different TLRs.
Proteolysis targeting chimera (PROTAC) for epidermal growth factor receptor enhances anti‐tumor immunity in non‐small cell lung cancer
Authors: Wang Kai , Zhou Hongping
Published: November 2020

While immunotherapy has dramatically revolutionized the treatment of non‐small cell lung cancer (NSCLC), it still faces challenges such as low therapeutic efficacy and immune‐related adverse events, indicating that safe and effective approaches to enhance NSCLC immunotherapy are still highly demanded. Epidermal growth factor receptor (EGFR) is an established target for molecularly targeted therapy of NSCLC. Overexpression and activating mutations of EGFR can promote the resistance of NSCLC to immunotherapy via upregulating inhibitory immune checkpoints such as programmed death receptor ligand 1 (PD‐L1) and indoleamine‐2,3‐dioxygenase‐1 (IDO1). Thus, therapeutic inhibition of EGFR also holds promise in modulating the immune microenvironment to advance NSCLC immunotherapy. In this study, we employed a proteolysis targeting chimera (PROTAC) that degrades EGFRL858R to investigate its potential in dually inhibiting PD‐L1 and IDO1 to potentiate the anti‐tumor immunity in NSCLC. We demonstrated that PROTAC significantly downregulated the protein levels of both PD‐L1 and IDO1 in NSCLC H3255 cell and tumor. We also confirmed that PROTAC significantly suppressed the H3255 tumor growth and enhanced the anti‐tumor immune response in H3255 tumor. Overall, our study provides a novel strategy for future NSCLC therapy.
Detection of ethinyl estradiol and resorcylic acid lactones in poultry meat according to the national residue plan
Authors: Annunziata Loredana , Visciano Pierina , De Massis Maria Rosaria , Schirone Maria , Colagrande Maria Novella , Campana Guido , Migliorati Giacomo
Published: November 2020

The aim of this study was the detection of ethinyl estradiol and resorcylic acid lactones (zeranol and taleranol) in poultry meat samples as unauthorized substances included in the Italian national residue plan. The samples were purified by a solid phase extraction using a C18 column combined with alumina, and the analytes were detected by two specific enzyme‐linked immunosorbent assay (ELISA) kits. As they were collected in the frame of official control activities, the method was also validated according to the Commission Decision 2002/657/EC requirements for screening methods with qualitative purpose. Specificity and detection capability were the performance criteria considered for the validation study, and the latter parameter showed a value of 0.5 μg/kg for both the investigated compounds. Such result was well comparable with the data reported by using chromatographic techniques as confirmation methods, and therefore, the ELISA kits tested in this study could be used for the screening of large numbers of samples.
Demographic modeling to fine‐tune conservation targets: importance of pre‐adults for the decline of an endangered raptor
Authors: Sergio Fabrizio , Tavecchia Giacomo , Blas Julio , Tanferna Alessandro , Hiraldo Fernando
Published: November 2020

Large, long‐lived species with slow life histories and protracted pre‐breeding stages are particularly susceptible to declines and extinction, often for unknown causes. Here, we show how demographic modeling of a medium‐sized raptor, the Red Kite Milvus milvus, can aid to refocus conservation research and attention on the most likely mechanisms driving its decline. Red Kites’ survival and reproduction increased through three sequential stages for 1–2, 3–6, and 7–30 yr of age, mainly corresponding to individuals that are dispersing, attempting to gain a territory, and breeding. As typical of long‐lived species, elasticities were highest for adult (≥7 yr old) survival, but this was high, with little scope for improvement. Instead, the declines were driven by an extremely low survival of pre‐adults in their first years of life, which weakened the whole demographic system by nullifying the offspring contribution of adults and curtailing their replacement by recruits. For example, 27 pairs were necessary to generate a single prime age adult. Simulation of management scenarios suggested that the decline could be halted most parsimoniously by increasing pre‐adult survival to the mean levels recorded for other areas, while only the synergistic, simultaneous improvement of breeding success, adult and pre‐adult survival could generate a recovery. We propose three actions to attain such goals through selective supplementary feeding of both breeding and non‐breeding individuals, and through mortality improvement by GPS remote‐sensing devices employed as surveillance monitoring tools. Our results show how improving demographic models by using real, local vital rates rather than “best guess” vital rates can dramatically improve model realism by refocusing attention on the actual stages and mortality causes in need of manipulation, thus building precious time and resources for conservation management. These results also highlight the frequent key role of pre‐adult survival for the management of long‐lived species, coherent with the idea of demographic systems as integrated chains only as strong as their weakest link.
Disparities in the characteristics and outcomes of patients hospitalized with acute decompensated heart failure admitted to internal medicine and cardiology departments: a single‐centre, retrospective cohort study
Authors: Maymon Shiri Lea , Moravsky Gil , Marcus Gil , Shuvy Mony , Pereg David , Epstein Danny , Litovchik Ilya , Fuchs Shmuel , Minha Sa'ar
Published: November 2020

Aims

Efforts are constantly made to decrease the rates of readmission after acute decompensated heart failure (ADHF). ADHF admissions to internal medicine departments (IMD) were previously associated with higher risk for readmission compared with those admitted to cardiology departments (CD). It is unknown if the earlier still applies after recent advancement in care over the last decade. This contemporary cohort compares characteristics and outcomes of ADHF patients admitted to IMD with those admitted to CD.

Methods and results

The data for this single‐centre, retrospective study utilized a cohort of 8332 ADHF patients admitted between 2007 and 2017. We compared patients' baseline characteristics and clinical and laboratory indices of patients admitted to CD and IMD with the outcome defined as 30 day readmission rate. In comparison with those admitted to CD, patients admitted to IMD (89.5% of patients) were older (79 [70–86] vs. 69 [60–78] years; P < 0.001) and had a higher incidence of co‐morbidities and a higher ejection fraction. Readmission rates at 30 days were significantly lower in patients admitted to CD (15.9% vs. 19.6%; P = 0.01). Conflicting results of three statistical models failed to associate between the admitting department and 30 day readmission (odds ratio for 30 day readmission in CD: forced and backward stepwise logistic regression 0.8, 95% confidence interval 0.65–0.97, P = 0.02; stabilized inverse probability weights model odds ratio 1.0, confidence interval 0.75–1.37, P = 0.96).

Conclusions

This contemporary analysis of ADHF patient cohort demonstrates significant differences in the characteristics and outcomes of patients admitted to IMD and CD. Thus, focusing strategies for readmission prevention in patients admitted to IMD may be beneficial.
Time‐weighted lactate as a predictor of adverse outcome in acute heart failure
Authors: Bosso Giorgio , Mercurio Valentina , Diab Nermin , Pagano Antonio , Porta Giovanni , Allegorico Enrico , Serra Claudia , Guiotto Giovanna , Numis Fabio Giuliano , Tocchetti Carlo Gabriele , Schiraldi Fernando
Published: November 2020

Aims

The role of dynamic changes in lactate concentrations on prognosis in acute heart failure has been poorly investigated. The aim of this study was to explore the predictive value of 24 h time‐weighted lactate (LACTW) in patients with acute heart failure.

Methods and results

Ninety‐six consecutive acute heart failure patients presenting to the Emergency Department of San Paolo Hospital, Naples, Italy, were prospectively enrolled. Arterial blood lactate was measured at admission and during the following 24 h at random time intervals. LACTW was obtained by the sum of the average lactate values among consecutive time points multiplied by the intervals between consecutive time points and dividing the sum by the total time (24 h). The outcome was a composite of need of admission to the intensive care unit, hospitalization duration >7 days, or intra‐hospital death. Admission lactate, maximum measured lactate, and LACTW were collected. Univariate and multivariate Cox regression analysis was applied to determine the hazard ratio (HR) of developing the outcome. Forty‐three patients experienced the pre‐specified outcome. In sex‐adjusted and age‐adjusted multivariable analysis, LACTW predicted the outcome occurrence (HR: 1.51, 95% confidence interval: 1.24, 1.84, P < 0.001). Risk stratification analysis based on LACTW tertiles demonstrated a gradual increase in risk of developing the outcome (HR: 17.32, 95% confidence interval: 2.30, 130.23, P = 0.006) for the highest LACTW tertile.

Conclusions

In acute heart failure patients, 24 h LACTW had a significant independent predictive value for adverse intra‐hospital outcome. LACTW could be a useful index at identifying high‐risk patients who may require a more aggressive treatment during hospitalization.