bluuebunny/crossref_metadata_2025 huggingface dataset:
Smart Materials Based on Synthetic Host Molecules: The Role of Host–Guest Chemistry in the Fabrication and Application
Authors: Liu Peiren , Fang Fang , Wang Haochen , Khashab Niveen M.
Published: April 2023

Stimuli‐responsive or smart materials have recently shown a significant impact on the frontier of material science and engineering. The exponential development of synthetic host molecules (SHMs) over the last decades and their corresponding host–guest chemistry, have empowered researchers with new opportunities to design and construct tailored or guest‐specific smart materials. In this Minireview, we present the recent advancements in synthetic host based smart materials, ranging from the fabrication strategies to the state‐of‐art applications including adsorption, separation, luminescence, self‐healing and actuation. The role that the host–guest chemistry plays in these systems is highlighted throughout to give a better prospective of the available possibilities for emerging materials of future economies.
Charge Separation in Metal‐Organic Framework Enables Heterogeneous Thiol Catalysis
Authors: Cheng Shengxian , Ouyang Jing , Li Muqing , Diao Yingxue , Yao Jiachen , Li Fengxing , Lee Yat‐For , SUNG Herman Ho‐Yung , Williams Ian , Xu Zhengtao , Quan Yangjian
Published: April 2023

Photoinduced metal–organic framework (MOF) enabled heterogeneous thiol catalysis has been achieved for the first time. MOF Zr‐TPDCS‐1, consisting of Zr6‐clusters and TPDCS linkers (TPDCS=3,3′′,5,5′′‐tetramercapto[1,1′:4′,1′′‐terphenyl]‐4,4′′‐dicarboxylate), effectively catalyzed the borylation, silylation, phosphorylation, and thiolation of organic molecules. Upon irradiation, the fast electron transfer from TPDCS to Zr6‐cluster is believed to facilitate the formation of the thiyl radical, a hydrogen atom transfer catalyst, which competently abstracts the hydrogen from borane, silane, phosphine, or thiol for generating the corresponding element radical to engender the chemical transformations. The elaborate control experiments evidenced the generation of thiyl radicals in MOF and illustrated a radical reaction pathway. The gram‐scale reaction worked well, and the product was conveniently separated via centrifugation and vacuum with a turnover number (TON) of ≈3880, highlighting the practical application potential of heterogeneous thiyl‐radical catalysis.
Mechanismus der CO Oxidation an einem molekular‐definierten Kupfer‐Einzelatom‐Katalysator auf einer metallorganischen Gerüstverbindung
Authors: Abdel‐Mageed Ali M. , Rungtaweevoranit Bunyarat , Impeng Sarawoot , Bansmann Joachim , Rabeah Jabor , Chen Shilong , Häring Thomas , Namuangrak Supawadee , Faungnawakij Kajornsak , Brückner Angelika , Behm R. Jürgen
Published: April 2023

In der Heterogenen Katalyse ist die Aufklärung des Reaktionsmechanismus essentiell für die systematische Optimierung der Katalysatoren, aber aufgrund der unbekannten Natur der aktiven Zentren herausfordernd. Für einen molekular‐definierten, auf einer metallorganischen Gerüstverbindung (UiO‐66) geträgerten Kupfer‐Einzelatom‐Katalysators konnten wir ein detailliertes mechanistisches Bild der CO Oxidation erarbeiten. Basierend auf einer Kombination von in situ/operando Spektroskopien, kinetischen Messungen inklusive kinetischer Isotopeneffekte sowie Dichtefunktional‐Theorie basierten Rechnungen konnten wir den aktiven Platz, Reaktionsintermediate und Übergangszustände des dominierenden Reaktionszyklus sowie Veränderungen in den Cu Oxidations‐ und Spinzuständen während der Reaktion identifizieren. Die Reaktion verläuft über die reaktive Dissoziation von adsorbiertem O2, durch Reaktion von O2,ad mit koadsorbiertem COad, als ratenlimitierendem Schritt. Das verbleibende O Atom, das das Cu Zentrum mit einem benachbarten Zr4+ Ion verbindet, wird in einem zweiten aktivierten Schritt abreagiert.
Donor‐Acceptor Aminocyclobutane Monoesters: Synthesis and Silylium‐Catalyzed (4+2) Annulation with Indoles
Authors: Robert Emma G. L. , Pirenne Vincent , Wodrich Matthew D. , Waser Jérôme
Published: April 2023

A convenient one‐step synthesis of β‐aminocyclobutane monoesters starting from commercially available reagents is reported. The obtained strained rings undergo (4+2) dearomative annulation with indole partners using silylium catalysis. This organocatalyzed annulation provided tricyclic indolines with four new stereocenters in up to quantitative yield and >95 : 5 diastereoselectivity and can proceed both intra‐ and intermolecularly. When performed intramolecularly, the tetracyclic structure of either akuamma or malagasy alkaloids was obtained selectively depending on the temperature of the reaction. This divergent outcome could be rationalized based on DFT calculations.
Deciphering Reversible Homogeneous Catalysis of the Electrochemical H2 Evolution and Oxidation: Role of Proton Relays and Local Concentration Effects**
Authors: Reuillard Bertrand , Costentin Cyrille , Artero Vincent
Published: April 2023

Nickel bisdiphosphine complexes bearing pendant amines form a unique series of catalysts (so‐called DuBois’ catalysts) capable of bidirectional/reversible electrocatalytic oxidation and production of dihydrogen. This unique behaviour is directly linked to the presence of proton relays installed close to the metal center. We report here for the arginine derivative [Ni(P2CyN2Arg)2]6+ on a mechanistic model and its kinetic treatment that may apply to all DuBois’ catalysts and show that it allows for a good fit of experimental data measured at different pH values, catalyst concentrations and partial hydrogen pressures. The bidirectionality of catalysis results from balanced equilibria related to hydrogen uptake/evolution on one side and (metal)‐hydride installation/capture on the other side, both controlled by concentration effects resulting from the presence of proton relays and connected by two square schemes corresponding to proton‐coupled electron transfer processes. We show that the catalytic bias is controlled by the kinetic of the H2 uptake/evolution step. Reversibility does not require that the energy landscape be flat, with redox transitions occurring at potentials up to 250 mV away for the equilibrium potential, although such large deviations from a flat energy landscape can negatively impacts the rate of catalysis when coupled with slow interfacial electron transfer kinetics.
Unveiling One‐to‐One Correspondence Between Excited Triplet States and Determinate Interactions by Temperature‐Controllable Blue‐Green‐Yellow Afterglow
Authors: Liu Xiuxing , Liao Qiuyan , Yang Jie , Li Zhen , Li Qianqian
Published: April 2023

Phosphorescence of organic materials is highly dependent on intermolecular interactions, for the sensitive triplet excitons toward environment and aggregated structures. However, until now, relationship between phosphorescence and intermolecular interactions is still unclear for complicated influence factors and uncontrollable aggregated behaviors. Herein, taking temperature as the controlled variable, the afterglow can continuously change from blue to green, then to yellow, even achieve the white emission with deuteration process. It is mainly due to the hierarchical architectures of molecular aggregates with rational distribution of intermolecular interactions, as well as gradually unlocking process of interactions with different energies. Accordingly, the one‐to‐one correspondence between the determinate interactions and excited triplet states have been established, guiding accurate design of desirable phosphorescence materials by hierarchical control of aggregated structures.
Dynamic Hydrogen‐Bonded Zinc Adeninate Framework (ZAF) for Immobilization of Catalytic DNA
Authors: Baslyman Walaa S. , Alahmed Othman , Chand Santanu , Qutub Somayah , Khashab Niveen M.
Published: April 2023

Effective immobilization and delivery of genetic materials is at the forefront of biological and medical research directed toward tackling scientific challenges such as gene therapy and cancer treatment. Herein we present a biologically inspired hydrogen‐bonded zinc adeninate framework (ZAF) consisting of zinc adeninate macrocycles that self‐assemble into a 3D framework through adenine‐adenine interactions. ZAF can efficiently immobilize DNAzyme with full protection against enzyme degradation and physiological conditions until it is successfully delivered into the nucleus. As compared to zeolitic imidazolate frameworks (ZIFs), ZAFs are twofold more biocompatible with a significant loading efficiency of 96 %. Overall, our design paves the way for expanding functional hydrogen‐bonding‐based systems as potential platforms for the loading and delivery of biologics.
Synthesis of Sequence‐specific Poly(ester‐carbonate) Copolymers via Chemoselective Terpolymerization Controlled by the Stoichiometric Ratio of Phosphazene/Triethylborane
Authors: Ma Yukun , You Xiaoxia , Zhang Jinbo , Wang Xiaowu , Kou Xinhui , Liu Shaofeng , Zhong Ronglin , Li Zhibo
Published: April 2023

Chemoselective terpolymerization can produce polymer materials with diverse compositions and sequential structures, and thus have attracted considerable attention in the field of polymer synthesis. However, the intrinsic complexity of three‐component system also brings great chanllenge, in regard to the reactivity and selectivity of different monomers. Herein, we report the terpolymerization of CO2/epoxide/anhydride by a binary organocatalytic C3N3‐Py‐P3/TEB (triethylborane) system. Both the activity and chemoselectivity were highly dependent upon the molar ratio of C3N3‐Py‐P3 to TEB, and sequence‐controlled poly(ester‐carbonate) copolymers were readily synthesized through one‐pot/one‐step methodology by tuning the stoichiometric ratio of phosphazene/TEB. In particular, C3N3‐Py‐P3/TEB with a molar ratio of 1/0.5 exhibited an unprecedentedly high chemoselectivity for ring‐opening alternating copolymerization (ROAC) of cyclohexene oxide (CHO) and phthalic anhydride (PA) first and then ROAC of CO2/CHO. Thus, well‐defined triblock polycarbonate‐b‐polyester‐b‐polycarbonate copolymers can be produced from the mixture of CO2, CHO and PA using a bifunctional initiator. With C3N3‐Py‐P3/TEB=1/1, tapered copolymers were obtained, while random copolymers with high content of polycarbonate (PC) were synthesized with further increasing the amount of TEB. The mechanism of the unexpected chemoselectivity was further investigated by DFT calculations.
Modern Strategies for Carbon Isotope Exchange
Authors: Labiche Alexandre , Malandain Augustin , Molins Maxime , Taran Frédéric , Audisio Davide
Published: April 2023

In contrast to stable and natural abundant carbon‐12, the synthesis of organic molecules with carbon (radio)isotopes must be conceived and optimized in order to navigate through the hurdles of radiochemical requirements, such as high costs of the starting materials, harsh conditions and radioactive waste generation. In addition, it must initiate from the small cohort of available C‐labeled building blocks. For long time, multi‐step approaches have represented the sole available patterns. On the other side, the development of chemical reactions based on the reversible cleavage of C−C bonds might offer new opportunities and reshape retrosynthetic analysis in radiosynthesis. This review aims to provide a short survey on the recently emerged carbon isotope exchange technologies that provide effective opportunity for late‐stage labeling. At present, such strategies have relied on the use of primary and easily accessible radiolabeled C1‐building blocks, such as carbon dioxide, carbon monoxide and cyanides, while the activation principles have been based on thermal, photocatalytic, metal‐catalyzed and biocatalytic processes.
Minor Actinides Can Replace Essential Lanthanides in Bacterial Life**
Authors: Singer Helena , Steudtner Robin , Klein Andreas S. , Rulofs Carolin , Zeymer Cathleen , Drobot Björn , Pol Arjan , Cecilia Martinez‐Gomez N. , Op den Camp Huub J. M. , Daumann Lena J.
Published: April 2023

Certain f‐block elements—the lanthanides—have biological relevance in the context of methylotrophic bacteria. The respective strains incorporate these 4 f elements into the active site of one of their key metabolic enzymes, a lanthanide‐dependent methanol dehydrogenase. In this study, we investigated whether actinides, the radioactive 5 f elements, can replace the essential 4 f elements in lanthanide‐dependent bacterial metabolism. Growth studies with Methylacidiphilum fumariolicum SolV and the Methylobacterium extorquens AM1 ΔmxaF mutant demonstrate that americium and curium support growth in the absence of lanthanides. Moreover, strain SolV favors these actinides over late lanthanides when presented with a mixture of equal amounts of lanthanides together with americium and curium. Our combined in vivo and in vitro results establish that methylotrophic bacteria can utilize actinides instead of lanthanides to sustain their one‐carbon metabolism if they possess the correct size and a +III oxidation state.
Electrocatalytic Synthesis of Essential Amino Acids from Nitric Oxide Using Atomically Dispersed Fe on N‐doped Carbon
Authors: Xian Jiahui , Li Suisheng , Su Hui , Liao Peisen , Wang Shihan , Zhang Yawei , Yang Wenqian , Yang Jun , Sun Yamei , Jia Yaling , Liu Qinglin , Liu Qinghua , Li Guangqin
Published: April 2023

How to transfer industrial exhaust gases of nitrogen oxides into high‐values product is significantly important and challenging. Herein, we demonstrate an innovative method for artificial synthesis of essential α‐amino acids from nitric oxide (NO) by reacting with α‐keto acids through electrocatalytic process with atomically dispersed Fe supported on N‐doped carbon matrix (AD‐Fe/NC) as the catalyst. A yield of valine with 32.1 μmol mgcat−1 is delivered at −0.6 V vs. reversible hydrogen electrode, corresponding a selectivity of 11.3 %. In situ X‐ray absorption fine structure and synchrotron radiation infrared spectroscopy analyses show that NO as nitrogen source converted to hydroxylamine that promptly nucleophilic attacked on the electrophilic carbon center of α‐keto acid to form oxime and subsequent reductive hydrogenation occurred on the way to amino acid. Over 6 kinds of α‐amino acids have been successfully synthesized and gaseous nitrogen source can be also replaced by liquid nitrogen source (NO3−). Our findings not only provide a creative method for converting nitrogen oxides into high‐valued products, which is of epoch‐making significance towards artificial synthesis of amino acids, but also benefit in deploying near‐zero‐emission technologies for global environmental and economic development.
Exploiting Reusable Edge‐Functionalized Metal‐Free Polyphthalocyanine Networks for Efficient Polymer Synthesis at Near Infrared Wavelengths
Authors: Wei Wen Fang , Li Xue , Jiang Kaiyue , Zhang Bin , Zhuang Xiaodong , Cai Tao
Published: April 2023

Heterogeneous catalysts are highly advantageous for industrial applications owing to their distinctive merits including easy separation and effective recovery. However, utilizing heterogeneous photocatalysts to harness longer wavelength light remains a critical area of research. This contribution explores the use of edge‐functionalized metal‐free polyphthalocyanine networks (PPc‐x) to promote efficient polymer synthesis under near infrared (NIR) light irradiation. Our screening process revealed that both phenyl‐edged PPc‐x (PPc‐p) and naphthyl‐edged PPc‐x (PPc‐n) offer promising performance for photopolymerization. With the assistance of ppm‐level PPc‐n catalyst, well‐defined polymers were synthesized within a few hours under the regulation of three NIR lights, regardless of shielded by synthetic and biological barriers. An excellent control over the molecular weight and molecular weight distribution was achieved. Furthermore, PPc‐x can be easily recovered and reused for multiple cycles, with negligible leaching and maintenance of the catalytic performance. This study expands a new avenue in developing versatile photocatalysts for the modern synthetic toolkits and offer benefits in diverse applications.
A screening process for carbonation of vegetable oils using an aluminum(salen) complex with a further application as weldable polymers
Authors: Alarcon Rafael T. , Lamb Katie J. , Cavalheiro Éder T. G. , North Michael , Bannach Gilbert
Published: April 2023

Carbon dioxide (CO2) occurs naturally, though its emissions have been increasing due to anthropogenic activities, and its increasing atmospheric concentration levels are causing a greenhouse effect. In efforts to develop new carbon dioxide utilization (CDU) methodologies, the catalyzed reaction of CO2 with epoxidized vegetable oil, obtained from Brazilian macaw oil and Baru oil, to form carbonated oils for novel and sustainable monomers was explored. A screening process is carried out to develop the best reaction conditions, by varying catalyst/cocatalyst loading, reaction time, CO2 pressure, and the reaction temperature, resulting in conversions of 100%. The aluminum(salen) complex shows a selective and efficient catalyst activity. Both carbonated oils are reacted with amines (1,6‐diaminohexane, lysine, and 4,4′‐methylenebis [cyclohexylamine]) to provide weldable polyhydroxyurethanes. Polymers synthesized from lysine provide a more selective reaction and higher cross‐linked structures, with fewer side reactions involving the glyceride groups. All the synthesized polymers are thermally stable above 200°C and differential scanning calorimetry (DSC) analysis shows two main thermal events, related to the glass transition (Tg) and the topology‐freezing transition temperature (Tv). The Tv result indicates that the polymer has weldable properties due to chemical bond exchange. Thus, these polymers can be healed into different shapes upon exposure to red light (660 nm).
Shell characterization of the youngest valid species of the European Eocene genus Neochelys (Pleurodira, Podocnemididae): The Spanish Bartonian Neochelys salmanticensis
Authors: Pérez‐García Adán , Guerrero Andrea , Martín de Jesús Santiago , Ortega Francisco
Published: April 2023

The freshwater pleurodiran turtle Neochelys is the best‐represented member of Podocnemididae in the European record, being known by eight Eocene species. The youngest of them is the Bartonian (middle Eocene) Neochelys salmanticensis, from the Duero Basin (Salamanca Province, Central Spain). It corresponds to the largest representative known for this genus, its shell reaching 50 cm in length. Despite this form was defined several decades ago, the information currently available on it is very limited, being restricted to shell remains of less than 10 individuals. In fact, this species lacks a valid diagnosis, considering the current knowledge about the genus. Numerous remains (i.e., more than 1,200) of the shell of this Spanish species are identified. Its detailed study is presented here, so that the anatomy of its shell is characterized in detail. In addition, several aspects related to its intraspecific variability are analyzed, relative to the individual, ontogenetic, and sexual variability. In this way, the shell of N. salmanticensis can be characterized with greater precision than that of any other species of the genus.
Designing and Judd–Ofelt evaluation of versatile luminescent Eu (III) complexes sensitized with β‐diketone ligand for multifarious applications
Authors: Dua Nishita , Punia Monika , Chhillar Pooja , Bedi Manisha , Khatkar Satyender Pal , Taxak Vinod Bala , Doon Priti Boora
Published: April 2023

The present research work entails the synthesis of one binary and four ternary red light−emitting Eu (III)‐based complexes with 3‐benzylidene‐2,4‐pentanedione as the main ligand and 1,10‐phenanthroline, bathophenanthroline, neocuproine, and 4,4′‐′dimethyl‐2,2′‐′bipyridyl as auxiliary ligands. The metal–organic framework of the series was elucidated using energy dispersive X‐ray analysis, elemental analysis, Fourier transform infrared spectroscopy, and proton nuclear magnetic resonance. This Eu (III) series exhibits optimum thermal stability, making them a promising candidate for organic light‐emitting diodes. On the basis of emission spectra, their optical parameters such as nonradiative and radiative decay rates, luminescence decay time, intrinsic quantum efficiency, and Judd–Ofelt intensity parameter were determined. The monocentric luminescence and Judd–Ofelt parameters reveal the absence of symmetry around the europium center. CIE chromaticity coordinates, correlated color temperature values, color purity, and asymmetric ratios authenticate the color coordinates of the complexes in red region. Optical band gap values lie within the range of wide band gap semiconductors, indicating their utilization in military radars and biological labeling.
P300 as a correlate of false beliefs and false statements
Authors: Wang Yang , Siu Carrey Tik Sze , Cheung Him
Published: April 2023

Introduction

This study investigates P300 as a component for false belief and false statement processing with and without a communicative context. The purpose is to understand why P300 has been shown to be commonly involved in false belief and lie processing.

Methods

Participants were presented with a story in which the protagonist holds a true belief and makes a true statement of it (true belief), holds a false belief and makes a true statement (false belief), or holds a true belief and makes a false statement (false statement) while electroencephalograms were recorded.

Results

In Experiment 1, featuring a solitary protagonist, stronger posterior P300 was shown in the false belief condition than the true belief and false statement condition. With the installation of a communicative context by including a second character listening to the protagonist, Experiment 2 showed enhanced frontal P300 in the false statement condition compared to the true belief and false belief condition. A late slow wave was more prominent in the false belief condition than in the other two conditions in Experiment 2.

Conclusion

The present results suggest a situation‐dependent nature of P300. The signal captures the discrepancy between belief and reality more readily than that between belief and words under a noncommunicative context. It becomes more sensitive to the discrepancy between belief and words than that between belief and reality in a communicative situation with an audience, which makes any false statement practically a lie.
The uneasy marriage of private standards and public policies for sustainable commodity governance
Authors: van der Ven Hamish , Barmes David
Published: April 2023

Global value chains for commodity agriculture have been the target of a broad array of sustainability governance efforts led by both public and private actors. In this paper, we ask: how do public policies and private standards interact in commodity‐exporting countries? To answer this question, we examine the interactions between voluntary sustainability standards and domestic public policies in three cases: soybean farming in Brazil, palm oil production in Indonesia, and pangasius aquaculture in Vietnam. We find that in each case, public and private governance interactions go through a period of competition before ending in a state of reluctant complementarity. We argue that this reluctant complementarity results from the need of governments in commodity‐producing countries to maintain export markets for their goods. This finding challenges the idea that complementarity between public and private sustainable commodity governance is driven by goal alignment and tempers expectations that standards and certifications can mitigate deforestation.
Syntheses and Biological Activities of Danicalipin A Derivatives
Authors: Umezawa Taiki , Maeda Takeshi , Akiyama Takuya , Iman Prakoso Nurcahyo , Jerin Mehjabin Jakia , Okino Tatsufumi , Matsuda Fuyuhiko
Published: April 2023

Synthesis of three derivatives of danicalipin A, tetrachloride, trisulfate and a fluorescent probe was achieved through Wittig reaction strategy. Toxicity of the derivatives against brine shrimp (Artemia salina) as also investigated to provide useful information for the biological activity; i) less chloride derivative showed similar toxicity to danicalipin A, ii) the amphiphilic property, a characteristic feature of danicalipin A, was crucial because trisulfate considerably decreased the toxicity and iii) fluorescent derivative kept brine shrimp toxicity of danicalipin A.
Endovascular treatment of femoro‐popliteal occlusions with retrograde tibial access after failure of the antegrade approach
Authors: Minici Roberto , Serra Raffaele , De Rosi Nicola , Ciranni Salvatore , Talarico Marisa , Petullà Maria , Guzzardi Giuseppe , Fontana Federico , Laganà Domenico
Published: April 2023

Background

Despite the development in endovascular technologies and the introduction of new tools in clinical practice, the endovascular crossing of femoropopliteal occlusions is not always possible with the antegrade approach, with a failure rate that can be up to 20%. This study aims to assess the feasibility, safety, and efficacy in terms of acute outcome of the endovascular retrograde crossing of femoro‐popliteal occlusions with tibial access.

Methods

This study is a single‐centre, retrospective analysis of prospectively collected data of 152 consecutive patients, who had undergone, from September 2015 to September 2022, endovascular treatment of femoro‐popliteal arterial occlusions with retrograde tibial access after the failure of the antegrade approach.

Results

The median lesion length was 25 cm and 66 patients (43.4%) had a calcium grading according to the peripheral arterial calcium scoring system of 4. Angiographically, 44.7% of the lesions were TASC II category D. In all cases, successful cannulation and sheath introduction were performed with an average cannulation time of 150.4 s. Femoropopliteal occlusions were successfully crossed with the retrograde route in 94.1% of cases; the intimal approach was performed in 114 patients (79.7%). The mean time from puncture to retrograde crossing was 20.5 min. Acute vascular access‐site complications were noted in 7 (4.6%) patients. Thirty‐day major adverse cardiovascular events rate and 30‐day major adverse limb events rate of 3.3% and 2%, respectively, were observed.

Conclusions

The results of our study indicate that retrograde crossing of femoro‐popliteal occlusions with tibial access is a feasible, effective, and safe approach in case of failed antegrade approach. The results presented represent one of the largest investigations ever published on tibial retrograde access and contribute to the small body of literature present on this topic to date.
Promising Catalytic Application by Pincer Metal Complexes: Recent Advances in Hydrogenation of Carbon‐Based Molecules
Authors: Manar Krishna K. , Cheng Jing , Yang Yang , Yang Xuemei , Ren Peng
Published: April 2023

In the last two decades, pincer metal complexes have been highly utilized as catalysts for a variety of organic transformations in both industrial and social applications. Owing to the extraordinary chemical characteristics, such as extra thermal stability and easy functionalization, they were extensively utilized for generating novel catalytic species. Besides, the catalytic activity of these pincer metal complexes was achieved with high atom economy and eco‐friendly routes. Recently, the catalysts exhibited excellent behaviour towards various immerging systems, such as the hydrogenation of CO2, nitriles, amides, esters, olefins and alkynes, which are valuable for industrial production, academic research, and green environment. The main goal of this reviewwas to highlight how pincer metal complexes function in these catalytic hydrogenation reactions, as well as their mechanistic studies. Specifically, we focus on the most updated advancements in hydrogenation in the last few years. Some outlooks and future suggestions for further related work conclude the paper.
Photothermal Perylene Bisimide Hydrogels
Authors: Thomson Lisa , Ginesi Rebecca E. , Osborne Daniel D. , Draper Emily R. , Adams Dave J.
Published: April 2023

Gels formed using a perylene bisimide (PBI) as a low molecular weight gelator can show the photothermal effect. Formation of the PBI radical anion results in new absorption bands forming, meaning that subsequent irradiation with a wavelength of light overlapping with the new absorption band leads to heating of the gel. This approach can be used to heat the gel, as well as the surrounding milieu. We show how we can use electrochemical methods as well as multicomponent systems to form the radical anion without the need for UV light, and how we can use the photothermal effect to induce phase transitions in the solutions above the gels by exploiting photothermal behavior.
Dichotomy of Delocalization/Localization and Charge‐Shift Bonding in Germanazene and its Heavier Group 14 Analogues: a Valence Bond Study
Authors: Jain Shailja , Danovich David , Radenković Slavko , Shaik Sason
Published: April 2023

We present here a valence bond analysis of structure and π‐delocalization in Ge3(NH)3, which models germanazene that was prepared by Power et al. To get a broader perspective, we explore the entire E3(NH)3 series (E=C, Si, Ge, Sn, Pb). Thus, while (4n+2)π systems of carbon rings are aromatic with cyclic π‐delocalization, the E3(NH)3 rings are dominated by a nonbonded structure, wherein π‐lone pairs are localized on the N atoms. Nevertheless, these molecules enjoy large covalent‐ionic resonance energies of 153.0, 86.6, 74.2, 61.2, and 58.9 kcal/mol, respectively, for E=C, Si, Ge, Sn, Pb. The covalent‐ionic mixing in E3(NH)3 creates π‐systems, which are stabilized by charge‐shift bonding. Thus, unlike in benzene, in Ge3(NH)3 delocalization of π‐electron pairs of the N atoms is primarily confined to the domains of their adjacent Ge atoms. These features carry over to the substituted germanazene, Ge3(NAr)3 (Ar=Ph).
Base‐Triggered Oxidative Addition to Gold
Authors: Marelli Enrico , Monot Julien , Martin‐Vaca Blanca , Mallet‐Ladeira Sonia , García‐Rodeja Yago , Miqueu Karinne , Bourissou Didier
Published: April 2023

The coordination of secondary phosphine oxides (SPO) was shown to efficiently promote the activation of C(sp2)−I bonds by gold, as long as a base is added (NEt3, K2CO3). These transformations stand as a new type of chelation‐assisted oxidative addition to gold. The role of the base and the influence of the electronic properties of the P‐ligand were analyzed computationally. Accordingly, the oxidative addition was found to be dominated by Au→(Ar−I) backdonation. In this case, gold behaves similarly to palladium, suggesting that the inverse electron flow reported previously (with prevailing (Ar−I)→Au donation, resulting in faster reactions of electron‐enriched substrates) is a specific feature of electron‐deficient cationic gold(I) complexes. The reaction gives straightforward access to (P=O,C)‐cyclometallated Au(III) complexes. The possibility to chemically derivatize the SPO moiety at Au(III) was substantiated by protonation and silylation reactions.
Ozonation/extraction coupled non‐catalytic desulphurization of VGO/natural gas condensate
Authors: Adhami Mohsen , Salman Movahedirad , Sobati Mohammad Amin , Khalili‐Garakani Amirhossein
Published: April 2023

The desulphurization of hydrocarbon fuels with high sulphur content and a wide variety of sulphur‐containing compounds brings significant challenges. In the present work, the non‐catalytic desulphurization of vacuum gas oil (VGO) and natural gas condensate mixed fuel has been investigated. In this regard, ozone was employed as the oxidant in a bubble column gas–liquid contactor, and an extraction step was further incorporated. The effects of the oxidation reactor scheme, ozonation time, and extraction with different solvents, applying pre‐ and post‐extraction strategies (i.e., ozonation/extraction/extraction and extraction/ozonation/extraction), have been studied. It was found that pre‐extraction of mixed fuel increases the oxidative desulphurization (ODS) efficiency due to the removal of light sulphur‐containing compounds (SCCs). N‐methyl‐2‐pyrrolidone (NMP) has been found to be the most effective extraction agent, removing 44% of sulphur by pure extraction and 77.4% by ozonation + extraction. However, in terms of fuel loss, dimethylformamide (DMF) performs better than NMP, and it has been shown to be the most appropriate solvent for achieving a 90% desulphurization ratio. Finally, it was found that the applied procedure could effectively remove the wide range of SCCs, especially refractive components such as benzothiophene (BT) and dibenzothiophene (DBT).
1H NMR Elucidation of Observed Stable Sugar‐NaCl‐water Complexes in Aqueous Solution**
Authors: Zhu Gan , Li Hui , Li Yiqun , Gu Liuqun
Published: April 2023

The solvation of sugars in aqueous media matters in the understanding of biological systems and carbohydrate transformations. The presence of NaCl is known to perturb hydrogen bonding of sugar hydrates, however, direct evidence to elucidate mechanism at atom level is very rare even though the “NaCl Effect” was well known in biomass transformations for chemicals/biofuels. Here we report experimental evidences of a clear staircase‐like correlation between induced 1H NMR changes of D‐glucose/fructose with concentration of NaCl aqueous solution at room temperature; and two stable bonding status was observed in the system. HDO in sugar/NaCl aqueous solution as a “dynamic” reference is a key to enable decoupling the global salt effect in this 1H NMR investigation of NaCl‐saccharide interaction. Via a further half‐quantitative study, three structures of stable sugar‐NaCl‐water complexes were mapped for the first time in tackling the NaCl‐monosaccharide interaction at atomic level in an aqueous solution. Based on the maximum of induced 1H NMR shifts, an ideal NaCl usage was proposed.
Targeted therapy for lung cancer: Beyond EGFR and ALK
Authors: Herrera‐Juárez Mercedes , Serrano‐Gómez Cristina , Bote‐de‐Cabo Helena , Paz‐Ares Luis
Published: April 2023

Precision oncology comprises the set of strategies that aim to design the best cancer treatment based on tumor biology. A recognized subset of patients with non‐small cell lung cancer (NSCLC) harbor actionable genomic aberrations that can benefit from targeted therapy. In lung cancer, epidermal growth factor receptor (EGFR) mutations and anaplastic lymphoma kinase (ALK) rearrangements are well characterized oncogenic drivers for which the therapeutic use of tyrosine kinase inhibitors has demonstrated improved outcomes compared with chemotherapy. Other druggable targets are also well characterized, and effective inhibitors have been developed and commercialized, leading to a paradigm shift in NSCLC treatment. Here, the authors provide a review of the oncogenic role of the most relevant molecular alterations in NSCLC and emerging treatments in this setting beyond EGFR‐driven and ALK‐driven diseases.
In situ characterizations for aqueous rechargeable zinc batteries
Authors: Wu Buke , Mu Yongbiao , He Jiafeng , Li Ming , Li Zheng , Chu Youqi , Li Yiju , Zeng Lin
Published: April 2023

Recently, aqueous rechargeable zinc batteries (ARZBs) have become a hot topic in secondary batteries. Constant attention has witnessed the development of ARZBs, such as active materials, reaction mechanisms, and mass transport, and huge successes have been achieved. However, as the fundamental basis of battery monitoring in real‐time and the theories of ARZBs, the in situ characterization techniques are equally worth discussing but the relevant review remains missing. Herein, this review focuses on the in situ characterization techniques of visualization and spectroscopy characterizations for ARZBs. Typical research of the in situ techniques is comprehensively discussed, including the setup of the in situ cells, the working principle of characterizations, the application, and the analysis applied in ARZBs. With the help of in situ characterizations, the reaction dynamics, transport kinetics, and thermodynamics in ARZBs can be thoroughly researched. Finally, the current primary challenges and future opportunities faced by in situ techniques toward ARZBs are also summarized.
Airway obstruction in respiratory viral infections due to impaired mucociliary clearance
Authors: Bessonov N. , Volpert V.
Published: April 2023

Respiratory viral infections, such as SARS‐CoV‐2 or influenza, can lead to impaired mucociliary clearance in the bronchial tree due to increased mucus viscosity and its hyper‐secretion. We develop in this work a mathematical model to study the interplay between viral infection and mucus motion. The results of numerical simulations show that infection progression can be characterized by three main stages. At the first stage, infection spreads through the most part of mucus producing airways (about 90% of the length) without significant changes in mucus velocity and thickness layer. During the second stage, when it passes through the remaining generations, mucus viscosity increases, its velocity drops down, and it forms a plug. At the last stage, the thickness of the mucus layer gradually increases because mucus is still produced but not removed by the flow. After some time, the thickness of the mucus layer in the small airways becomes comparable with their diameter leading to their complete obstruction.
Rimegepant 75 mg in Subjects With Hepatic Impairment: Results of a Phase 1, Open‐Label, Single‐Dose, Parallel‐Group Study
Authors: Bhardwaj Rajinder , Ivans Andrea , Stringfellow Joseph , Morris Beth , Coric Vladimir , Croop Robert , Bertz Richard
Published: April 2023

Rimegepant is a small‐molecule calcitonin gene–related peptide receptor antagonist (gepant) with demonstrated efficacy and safety in the acute and preventive treatment of migraine. Here, we report the pharmacokinetics and safety of a single 75‐mg oral dose of rimegepant in subjects with severe, moderate, or mild hepatic impairment and matched healthy subjects from an open‐label, single‐dose, 4‐group phase 1 study. Thirty‐six subjects aged 41‐71 years were enrolled, including 6 each with severe, moderate, or mild hepatic impairment and 18 healthy subjects. All subjects completed the study. A <20% increase in total and unbound pharmacokinetics was observed in subjects with mild hepatic impairment and ≤65% increase with moderate hepatic impairment versus matched healthy controls. Total and unbound systemic exposure increased 2.0‐ and 3.9‐fold in the severe hepatic impairment group. In subjects with severe hepatic impairment, geometric mean ratios (severe impairment/controls) for total concentrations were 202.2% for area under the plasma concentration–time curve from time 0 to the last quantifiable concentration, 202.2% for area under the plasma concentration–time curve from time 0 to infinity, and 189.1% for maximum observed plasma concentration. Corresponding geometric mean ratios using unbound concentrations were 388.8% and 388.7%, respectively. Three (8.3%) subjects reported 4 treatment‐emergent adverse events. Rimegepant is not recommended for use in adults with severe hepatic impairment.
Classification of stochastic processes with topological data analysis
Authors: Güzel İsmail , Kaygun Atabey
Published: April 2023

In this study, we demonstrate that engineered topological features can distinguish time series sampled from different stochastic processes with different noise characteristics, in both balanced and unbalanced sampling schemes. We compare our classification results against the results of the same classification on features coming from descriptive statistics and the wavelet transform. We conclude that machine learning models built on engineered topological features alone perform consistently better than those built on the standard statistical and wavelet features for time series classification tasks. We also apply dimension reduction techniques to our engineered features and compare the result of our classification models before and after dimensionality reduction. Finally, we also show that in our calculations of the engineered topological features, employing parallel computing methods does yield significant improvements in run time and memory footprint.
MANSOR: A module alignment method based on neighbor information for scientific workflow
Authors: Gu Yang , Cao Jian , Qian Shiyou , Zhu Nengjun , Guan Wei
Published: April 2023

Finding similar scientific workflow modules that can substitute essential components of the privacy workflows from public repositories to create a personalized workflow is growing in popularity. This is a cost‐effective and error‐free strategy for the scientific community. Currently, module alignment approaches heavily depend on syntactic information such as modules' names and types. However, the contextual semantic information of modules, which encompasses inputs, outputs, and datalinks connecting modules, can also convey their functions. Unfortunately, this information is scarcely utilized during the module alignment process. In this work, we propose a module alignment method based on neighbor information for scientific workflow (MANSOR). Specifically, we present a rule‐based attribute similarity computation approach for calculating initial module‐pair similarity in two workflows. The relation similarity is then employed to iteratively fine‐tune the matching degree with uncertainty of module pairs by considering the contextual semantics until reaching a steady state. After pairwise comparison of workflows, the module alignment results are determined based on their module‐pair similarity. Experimental results on the human‐curated corpus of ratings indicate that MANSOR outperforms the existing state‐of‐the‐art approaches with statistical significance.
Longitudinal associations of chronic health stress and COVID‐19‐related anxiety among outpatients with anxiety and mood disorders
Authors: Yamin Nikka , Brown Timothy A. , Rosellini Anthony J.
Published: April 2023

Background

The 2019 coronavirus (COVID‐19) pandemic led to elevated levels of psychological distress on a global scale. Given that individuals with pre‐existing physical conditions are at risk for worse COVID‐19 outcomes, those dealing with the stress of physical health problems (including knowing someone with health problems) may experience more severe distress during the pandemic.

Methods

Patients with emotional disorders who completed a diagnostic assessment in the 6 months prior to COVID‐19 were surveyed in May–June 2020 on their emotional reactions to COVID‐19 (N = 77).

Results

Multiple linear regression was used to test the hypothesis that chronic stress due to having and knowing others with physical health problems would predict COVID‐related worries and behaviours, holding pre‐COVID levels of depression, anxiety and worry about health constant. Chronic stress surrounding the health of others was significantly associated with experiencing more severe COVID‐related worry and behaviours. In comparison, chronic stress due to one's own health problems had weak and non‐significant associations with COVID‐related worries and behaviours.

Conclusions

Results indicate that outpatients who report stress about surrounding loved one's health are at risk for experiencing more severe distress during a health pandemic and thus, may benefit from targeted outreach, assessment and intervention.
Nonrandom X Chromosome Inactivation Detection
Authors: Caylor Raymond C.
Published: April 2023

X chromosome inactivation patterns may be clinically useful in assessing tumor clonality, determining carrier status for certain X‐linked disorders, and evaluating the pathogenicity of a genetic variant identified in an X‐linked gene. The protocols in this article utilize the highly polymorphic trinucleotide repeat within the first exon of the human androgen receptor gene (AR) and the methylation‐sensitive restriction enzyme HpaII to distinguish between the maternal and paternal alleles and simultaneously determine their methylation status. The data obtained from these protocols can be used to calculate the ratio of inactivation between the two alleles that ultimately reflects whether a female has a random or nonrandom pattern of X chromosome inactivation. © 2023 Wiley Periodicals LLC.

Basic Protocol 1: X chromosome inactivation assay

Basic Protocol 2: PCR amplification and labeling of digested and undigested DNA templates
A random access channel resources allocation approach to control machine‐to‐machine communication congestion over LTE‐advanced networks
Authors: Aragão David , Rodrigues Christiano , Vieira Dario , de Castro Miguel Franklin
Published: April 2023

The Internet of Things (IoT) is becoming a reality, and one of the core elements to make this reality come true is machine‐to‐machine (M2M) communication. With the fast‐growing rate in which devices are being deployed, communication among them has become crucial to support the development of IoT applications. The Long‐Term Evolution‐Advanced (LTE‐A) is a potential access network for these M2M devices. However, the LTE‐A inherited characteristics from older cellular network standards, which were designed for human‐to‐human (H2H) and human‐to‐machine (H2M) communication. Accordingly, supporting M2M communication poses some challenges to LTE‐A, with a highlight of the congestion and overload problems in the radio access network (RAN) during the random access channel (RACH) procedure. Such a problem arises due to the large number of devices sending access‐request messages to the network and the limited number of resources to satisfy this new demand. In this paper, we introduce a solution to mitigate the impact of M2M communication in the LTE‐A network. Precisely, we model how to divide the random access resources into different types of devices as a bankruptcy problem. Then, we propose two solutions: (i) A game theory approach to formulate the bankruptcy problem as a transferable utility game, and (ii) an axiomatic method where some elements are considered for judging the amount of resources each class should receive. The simulation results show that our approaches present improvements in terms of energy efficiency, impact control of M2M over H2H accesses, and priority respect among the different classes of devices.
Performance of orthogonal frequency division multiplexing based M‐ary quadrature amplitude modulation in asymmetrical dual‐hop mixed RF‐FSO transmission system
Authors: Hemanth C. , Sangeetha R. G. , Jaiswal Ishu
Published: April 2023

This paper investigates the performance of a dual‐hop mixed relay system with radio frequency (RF) and free‐space optics (FSO) communication under the effect of pointing error (PE) and atmospheric turbulence (AT). This paper considers a system where RF and FSO links are cascaded. The RF link is modeled by Nakagami‐m fading, and the FSO link is modeled as gamma–gamma (G‐G) fading channel. Both the channel models use orthogonal frequency division multiplexing (OFDM) with M‐ary quadrature amplitude modulation (QAM). The expressions for probability density function, cumulative distribution function, signal‐to‐noise ratio, and ergodic capacity are derived. The moment generating function (MGF) of fading and the bit error rate (BER) of the OFDM‐based M‐ary QAM scheme is derived in terms of Meijer's G‐function. It has been observed that, in fixed gain relay systems, the modulation scheme's BER is dominated by the SNR of the RF link. While in a variable gain relay system, the turbulence conditions of the FSO system affect the SNR and the BER of the modulation method. The feasibility of heterodyne detection and intensity modulation direct detection (IM/DD) is analyzed in terms of outage probability and ergodic capacity. The results can be used to choose the optimal modulation order and relay system for QAM‐OFDM‐based optical wireless systems.