bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis of Pharmaceutically Relevant Arylamines Enabled by a Nitroreductase from Bacillus tequilensis
Authors: Russo Sara , Luján Alejandro Prats , Fraaije Marco W. , Poelarends Gerrit J.
Published: March 2024

Arylamines are essential building blocks for the manufacture of valuable pharmaceuticals, pigments and dyes. However, their current industrial production involves the use of chemocatalytic procedures with a significant environmental impact. As a result, flavin‐dependent nitroreductases (NRs) have received increasing attention as sustainable catalysts for more ecofriendly synthesis of arylamines. In this study, we assessed a novel NR from Bacillus tequilensis, named BtNR, for the synthesis of pharmaceutically relevant arylamines, including valuable synthons used in the manufacture of blockbuster drugs such as vismodegib, sonidegib, linezolid and sildenafil. After optimizing the enzymatic reaction conditions, high conversion of nitroaromatics to arylamines (up to 97 %) and good product yields (up to 56 %) were achieved. Our results indicate that BtNR has a broad substrate scope, including bulky nitro benzenes, nitro pyrazoles and nitro pyridines. Hence, BtNR is an interesting biocatalyst for the synthesis of pharmaceutically relevant amine‐functionalized aromatics, providing an attractive alternative to traditional chemical synthesis methodologies.
Design of New Bis(1,2,3‐triazol‐1‐yl)methane‐Based Nitrogen Ligands: Synthesis and Coordination Chemistry
Authors: Martínez de Sarasa Buchaca Marc , de la Cruz‐Martínez Felipe , Naranjo Jesús , Rodríguez Ana M. , de la Torre María C. , Castro‐Osma José A. , Sierra Miguel A. , Lara‐Sánchez Agustín
Published: March 2024

The reaction between bis(1,2,3‐triazol‐1‐yl)methane derivatives and nBuLi and various aldehydes, yielded novel neutral ligand precursors incorporating alcohol functional groups. The resulting compounds exhibited distinct characteristics depending on the steric hindrance of the aldehyde employed. In instances where aromatic aldehydes were utilized, functionalization occurred at the methine group bridging both triazole rings. Conversely, the use of pivalic aldehyde prompted functionalization at the C5 position of the triazole ring. These compounds were subsequently employed as ligand precursors in the synthesis of organometallic aluminum and zinc complexes, yielding dinuclear complexes with high efficiency. The structural elucidation of all compounds was accomplished through spectroscopic methods and validated by X‐ray crystallography. Preliminary catalytic investigations into the coupling reaction of cyclohexene oxide and CO2 revealed that aluminum and zinc complexes catalyzed the selective formation of polyether and polycarbonate materials, respectively.
Unravelling the Role of Free Radicals in Photocatalysis
Authors: Chen Yao , Xu Shuyang , Fang Wen Chun , Zhang Hanyun , Zhang Ting , Lv Fujian , Yue Yinghong , Bian Zhenfeng
Published: March 2024

Free radicals are increasingly recognized as active intermediate reactive species that can participate in various redox processes, significantly influencing the mechanistic pathways of reactions. Numerous researchers have investigated the generation of one or more distinct photogenerated radicals, proposing various hypotheses to explain the reaction mechanisms. Notably, recent research has demonstrated the emergence of photogenerated radicals in innovative processes, including organic chemical reactions and the photocatalytic dissolution of precious metals. To harness the potential of these free radicals more effectively, it is imperative to consolidate and analyze the processes and action modes of these photogenerated radicals. This conceptual paper delves into the latest advancements in understanding the mechanics of photogenerated radicals.
Cycloaddition Reactions of Epoxides and CO2 Catalyzed by Bifunctional Rare‐Earth Metal Complexes Bearing Amino‐Bridged Tris(phenolato) Ligands
Authors: Chen Yongjie , Wang Yanwei , Nong Jun , Yuan Dan , Yao Yingming
Published: March 2024

Comprehensive Summary

Eight zwitterionic rare earth metal complexes stabilized by amino‐bridged tris(phenolato) ligands bearing quaternary ammonium side‐arms were synthesized and characterized. These complexes were used as single‐component catalysts for the cycloaddition of CO2 and epoxides, and their catalytic activities are obviously higher than those of their binary analogues. Further studies revealed that the halide anions (Cl–, Br–, I–) and the metal complexes influenced the catalytic activity, and the lanthanum complex bearing iodide anion showed the highest catalytic activity for this addition reaction. A variety of mono‐substituted epoxides were converted to cyclic carbonates in good to excellent yields (55%—99%) with high selectivity (> 99%) at 30 °C and 1 bar CO2, whereas internal epoxides required higher both reaction temperatures (60—120 °C) and catalyst loading (2 mol%) for high yields. The catalyst was recyclable for four times without noticeable loss of catalytic activity. Based on the results of kinetic studies and in situ IR reactions, a plausible reaction mechanism was proposed.
Metal‐Free Electrochemical Trifluoromethylation of Imidazole‐Fused Heterocycles with Trifluoromethyl Thianthrenium Triflate
Authors: Ge Chang , Qiao Lipeng , Zhang Yuyang , Sun Kai , An Jiangzhen , Peng Mei , Chen Xiaolan , Qu Lingbo , Yu Bing
Published: March 2024

Comprehensive Summary

A novel and eco‐friendly electrochemical activation of trifluoromethyl thianthrenium triflate (TT–CF3+OTf−) for trifluoromethylation of imidazole‐fused heteroaromatic compounds was established. This method involves the direct electrolysis of TT–CF3+OTf− without the requirement of external oxidants or catalysts, aligning with the principles of green chemistry. A wide range of imidazole‐fused heteroaromatic compounds including imidazo[1,2‐a]pyridines and benzo[d]imidazo[2,1‐b]thiazoles have been successfully trifluoromethylated using this technique, exhibiting excellent compatibility with various functional groups and a broad substrate scope. Moreover, the method's applicability for one‐pot sequential reactions enables the reduction of waste and resource consumption by eliminating the need for intermediate purification steps.
Iodinated 4,4’‐Bipyridines with Antiproliferative Activity Against Melanoma Cell Lines
Authors: Peluso Paola , Mamane Victor , Spissu Ylenia , Casu Giuseppina , Dessì Alessandro , Dallocchio Roberto , Sechi Barbara , Palmieri Giuseppe , Rozzo Carla
Published: March 2024

In the last decade, biological processes involving halogen bond (HaB) as a leading interaction attracted great interest. However, although bound iodine atoms are considered powerful HaB donors, few iodinated new drugs were reported so far. Recently, iodinated 4,4’‐bipyridines showed interesting properties as HaB donors in solution and in the solid state. In this paper, a study on the inhibition activity of seven halogenated 4,4’‐bipyridines against malignant melanoma (MM) cell proliferation is described. Explorative dose/response proliferation assays were first performed with three 4,4’‐bipyridines by using four MM cell lines and the normal BJ fibroblast cell line as control. Among them, the A375 MM cell line was the most sensitive, as determined by MTT assays, which was selected to evaluate the antiproliferative activity of all 4,4’‐bipyridines. Significantly, the presence of an electrophilic iodine impacted the biological activity of the corresponding compounds. The 3,3’,5,5’‐tetrachloro‐2‐iodo‐4,4’‐bipyridine showed significant antiproliferation activity against the A375 cell line, and lower toxicity on BJ fibroblasts. Through in silico studies, the stereoelectronic features of possible sites determining the bioactivity were explored. These results pave the way for the utilization of iodinated 4,4’‐bipyridines as templates to design new promising HaB‐enabled inhibitors of MM cell proliferation.
Radiation‐induced effects on TGF‐β and PDGF receptor signaling in cancer‐associated fibroblasts
Authors: Yang Nannan , Hellevik Turid , Berzaghi Rodrigo , Martinez‐Zubiaurre Inigo
Published: March 2024

Background

Cancer‐associated fibroblasts (CAFs) consist of heterogeneous connective tissue cells and are often constituting the most abundant cell type in the tumor stroma. Radiation effects on tumor stromal components like CAFs in the context of radiation treatment is not well‐described.

Aim

This study explores potential changes induced by ionizing radiation (IR) on platelet‐derived growth factor (PDGF)/PDGFRs and transforming growth factor‐beta (TGF‐β)/TGFβRs signaling systems in CAFs.

Methods and Results

Experiments were carried out by employing primary cultures of human CAFs isolated from freshly resected non‐small cell lung carcinoma tumor tissues. CAF cultures from nine donors were treated with one high (1 × 18 Gy) or three fractionated (3 × 6 Gy) radiation doses. Alterations in expression levels of TGFβRII and PDGFRα/β induced by IR were analyzed by western blots and flow cytometry. In the presence or absence of cognate ligands, receptor activation was studied in nonirradiated and irradiated CAFs. Radiation exposure did not exert changes in expression of PDGF or TGF‐β receptors in CAFs. Additionally, IR alone was unable to trigger activation of either receptor. The radiation regimens tested did not affect PDGFRβ signaling in the presence of PDGF‐BB. In contrast, signaling via pSmad2/3 and pSmad1/5/8 appeared to be down‐regulated in irradiated CAFs after stimulation with TGF‐β, as compared with controls.

Conclusion

Our data demonstrate that IR by itself is insufficient to induce measurable changes in PDGF or TGF‐β receptor expression levels or to induce receptor activation in CAFs. However, in the presence of their respective ligands, exposure to radiation at certain doses appear to interfere with TGF‐β receptor signaling.
Phosphaarsenes – Combining Phospha‐ and Arsa‐Wittig‐Reagents
Authors: Beer Henrik , Siewert Jan‐Erik , Schröder Mirjam , Fischer Malte , Corzilius Björn , Hering‐Junghans Christian
Published: March 2024

Dipnictenes of the type RPn=PnR (Pn=P, As, Sb, Bi) can be viewed as dimers of the corresponding pnictinidenes R−Pn. Phosphanylidene‐ and arsanylidenephosphoranes (R−Pn(PMe3); Pn=P, As) have been shown to be versatile synthetic surrogates for the delivery of pnictinidene fragments. We now report that thermal treatment of 1 : 1 mixtures of R−P(PMe3) and R’−As(PMe3) gives access to arsaphosphenes of the type RP=AsR’. Three examples are presented and the properties and reactivity of Mes*P=AsDipTer (1) (Mes*=2,4,6‐tBu3‐C6H2; DipTer=2,6‐(2,6‐iPr2C6H3)2‐C6H3) were studied in detail. Solid state 31P NMR spectroscopy revealed a large 31P NMR chemical shift anisotropy with a span of ca. 920 ppm for 1 while computational methods were employed to investigate this pronounced magnetic deshielding of the P atom in 1. In the presence of the carbene IMe4 (IMe4=:C(MeNCMe)2) 1 is shown to be split into the corresponding NHC adducts Mes*P(IMe4) and DipTerAs(IMe4), which is additionally shown for diarsenes.
Multi‐azo Photoswitches for Improved Molecular Solar Thermal Energy Storage
Authors: Dong Dongfang , Li Tao
Published: March 2024

Molecular solar thermal energy storage (MOST) based on photoisomerization represents a novel approach for the capture, conversion and storage of solar energy. Azo photoswitches can store energy by isomerization from their thermodynamically stable E isomers to higher energy metastable Z isomers. The energy density of azo photoswitches is crucial as it directly determines the storage capacity, but it is relatively low (160 J g−1). Therefore, enhancing the energy density through molecular structural design represents a central research focus in the field of MOST. A straightforward approach to enhance the energy density is to design multi‐azo photoswitches. This allows multiple azobenzene units to share a common framework while keeping the molecular weight as small as possible. In particular, when two azobenzene units are connected via a phenyl ring in a meta orientation, it facilitates efficient isomerization, thereby maximizing the energy density of the azo photoswitches (392 J g−1). This paper provides a brief overview of the development of multi‐azo photoswitches and highlights their outstanding performance as a MOST system. It also offers prospects for their future advancements in the field. We propose that, to further improve the energy density of multi‐azo photoswitches, one approach is to design wide spectrum of light photoisomerization of multi‐azo photoswitches. Additionally, introducing photo‐induced phase changes to multi‐azo photoswitches enables the simultaneous storage of both photon energy and ambient heat.
Multi‐metallic Layered Catalysts for Stable Electrochemical CO2 Reduction to Formate and Formic Acid
Authors: Nguyen Tu N. , Khiarak Behnam Nourmohammadi , Xu Zijun , Farzi Amirhossein , Sadaf Sharif Md. , Seifitokaldani Ali , Dinh Cao‐Thang
Published: March 2024

Electrochemical CO2 reduction (ECR) to value‐added products such as formate/formic acid is a promising approach for CO2 mitigation. Practical ECR requires long‐term stability at industrially relevant reduction rates, which is challenging due to the rapid degradation of most catalysts at high current densities. Herein, we report the development of a bismuth (Bi) gas diffusion electrode on a polytetrafluoroethylene‐based electrically conductive silver (Ag) substrate (Ag@Bi), which exhibits high Faradaic efficiency (FE) for formate of over 90 % in 1 M KOH and 1 M KHCO3 electrolytes. The catalyst also shows high selectivity of formic acid above 85 % in 1 M NaCl catholyte, which has a bulk pH of 2–3 during ECR, at current densities up to 300 mA cm−2. In 1 M KHCO3 condition, Ag@Bi maintains formate FE above 90 % for at least 500 hours at the current density of 100 mA cm−2. We found that the Ag@Bi catalyst degrades over time due to the leaching of Bi in the NaCl catholyte. To overcome this challenge, we deposited a layer of Ag nanoparticles on the surface of Ag@Bi to form a multi‐layer Ag@Bi/Ag catalyst. This designed catalyst exhibits 300 hours of stability with FE for formic acid ≥70 % at 100 mA cm−2. Our work establishes a new strategy for achieving the operational longevity of ECR under wide pH conditions, which is critical for practical applications.
Energy optimized artificial hummingbird algorithm for routing in IoT‐based software‐defined WSN
Authors: Beniwal Rohit , Kumar Nitesh
Published: March 2024

The Internet of Things (IoT) has become widely used in applications such as smart homes, industrial automation, and transportation due to its affordable hardware and fast internet connectivity. However, the increase in IoT‐enabled gadgets, particularly those running on batteries or connected to other sources, is putting strain on the world's energy requirements. Therefore, this study focuses on a green routing solution for battery‐powered IoT‐enabled Software‐defined Wireless Sensor Networks (IoT‐SDWSN). Finding green solutions for IoT‐based networks to address this energy challenge has become crucial. This study focuses on developing a green routing solution for battery‐powered IoT‐SDWSN. Energy efficiency in IoT‐SDWSN is attained by the process of clustering nodes. The network is partitioned into small clusters, and a Control Node (CN) is set up by a Control Server (CS) to transmit the data packets sent by sensor nodes. Choosing a CN in these networks is a critical concern due to the substantial energy consumption involved in delivering data to the CS. This research focuses on the problem of energy‐efficient cluster routing in IoT‐based SD‐WSN. It introduces the Energy‐optimized Artificial Hummingbird Algorithm (EOAHA) as a green routing technique. EOAHA aims to extend the lifespan of IoT‐based SD‐WSNs by intelligently selecting (based on a new fitness function) CNs to distribute the network load and increase its overall longevity. To evaluate the performance of EOAHA, a comparative analysis is conducted against other state‐of‐the‐art algorithms. The results demonstrate that EOAHA outperforms these algorithms by a minimum of 13.5% in terms of network longevity.
Timely dying in dementia: Use patients' judgments and broaden the concept of suffering
Authors: Terman Stanley A. , Steinberg Karl E. , Hinerman Nathaniel
Published: March 2024

Patients living with advanced dementia (PLADs) face several challenges to attain the goal of avoiding prolonged dying with severe suffering. One is how to determine when PLADs’ current suffering becomes severe enough to cease all life‐sustaining treatments, including withdrawing assistance with oral feeding and hydrating, a controversial order. This article broadens the concept of suffering by including suffering that cannot be observed contemporaneously and the suffering of loved ones. Four paradigm shifts operationalize these concepts. During advance care planning, patients can judge which future clinical conditions would cause severe suffering. To decide when to allow patients to die, treating physicians/providers only need to assess if patients have reached patients' previously judged, qualifying conditions. Questions: Will this protocol prevent PLADs’ prolonged dying with suffering? Deter early‐stage dementia patients from committing preemptive suicide? Sway decision‐making surrogates from withholding life‐sustaining treatments from patients with middle‐stage dementia? Provoke providers’ resistance to relinquish their traditional, unilateral authority to determine patients’ suffering?
Hydrologic remobilisation of tephra‐fall deposits: A sedimentological analysis throughout fluvio‐lacustrine systems of North‐West Patagonia
Authors: Losano Nahuel , Villarosa Gustavo , Beigt Débora , Amat Pablo , Cottet Julieta , Outes Valeria
Published: March 2024

This paper explores the response to Holocene ash inundation in different sub‐environments of two fluvio‐lacustrine systems, Las Piedritas and Totoral, focussing on the processes of volcaniclastic remobilisation. Sediment cores and outcrops were used to recognise three deposit types, noting how some differ from lahars, through sedimentological and stratigraphic analysis: (1) thick, laterally discontinuous, pumice‐dominated deposits occur overlying alluvial plain and lower terrace surfaces across both watersheds; (2) chaotic, extremely poorly sorted and matrix‐supported beds composed of both epiclastic and pyroclastic material occur as two conspicuous deposits at Las Piedritas outcrops, in a low‐gradient confined channel setting; and (3) layers with an exclusively pyroclastic composition and no flow sedimentary structures or fragment roundness were found draping each of the two chaotic intervals and intercalating with the background sediment in Las Piedritas prodelta. Thick pumice packages capping the floodplains resulted from the overflow of streams carrying a floating pumice load. Due to its positive buoyancy, the pumice is transported as a slowly moving overlying mantle without mixing with the streamflow. The disorganised pattern and poor sorting of the matrix‐rich polymictic beds are consistent with laminar, gravity‐driven, high‐concentration flows. They constitute secondary lahars, originating upstream from large run‐off processes that reworked a pyroclastic substrate. The lack of reworking features in the vitric‐rich units identified in the lake core retrieved from Las Piedritas prodelta, as well as the continuous and widespread occurrences of those interbedded in upstream outcrops, indicate an airfall origin. No reworked tephra unit is recognised in the prodelta sediment record, although various deposits from the hydrologic remobilisation of airfall tephra are found along the subaerial portion of both watersheds. Apparently, large amounts of flotation‐remobilised tephra were retained on the delta plain, while another considerable fraction would have been carried away from the creek mouth under the influence of dominant regional winds.
Infant exposure to drugs of abuse investigated by hair analysis
Authors: Clara Cestonaro , Claudio Terranova , Alessandro Cinquetti , Alessia Russo , Anna Aprile , Donata Favretto
Published: March 2024

Infant exposure to drugs of abuse represents a worldwide problem whose extent is difficult to estimate. Despite the potentially serious health consequences, few data concerning exposure in children under 1 year of age are available. Since in clinical and forensic settings, neonatal and infant hair testing represents a useful method for investigating suspected drug exposures, an observational retrospective study was performed on hair analysis of children under 1 year of age evaluated at the University Hospital of Padova between 2018 and 2022 with the aim of estimate the extent and define the characteristics of this phenomenon in the reference setting. The sample included 102 infants. Chemical‐toxicological analyses were requested in 38 cases (37.3%) because of clinically suspicious symptoms of the child (e.g., neuropsychiatric symptoms and suspected neonatal abstinence syndrome) and in 64 cases (62.7%) because of other reasons (e.g., maternal drug history, at‐risk environment, and suspected maltreatment). Based on the presence or absence of symptoms in the request, the sample was subdivided into two groups. Hair analysis in these two showed the presence of drug of abuse, respectively, in 44.7% and 67.2% of the cases (p = 0.026). Cocaine was the most frequently detected substance, followed by opiates, and it was detected less frequently in cases investigated for suspicious clinical symptoms (p < 0.05). The results confirm the difficulties in interpreting the clinical picture and in defining the extent of exposure to drugs of abuse. An integrated assessment is fundamental to interpret the case and achieve adequate care of the child.
The potential role of occupational therapy in the treatment of avoidant/restrictive food intake disorder
Authors: Willman Rebecca , Hobbs Midge , Thomas Jennifer J.
Published: March 2024

Most individuals with avoidant/restrictive food intake disorder (ARFID) never receive treatment, and treatment needs far exceed the current capacity of mental health services. Occupational therapy (OT) focuses on enhancing function in daily activities, including eating and feeding. Given OT's rich history in mental health and pediatric feeding disorder treatment, we spotlight the potential role of OT in ARFID treatment, current knowledge, and opportunities for future research. Through a preliminary exploratory inquiry involving a review of current literature and clinical practice, we investigated OT's current involvement, knowledge, and interprofessional collaborative practice gaps in ARFID treatment. While many occupational therapy practitioners (OTPs) engage in ARFID treatment, interventions lack rigorous evaluation, and there is limited evidence defining OT's distinct role in interprofessional ARFID treatment. OTPs are uniquely positioned to provide interventions for individuals with ARFID across the lifespan, though research is needed to evaluate the efficacy of OT interventions. Future research suggestions include standardizing OT approaches to ARFID treatment and conducting single‐case experiments and randomized controlled trials to compare OT approaches with alternative methods. Recommendations to address practice gaps include enhancing ARFID education for OT students and practitioners and fostering a greater understanding of OT's role on the interprofessional team.

Public Significance

Individuals with ARFID face barriers to eating that impact their health and function. On a multidisciplinary team, OTPs can treat diverse client populations by identifying and addressing barriers to daily participation, such as physical impairments, trauma history, and environmental barriers. More research is needed to evaluate the efficacy of OT practices in ARFID treatment.
No fitness effects of same‐sex copulations in male red flour beetles
Authors: Martens Birte M. , Martin Oliver Y. , Janicke Tim , Winkler Lennart
Published: March 2024

Same‐sex sexual behavior occurs in diverse animal taxa, yet its evolutionary maintenance is poorly understood as such behavior seems to be costly and does not directly increase reproductive success. We used male Tribolium castaneum beetles, which frequently engage in same‐sex copulations, to test if same‐sex sexual behavior influences future male mating behavior and reproductive success of males. Furthermore, we tested whether same‐sex sexual behavior has benefits via indirect sperm translocation. We conducted a series of mating trials demonstrating that males exposed to same‐sex behavior did not sire less offspring compared to control males that did not engage in same‐sex behavior. This suggests that same‐sex copulations did not lead to fitness costs in subsequent mating interactions. In addition, we found no evidence that indirect sperm translocation via an intermediate male occurs in T. castaneum. Taken together, these results imply that same‐sex sexual behavior in males is associated with no costs in terms of lower mating rate and reduced siring success and does not seem to entail benefits. Moreover, our data conform to the hypothesis that sexual indiscrimination is prevalent in this species, which may explain the relatively high frequency of same‐sex sexual behavior in T. castaneum.
Agave distribution and floral display influence foraging rates of an endangered pollinating bat and implications for conservation
Authors: Lear Kristen M. , Moore Clinton T. , King Elizabeth G. , Gómez‐Ruiz Emma , Flores Maldonado Jose Juan , Ibarra Sanchez Cuauhtemoc , Castañeda Aguilera Ana , Prebyl Thomas J. , Hepinstall‐Cymerman Jeffrey
Published: March 2024

Wildlife conservation involves making management decisions with incomplete knowledge of ecological relationships. Efforts to augment foraging resources for the endangered Mexican long‐nosed bat (Leptonycteris nivalis) are progressing despite limited knowledge about the species' foraging behavior and requirements. This study aimed to understand L. nivalis responses to floral resource availability, focusing on individual agave‐ and local‐scale characteristics influencing visitation rates to flowering agaves. We observed bat visitation at 62 flowering agaves around two roosts in northeast Mexico on 46 nights in the summers of 2017 and 2018. We found visitation rate had positive relationships with two agave‐scale characteristics: the number of umbels with open flowers and the lower vertical position on the stalk of those umbels (i.e., earlier phenological stages of flowering). However, these factors exhibited strong negative interaction: with few umbels with open flowers, the position of flowering umbels had little effect on visitation rate, but when umbels with open flowers were abundant, visitation rate was more strongly related to the lower flowering umbel position. We also found relationships between visitation rate and two local‐scale characteristics: negative for the density of flowering conspecifics within 30 m of the focal agave and positive for the density of dead standing agave stalks within 30 m. Our findings suggest opportunities to augment foraging resources for L. nivalis in ways that are consistent with their foraging behavior, including: increasing the supply of simultaneously blooming flowers by planting agave species that tend to have more umbels with simultaneously open flowers; planting multiple species of agaves with different flowering times to increase the availability of agaves with open flowers on lower‐positioned umbels throughout the period when bats are present in the region; planting agaves in clusters; and keeping dead standing agave stalks on the landscape. Our study points to useful management strategies that can be implemented and monitored as part of an adaptive management approach to aid in conservation efforts.
Oomycete communities are influenced by land use and disease status in Christmas tree production in Southern Québec, Canada
Authors: Van der Heyden Hervé , Duceppe Marc‐Olivier , Charron Guillaume , Tanguay Philippe , Bilodeau Guillaume J.
Published: March 2024

Forests are threatened by many natural stressors intensified by climate change and anthropogenic activities, which tend to increase their susceptibility to pests and pathogens. Consequently, oomycete‐related forest decline or dieback cases are increasing in natural, urban, and agricultural landscapes. It is in this context that Christmas tree growers from Southern Québec, Canada, are experiencing root rot problems, with reported incidences up to 25%. In a previous study, seven Phytophthora spp. were associated with this root rot problem, but the overall diversity of oomycetes has not yet been investigated. Hence, in this study, we use a metabarcoding approach to provide an overview of the diversity, richness, and composition of the oomycete community in fir plantations compared to surrounding natural forests. We showed that the P. cryptogea cluster, P. europaea cluster, P. sansomeana, and P. chlamydospora cluster were significantly more abundant in soils collected from plantations under diseased trees and confirmed that the P. europaea cluster (including P. abietivora) was most frequently associated with trees showing Phytophthora root rot‐like symptoms. Finally, we report that land use (anthropogenic activities) shapes oomycete diversity, while plantations can act as a gateway for invading natural forests. In fact, the results presented here suggested that the P. europaea cluster might already have crossed this boundary and that other species might follow, advocating the importance of improved surveillance of oomycete diversity in various environments.
High‐Performance Anion Exchange Membrane Fuel Cells Enabled by Nitrogen Configuration Optimization in Graphene‐Coated Nickel for Enhanced Hydrogen Oxidation
Authors: Li Pan , Zhong Jiang , Fu Yanqing , Du Zhentao , Jiang Lan , Han Yi , Luxa Jan , Wu Bing , Sofer Zdenek , Wei Qiliang , Yang Weiyou
Published: March 2024

Anion exchange membrane fuel cell (AEMFC) technology is attracting intensive attention, due to its great potential by using non‐precious‐metal catalysts (NPMCs) in the cathode and cheap bipolar plate materials in alkaline media. However, in such case, the kinetics of hydrogen oxidation reaction (HOR) in the anode is two orders of magnitude sluggish than that of acidic electrolytes, which is recognized as the grand challenge in this field. Herein, we report the rationally designed Ni nanoparticles encapsulated by N‐doped graphene layers (Ni@NG) using a facile pyrolysis strategy. Based on the density functional theory calculations and electrochemical performance analysis, it is witnessed that the rich Pyridinic‐N within the graphene shell optimizes the binding energy of the intermediates, thus enabling the fundamentally enhanced activity for HOR with robust stability. As a proof of concept, the resultant Ni@NG sample as the anode with a low loading (1.8 mg cm−2) in AEMFCs delivers a high peak power density of 500 mW cm−2, outperforming all of those of NPMC‐based analogs ever reported.
Sodium–glucose cotransporter 2 inhibitors for transthyretin amyloid cardiomyopathy: Analyses of short‐term efficacy and safety
Authors: Lang Frederick M. , Teruya Sergio , Weinsaft Ariel , Cuomo Margaret , Santos Alfonsina Mirabal , Nalbandian Ani , Bampatsias Dimitrios , Maurer Mathew S.
Published: March 2024

Aims

Despite their potential, sodium–glucose cotransporter 2 inhibitors (SGLT2i) have not been well‐studied in transthyretin amyloid cardiomyopathy (ATTR‐CM) as randomized trials have excluded patients with this morbid disease. We performed a retrospective study assessing the short‐term efficacy and safety of SGLT2i in ATTR‐CM.

Methods and results

We screened consecutive patients seen at a tertiary care centre and identified 87 ATTR‐CM patients treated with SGLT2i and 95 untreated control patients. Endpoints included changes in weight, loop diuretic dose, and cardiac/renal biomarkers. The median age of the overall population was 79 (interquartile range [IQR] 11) years. Nearly 90% of patients were male, and 93% were on a transthyretin stabilizer. Control patients demonstrated generally less severe disease at baseline compared to SGLT2i‐treated patients, with lower median Columbia risk score (p < 0.001). Median follow‐up time was 5.6 (IQR 5.2) and 8.4 (IQR 2.1) months in the SGLT2i and control cohorts, respectively. Compared with controls, SGLT2i treatment was associated with significantly greater reductions from baseline in weight, loop diuretic dose, and uric acid during follow‐up (p < 0.001). While no significant between‐group differences were observed on cardiac biomarkers, estimated glomerular filtration rate was significantly reduced versus controls 1 month after SGLT2i initiation (p = 0.002), but no significant differences were observed at later timepoints. Results were similar in a propensity score‐matched analysis (n = 42 per cohort). A total of 10 (11.5%) patients discontinued SGLT2i, most commonly due to genitourinary symptoms.

Conclusion

Sodium–glucose cotransporter 2 inhibitors were well tolerated by most patients with ATTR‐CM and appeared to improve volume status and combat diuretic resistance. Randomized studies are needed to confirm these findings.
Organocatalyzed Asymmetric Michael Addition of 4‐Monosubstituted‐pyrazol‐5‐ones to Enones: Construction of Vicinal Quaternary and Tertiary Stereocenters
Authors: Goyal Pooja , Dubey Akhil K. , Chowdhury Raghunath
Published: March 2024

Pyrazolone moiety bearing an all‐carbon quaternary stereogenic center is frequent in biologically active products and pharmaceuticals. The catalytic route for the construction of quaternary carbon centers poses a formidable challenge . In this report, catalytic asymmetric Michael addition of 4‐monosubstituted‐pyrazol‐5‐ones to simple enones catalyzed by primary amine‐Brønsted acid composite has been developed. An array of pyrazolone derivatives bearing vicinal all carbon quaternary and tertiary stereocenters, were obtained in moderate to good diastereoselectivities (up to 92 : 8 dr) and good to excellent enantiomeric excess (up to 99 % ee). In addition, antipode for enantiomers of the pyrazolone derivatives were also realized in good to high stereoselectivities (up to 92 : 8 dr and up to 98 % ee).
Molybdenum‐Catalyzed One‐Pot Multi‐Step Synthesis of N‐Polyheterocycles from Nitroarenes and Glycols
Authors: Gómez‐Gil Sara , Cases Nuria , Hernández‐Ruiz Raquel , Rubio‐Presa Rubén , Suárez‐Pantiga Samuel , Pedrosa María R. , Sanz Roberto
Published: March 2024

We report the efficient, sustainable one‐pot synthesis of a wide variety of N‐polyheterocycles, such as imidazo‐quinolines and quinoxalines, and furoquinolines, from easily available nitroaromatics and glycols via a molybdenum catalytic domino reduction‐imine formation‐intramolecular cyclization‐oxidation sequence. It is worth highlighting that the recycling and incorporation of the waste carbonyl byproduct, generated in the reduction step, into the final compound is realized. In addition, the overall efficiency and atom economy of the process are further improved owing to the participation of one reaction intermediate as reductant that allows lowering the amount of external reducing agent employed.
Investigations on Superbase Mediated Reactivity of N‐Tosylhydrazones with Aza‐ortho‐Quinone Methide Precursors
Authors: P. Rahul , T. K. Arunkumar , Sebastian Seena , Raveendran Haritha , Varughese Sunil , Mathew Jomon , John Jubi
Published: March 2024

We have encountered a superbase‐mediated chemoselective reaction of N‐tosylhydrazones with aza‐ortho‐quinone methide precursors. When tosylhydrazone was treated with ortho‐aminobenzyl alcohol in super basic conditions (KOH+DMSO), we observed the formation of 2‐substituted quinoline. The reaction was found to be general, and by this method, mono‐, di‐ and tri‐substituted quinolines could be made. We could prove experimentally and theoretically that the reaction proceeded via the formation of an azine from the basic decomposition of N‐tosylhydrazones. Finally, the reaction of tosylhydrazone with N‐(2‐(chloromethyl)phenyl)‐4‐methylbenzenesulfonamide (aza‐ortho‐quinone methide precursor) under super basic conditions afforded hydrazine substituted sulfonamides.
Effects of a Larger N‐Heterocyclic Ring in Rofecoxib Analogues on AIE Activity and Multifunctional Applications
Authors: Liu Wei , Yao Yinyin , Ke Yanbing , Zhou Jingming , Zhang Weiwei , Li Renfu , Lu Yusheng , Jiang Hong , Xie Lijun
Published: March 2024

Two analogues of rofecoxib, 2‐Pyr‐ROF and 2‐Pip‐ROF, were designed according to the strategy of heterocyclic ring enlargement and facilely synthesized in a facile manner by Knoevenagel reactions. The first compound, 2‐Pyr‐ROF, had low quantum yields (QY) of 3.0 % in the solid states. After replacing the pyrrolidinyl with piperidinyl, the resulting 2‐Pip‐ROF had a significantly increased QY, with a value of 28 %. The root‐mean‐square deviation (RMSD) values between S0 and S1 of 2‐Pyr‐ROF and 2‐Pip‐ROF in tetrahydrofuran were 0.51, 0.35 Å, respectively. As compared with 2‐Pyr‐ROF, compound 2‐Pip‐ROF exhibited a smaller RMSD, which indicated a lower non‐radiative transition rate. A single‐crystal X‐ray diffraction study and Hirshfeld surfaces analysis revealed that 2‐Pip‐ROF had a more nonplanar molecule structure and a weaker π‐π interaction, which might result in a higher fluorescence intensity and QY. Owing to its better aggregation‐induced emission (AIE) behavior, compound 2‐Pip‐ROF showed more multi‐functional applications, including mechanochromism, acidochromism, and lipid droplets imaging ability. These results imply that the strategy of heterocyclic ring enlargement provides a new paradigm for the design of new luminogens with AIE properties.
Dynamic Covalent Synthesis Applied to Optoelectronic and Energy Materials: Design, Applications and Limitations
Authors: Chatir Elarbi , David Arthur H. G. , Gapin Adèle , Goujon Antoine
Published: March 2024

Dynamic Covalent Chemistry, consisting in the use of dynamic covalent bonds (DCBs) to create complex objects by working at the thermodynamic equilibrium, has undeniable advantages for the preparation of conjugated systems with tailored optoelectronic properties for organic electronics. Chemists can combine simple building blocks with simple functional groups of appropriate geometry, structure and stoichiometry to build multidimensional conjugated architectures. Dynamic covalent reactions are often precious metal‐free, generate little to no side products and are very efficient. DCBs however afford sensitive materials, and consequently a balance needs to be found between the ease of synthesis, the stability and the performances. The dynamicity of the target materials hence can considerably reduce their applicability in organic electronics where strongly stable materials are needed, but opens the door to stimuli‐responsive behaviour and recyclability. A way to overcome dynamicity issues is to lock DCBs, but often at the cost of decreased conjugation. In this review, we will highlight how DCBs are employed to prepare functional optoelectronically active materials, such as discrete molecules, polymers or covalent organic frameworks, applied in fields ranging from organic light‐emitting diodes and solar cells to organic batteries and transistors. We will also discuss their limitations, benefits and the current challenges to overcome.
Visible‐Light Promoted Minisci–Type Cyanoalkylation of Azauracils via C−C Bond Cleavage
Authors: Xiang Chengli , Yu Sheng , Fei Haiyang , Pan Changduo , Yu Jin‐Tao
Published: March 2024

A photo‐induced Minisci–type cyanoalkylation of azauracils was developed under metal‐free and base‐free conditions. Readily available cyclobutanone oxime esters were used as the cyanoalkylating reagents via C−C bond cleavage to generate the γ‐cyanoalkyl azauracil derivatives in good to moderate yields. The introduced cyano group can be easily converted into many other functional groups, thus makes current protocol more practical.
A dual‐reference study design for understanding and improving AAV genome size analysis
Authors: Sun Yali , Lu Zhi‐xiang , Miller Michael , Valcour Ying , Khimani Anis H , Bauer Jana , Salomon Michael , Tong Yanhong
Published: March 2024

Recombinant adeno‐associated virus (rAAV) is the leading platform of gene delivery for its long‐lasting gene transformation and low immunogenicity. Characterization of the integrity and purity of the rAAV genome is critical to ensure clinical potency and safety. However, current rAAV genome characterization methods that can provide size assessment are either time‐consuming or not easily accessible to general labs. Additionally, there is a lack of right reference standard for analyzing long single‐stranded DNA (ssDNA) fragments. Here, we have developed an ssDNA assay on a microfluidic capillary electrophoresis platform using ssDNA reference standard. This assay provides size calling for ssDNA fragment, a detection sensitivity at ∼89 pg/µL (3 × 1010 GC/mL AAV) for 5.1 kb ssDNA fragment, and a turnaround time at ∼100 s per sample with a high throughput sample analyzing capability. Moreover, we have observed that the annealing of AAV ssDNA subsequent to its release from the capsid might introduce an additional double‐stranded DNA (dsDNA) peak. This phenomenon is dependent on the sample processing workflow. To avoid the risk of mischaracterization, we recommend the use of dual‐reference standards in combination with other orthogonal methods to have a comprehensive understanding of the rAAV genome size and integrity.
Damage mechanisms and recent research advances in Ni‐rich layered cathode materials for lithium‐ion batteries
Authors: Chen Kai , Cai Wenqin , Hu Zhihua , Huang Qingke , Wang Ao , Zeng Zeng , Song Jiahao , Sun Yan , Kong Qingquan , Feng Wei , Chen Ting , Wu Zhenguo , Song Yang , Guo Xiaodong
Published: March 2024

Nickel‐rich cathode is considered to be the cathode material that can solve the short‐range problem of electric vehicles with excellent electrochemical properties and low price. However, microcracks, lithium–nickel hybridization, and irreversible phase transitions during cycling limit their commercial applications. These issues should be resolved by modifications. In recent years, it has been favored by researchers to solve a large number of problems by combining multiple modification strategies. Therefore, this paper reviews recent developments in various modification techniques for nickel‐rich cathode materials that have improved their electrochemical characteristics. The summary of multiple modifications of nickel‐rich materials will play a guiding role in future development.
Experimental and Computational Study of the Thermal Insulation Properties of Hollow Glass Microspheres
Authors: Wang Yuyang , Chen Shuping , Liu Fulu , Dang Zhanwei
Published: March 2024

Hollow glass microspheres (HGM) are expected to be used in cryogenic liquid storage tanks as an insulating material with better insulation performance and lower maintenance cost instead of perlite. Obtaining the effective thermal conductivity of HGM can help to improve the insulation performance of cryogenic tanks. Herein, a test system based on the transient plane source method is designed and constructed, and the effective thermal conductivity of six models of HGMs from four suppliers at 200–300 K is measured. The results show that under atmosphere pressure of 200 K, the effective thermal conductivity of HGM is only 25.87–35.84 mW m−1 K−1. The effective thermal conductivity at room and low temperatures is calculated using the derived system of equations for integrated thermal conductivity and radiative heat transfer, with the error of no more than 13% from the current experimental results. The integrated thermal conductivity is still dominant in low pressure and low temperature, and the reduction of the true density contributes to the improvement of the HGM insulation performance.
Development of a Two‐Stage Hydrogen‐Based Thermochemical Energy Storage System
Authors: Chandra Mouli Badiganti , Choudhari Manoj S. , Sharma Vinod Kumar , Sanjay  , Paswan Manikant
Published: March 2024

Both energy conservation and the use of renewable resources are necessary due to the global increase in energy demand. A useful technique for energy storage, when renewable energy sources are available, is a thermochemical energy storage system that relies on the interaction of gases with solids. From this vantage point, hydrogen offers a sustainable and regenerative response to this pressing issue. In line with that, herein, the operation of a novel two‐stage hydrogen‐based thermochemical energy storage system (TS‐H‐TCES) is proposed to attain a higher energy density and is analyzed with the help of the thermodynamic cycle. The proposed system operates at 298, 373, 403, and 423 K as atmospheric temperature (Tatm), waste heat input temperature (Tm), storage temperature (Ts), and upgraded/enhanced heat output temperature (Th), respectively. For the given operating temperature, the thermodynamic performance of TS‐H‐TCES is evaluated using experimentally measured pressure–concentration isotherms of LaNi4.7Al0.3, LaNi4.6Al0.4, and MmNi4.6Al0.4. The maximum coefficient of performance, second law efficiency (ηII), and thermal energy storage density are found to be 0.67, 0.70, and 220.98 kJ kg−1, respectively. The impact of operating temperatures on system performance is also investigated, which is important in choosing the best temperature range for a certain application.
Deformable nanocarriers for enhanced drug delivery and cancer therapy
Authors: Cao Ziyang , Liu Jing , Yang Xianzhu
Published: March 2024

Recently, the field of nanomedicine has witnessed substantial advancements in the development of nanocarriers for targeted drug delivery, emerges as promising platforms to enhance therapeutic efficacy and minimize adverse effects associated with conventional chemotherapy. Notably, deformable nanocarriers have garnered considerable attention due to their unique capabilities of size changeable, tumor‐specific aggregation, stimuli‐triggered disintegration, and morphological transformations. These deformable nanocarriers present significant opportunities for revolutionizing drug delivery strategies, by responding to specific stimuli or environmental cues, enabling achieved various functions at the tumor site, including size‐shrinkage nanocarriers enhance drug penetration, aggregative nanocarriers enhance retention effect, disintegrating nanocarriers enable controlled drug release, and shape‐changing nanocarriers improve cellular uptake, allowing for personalized treatment approaches and combination therapies. This review provides an overview of recent developments and applications of deformable nanocarriers for enhancing tumor therapy, underscores the diverse design strategies employed to create deformable nanocarriers and elucidates their remarkable potential in targeted tumor therapy.