bluuebunny/crossref_metadata_2025 huggingface dataset:
Late‐Stage Formal Double C−H Oxidation of Prenylated Molecules to Alkylidene Oxetanes and Azetidines by Strain‐Enabled Cross‐Metathesis
Authors: Albitz Krisztián , Csókás Dániel , Dobi Zoltán , Pápai Imre , Soós Tibor
Published: January 2023

Prenylation is a ubiquitous late‐stage modification in nature that often confers significantly improved bioactivity for secondary metabolites. While this lipophilic modification renders enhanced potency, the lipophilic tag(s) can diminish bioavailability and adversely alter drug transportation and metabolism. Thus, a functional‐group‐tolerant, mild, and selective late‐stage C−H functionalization of prenyl tags would present a great potential in drug discovery programs but could also impact other fields, such as agrochemistry and chemical biology. Herein we report an exocyclic‐strain‐driven cross‐metathesis reaction of prenyl tags, a formal double C−H oxidation protocol, that can be used for the selective late‐stage derivatization of prenylated compounds and natural products. This methodology avoids the need for prefunctionalization of target molecules and affords ready access to an unprecedented library of oxo‐ and aza‐prenylated complex molecules. Thus, in a broader context, this methodology extends late‐stage functionalization beyond that available to nature.
Oral Anticancer Heterobimetallic PtIV−AuIComplexes Show High In Vivo Activity and Low Toxicity
Authors: Babu Tomer , Ghareeb Hiba , Basu Uttara , Schueffl Hemma , Theiner Sarah , Heffeter Petra , Koellensperger Gunda , Metanis Norman , Gandin Valentina , Ott Ingo , Schmidt Claudia , Gibson Dan
Published: January 2023

AuI‐carbene and PtIV−AuI‐carbene prodrugs display low to sub‐μM activity against several cancer cell lines and overcome cisplatin (cisPt) resistance. Linking a cisPt‐derived PtIV(phenylbutyrate) complex to a AuI‐phenylimidazolylidene complex2, yielded the most potent prodrug. While in vivo tests against Lewis Lung Carcinoma showed that the prodrug PtIV(phenylbutyrate)‐AuI‐carbene (7) and the 1 : 1 : 1 co‐administration of cisPt: phenylbutyrate:2efficiently inhibited tumor growth (≈95 %), much better than2(75 %) or cisPt (84 %),7exhibited only 5 % body weight loss compared to 14 % for2, 20 % for cisPt and >30 % for the co‐administration.7was much more efficient than2at inhibiting TrxR activity in the isolated enzyme, in cells and in the tumor, even though it was much less efficient than2at binding to selenocysteine peptides modeling the active site of TrxR. Organ distribution and laser‐ablation (LA)‐ICP‐TOFMS imaging suggest that7arrives intact at the tumor and is activated there.
Interfacial Engineering of Ni/V2O3 Heterostructure Catalyst for Boosting Hydrogen Oxidation Reaction in Alkaline Electrolytes
Authors: Duan Yu , Zhang Xiao‐Long , Gao Fei‐Yue , Kong Yuan , Duan Ying , Yang Xiao‐Tu , Yu Xing‐Xing , Wang Yan‐Ru , Qin Shuai , Chen Zhi , Wu Rui , Yang Peng‐Peng , Zheng Xu‐Sheng , Zhu Jun‐Fa , Gao Min‐Rui , Lu Tong‐Bu , Yu Zi‐You , Yu Shu‐Hong
Published: January 2023

Alkaline fuel cells can permit the adoption of platinum group metal‐free (PGM‐free) catalysts and cheap bipolar plates, thus further lowering the cost. With the exploration of PGM‐free hydrogen oxidation reaction (HOR) catalysts, nickel‐based compounds have been considered as the most promising HOR catalysts in alkali. Here we report an interfacial engineering through the formation of nickel‐vanadium oxide (Ni/V2O3) heterostructures to activate Ni for efficient HOR catalysis in alkali. The strong electron transfer from Ni to V2O3 could modulate the electronic structure of Ni sites. The optimal Ni/V2O3 catalyst exhibits a high intrinsic activity of 0.038 mA cm−2 and outstanding stability. Experimental and theoretical studies reveal that Ni/V2O3 interface as the active sites can enable to optimize the hydrogen and hydroxyl bindings, as well as protect metallic Ni from extensive oxidation, thus achieving the notable activity and durability.
Photo‐Induced Switching of CO2 Hydrogenation Pathway towards CH3OH Production over Pt@UiO‐66‐NH2(Co)
Authors: Chen Jianmin , Wang Yajing , Wang Fengliang , Li Yingwei
Published: January 2023

It is highly desired to achieve controllable product selectivity in CO2 hydrogenation. Herein, we report light‐induced switching of reaction pathways of CO2 hydrogenation towards CH3OH production over actomically dispersed Co decorated Pt@UiO‐66‐NH2. CO, being the main product in the reverse water gas shift (RWGS) pathway under thermocatalysis condition, is switched to CH3OH via the formate pathway with the assistance of light irradiation. Impressively, the space‐time yield of CH3OH in photo‐assisted thermocatalysis (1916.3 μmol gcat−1 h−1) is about 7.8 times higher than that without light at 240 °C and 1.5 MPa. Mechanism investigation indicates that upon light irradiation, excited UiO‐66‐NH2 can transfer electrons to Pt nanoparticles and Co sites, which can efficiently catalyze the critical elementary steps (i.e., CO2‐to‐*HCOO conversion), thus suppressing the RWGS pathway to achieve a high CH3OH selectivity.
A Multifluorination Strategy Toward Wide Bandgap Polymers for Highly Efficient Organic Solar Cells
Authors: Chen Jinming , Li Dongyan , Su Mingbin , Xiao Yonghong , Chen Hui , Lin Man , Qiao Xiaolan , Dang Li , Huang Xiao‐Chun , He Feng , Wu Qinghe
Published: January 2023

Creating new electron‐deficient unit is highly demanded to develop high‐performance polymer donors for non‐fullerene organic solar cells (OSCs). Herein, we reported a multifluorinated unit 4,5,6,7‐tetrafluoronaphtho[2,1‐b : 3,4‐b′]dithio‐phene (FNT) and its polymers PFNT‐F and PFNT‐Cl. The advantages of multifluorination: (1) it enables the polymers to exhibit low‐lying HOMO (≈−5.5 eV) and wide band gap (≈2.0 eV); (2) the short interactions (F⋅⋅⋅H, F⋅⋅⋅F) endow the polymers with properties of high film crystallinity and efficient hole transport; (3) well miscibility with NFAs that leads to a more well‐defined nanofibrous morphology and face‐on orientation in the blend films. Therefore, the PFNT‐F/Cl : N3 based OSCs exhibit impressive FF values of 0.80, and remarkable PCEs of 17.53 % and 18.10 %, which make them ranked the best donor materials in OSCs. This work offers new insights into the rational design of high‐performance polymers by multifluorination strategy.
Synthetic Receptors with Micromolar Affinity for Chloride in Water
Authors: Sudan Sylvain , Chen Damien W. , Berton Cesare , Fadaei‐Tirani Farzaneh , Severin Kay
Published: January 2023

A water‐soluble coordination cage was obtained by reaction of Pd(NO3)2 with a 1,3‐di(pyridin‐3‐yl)benzene ligand featuring a short PEG chain. The cavity of the metal‐organic cage contains one nitrate anion, which is readily replaced by chloride. The apparent association constant for chloride binding in buffered aqueous solution is Ka=1.8(±0.1)×105 M−1. This value is significantly higher than what has been reported for other macrocyclic chloride receptors. The heavier halides Br− and I− compete with binding or self‐assembly, but the receptor displays very good selectivity over common anions such as phosphate, acetate, carbonate, and sulfate. A further increase of the chloride binding affinity by a factor of 3 was achieved using a fluorinated dipyridyl ligand.
A Co(II)–organic framework and peroxidase mimetic Hemin@metal–organic framework and its application in the colorimetric analysis of glucose
Authors: Qi Weifeng , Li Zheng , Wang Xiong , Wang Honghao , Li Xia
Published: January 2023

A Co(II)‐organic framework (Co‐MOF), [Co3(3,5‐bimpy)2(5‐cpia)2(H2O)2], was constructed via the hydrothermal reaction of 3,5‐bis(1‐imidazoly)pyridine (3,5‐bimpy) and 5‐(2′‐carboxylphenoxy)isophthalic acid (5‐H3cpia). The Co‐MOF possessed a three‐dimensional (3D) porous architecture with the porosity of 22.4% per unit volume. The Co‐MOF@Hemin composite was further constructed via the encapsulation of Hemin into the Co‐MOF material. The constructed Co‐MOF@Hemin exhibited satisfactory peroxidase‐like activity through catalytic oxidation of the colorless peroxidase substrate 3,3,5,5‐tetramethylbenzidine (TMB) to a blue‐colored oxTMB in the presence of H2O2. Hence, the detection of H2O2 was achieved with a wide linear range from 0.005 to 0.5 mM (R2 = 0.992) and a low detection limit of 1.26 μM. More importantly, the peroxidase‐like Co‐MOF@Hemin was suitable for the sensitive and selective detection of glucose under the presence of glucose oxidase (GOx), which reduced O2 to H2O2. This analytical procedure for the detection of glucose had a linear range from 0.3 to 3 mM (R2 = 0.997), with a detection limit of 49 μM. The experimental results display the broad application prospects of the enzyme‐based MOFs in green and selective targets analyses.
May PdCu@f‐MWCNT NPs be an ecotoxicologic risk?
Authors: Alak Gonca , Yeltekin Aslı Çilingir , Köktürk Mine , Nas Mehmet Salih , Parlak Veysel , Calimli Mehmet Harbi , Ucar Arzu , Atamanalp Muhammed
Published: January 2023

The mechanisms of various metal nanoparticles (NPs) are still a matter of debate in aquatic toxicology. In order to close this gap, the number of studies on this subject is increasing. The aims of this study are to explore the interactions of PdCu@f‐MWCNT NPs with zebrafish and get to know if it has an ecotoxicological risk. In this study, we synthesized, characterized PdCu@f‐MWCNT NPs, and investigated its ecotoxicological effects. The chemical and morphological structures of PdCu@f‐MWCNT nanomaterials were elucidated with advanced analysis techniques such as scanning electron microscope (SEM), X‐ray spectrophotometer (EDX), transmission electron microscope (TEM), and X‐ray diffraction (XRD) analyses. The ecotoxicological risks were investigated by conducting biochemical analyses and malformation defects in zebrafish. The results were obtained using multiple marker applications including oxidative stress parameters, proinflammatory cytokine expressions, DNA damage, and apoptosis markers. The obtained findings showed embryonic development, survival rate, and incidence of malformation increasing in parallel with the dose increase in zebrafish exposed to PdCu@f‐MWCNT NPs at 10–1000 μg/L levels. Despite the observed decreases in antioxidant enzyme activities, GSH level, AChE activity, and NRF‐2 level, inductions in malondialdehyde (MDA) level, IL‐6, TNF‐α, NF‐kB, DNA damage, and apoptosis levels were observed with increasing dose. Considering these findings, it has been determined that there are toxic effects in zebrafish at all levels above the concentration that we examine as a safe dose (10 μg/L). The effects of all studied concentrations of this NP above the safe dosage, especially on oxidative stress, malformation, and immune system, were found to be quite significant. The more widespread use of nanotechnology in the future will mean more contact of aquatic organisms with NPs. As a result, it is clearly seen that these organisms, which form the important link of the food chain, and the aquatic environment are living at risk conditions.
A novel and efficient CaCO3 scale inhibitor in high‐temperature and high‐salinity geothermal systems: A deprotonated quadripolymer
Authors: Qiao Shixuan , Chen Youyuan , Li Jiaxing , Li Yangpei , Peng Tao , Liang Jun , Zheng Tianyuan , Fu Kaiming , Chang Qinpeng
Published: January 2023

Scale inhibitors are effective in preventing CaCO3 scaling in geothermal systems, but the scale inhibition performance and price of commercial scale inhibitors in high‐temperature and high‐salinity water are still not ideal. In this work, a novel modified carboxymethylated β‐cyclodextrin tetrameric (CAAS) scale inhibitor was synthesized using carboxymethylated β‐cyclodextrin, acrylic acid, 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS), and p‐styrenesulfonate (SSS) by free radical polymerization, and deprotonated CAAS (D‐CAAS) was prepared based on CAAS. The results of the static test showed that the CaCO3 scale inhibition efficiency of D‐CAAS reached 90.8% at 100°C and 800 mg/L Ca2+. Compared with that of previous commercial scale inhibitors, the scale inhibition efficiency of D‐CAAS was increased by 13.5%, and the price can be decreased by 26.1%. The results of SEM, XRD and molecular dynamics (MD) simulation showed that at 100°C–120°C, the deprotonation of D‐CAAS enhanced the weak interaction between D‐CAAS and CaCO3, inducing the transformation between calcite and vaterite and forming a loose scale. Deprotonation weakens the hydrogen bond between D‐CAAS and water to reduce the energy required for the binding of D‐CAAS to the surface of CaCO3. This study is expected to provide a low‐cost and high‐efficiency CaCO3 scale inhibitor for geothermal applications.
Rational design of the S,N‐heteroacene‐based nonfullerene by introducing the fluorine atom for efficient high‐performance organic solar cells
Authors: Oh Sora , Amjad Mufarah , Ahn Taek , Lee Sang Kyu
Published: January 2023

Fluorination has been established as an effective structural modification strategy to influence properties and has attracted attention in organic solar cells. Here, we design and synthesize three fused‐ring electron acceptors based on ladder‐type pentacyclic heteroacenes as the electron‐rich unit and 1,1‐dicyanomethylene‐3‐indanones with 0–2 fluorine substituents as the electron‐deficient units. Among these three molecules, two fluorine substituents nonfullerene acceptor, DTP‐2F exhibit strong absorption with high extinction coefficients and deep HOMO and LUMO level as compared with DTP‐0F and DTP‐1F. Device studies show that fluorinated nonfullerene acceptors (NFAs) lead to reduced VOC but increased JSC and FF, and therefore, the ultimate influence to efficiency depends on the compensation of VOC loss and gains of JSC and FF. Furthermore, fluorination affect to film morphology and miscibility between donor and acceptor. The fluorination of NFAs is one of the best design method of the donor and acceptor materials for efficient high‐performance organic solar cell.
Brain abscess due to Nocardia asiatica in a 63‐year‐old patient with adult‐onset still disease: A case report
Authors: Salazar Reinoso Fernando Raul , Romero‐Santana Gioconda Stefania , Mawyin Juez Andrea Emilia , Calderon Navas Jorge Andrés , Ronquillo Piloso Andrés Santiago
Published: January 2023

Cerebral nocardiosis is a rare and opportunistic cerebral infection caused by Nocardia spp., a gram‐positive, aerobic bacteria of the Actinomycetes order. Patients with cell‐mediated immunodeficiencies are often targeted by this microorganism, for which early diagnosis and therapeutic approach are essential.
Ni3S2@MoS2@Ni3Si2 Seaweed‐like Hybrid Structures In‐situ Grown on Ni Foam as Efficient Bifunctional Electrocatalysts
Authors: Xu Xuequan , Zhao Xuewen , Zhao Rongzheng , Gu Mengyue , Cheng Yonghong , Zhang Jinying
Published: January 2023

Water electrolysis is a promising method for sustainable hydrogen production. The exploration of noble metal free bifunctional electrocatalysts with both good hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalytic activity is crucial for efficient overall water splitting. The design of electrocatalysts to enhance electrocatalytic performance for both HER and OER is still a big challenge. Long Ni3Si2 nanowires have been in‐situ grown on Ni foam by low pressure chemical vapor deposition. A facile hydrothermal method was then adopted to grow Ni3S2@MoS2@Ni3Si2 seaweed‐like structures with high active sites on the Ni3Si2 blades and high charge transport along central stipes. The as‐produced Ni3S2@MoS2@Ni3Si2 seaweed‐like hybrid structures have been demonstrated to have both excellent HER and OER catalytic performance as integrated electrodes. Low overpotentials of 84 mV (η10)/283 mV (η50) and Tafel slopes of 36.0/53.7 mV dec−1 have been achieved for HER/OER, respectively. Excellent long‐term stabilities have been obtained for both HER and OER.
Ultralong nitrogen/sulfur Co‐doped carbon nano‐hollow‐sphere chains with encapsulated cobalt nanoparticles for highly efficient oxygen electrocatalysis
Authors: Zhang Wei , Guo Xingmei , Li Cong , Xue Jiang‐Yan , Xu Wan‐Ying , Niu Zheng , Gu Hongwei , Redshaw Carl , Lang Jian‐Ping
Published: January 2023

The development of simple and effective strategies to prepare electrocatalysts, which possess unique and stable structures comprised of metal/nonmetallic atoms for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), is currently an urgent issue. Herein, an efficient bifunctional electrocatalyst featured by ultralong N, S‐doped carbon nano‐hollow‐sphere chains about 1300 nm with encapsulated Co nanoparticles (Co‐CNHSCs) is developed. The multifunctional catalytic properties of Co together with the heteroatom‐induced charge redistribution (i.e., modulating the electronic structure of the active site) result in superior catalytic activities toward OER and ORR in alkaline media. The optimized catalyst Co‐CNHSC‐3 displays an outstanding electrocatalytic ability for ORR and OER, a high specific capacity of 1023.6 mAh gZn−1, and excellent reversibility after 80 h at 10 mA cm−2 in a Zn‐air battery system. This work presents a new strategy for the design and synthesis of efficient multifunctional carbon‐based catalysts for energy storage and conversion devices.
[ReH3(PPh3)4] – A Key Compound in the Rhenium Hydride Chemistry
Authors: Roca Jungfer Maximilian , Abram Ulrich
Published: January 2023

The chemistry of the rhenium trihydrido complex [ReH3(PPh3)4] (1) has been reinvestigated. An improved synthesis and the solid‐state structure of the compound as well as several reactions are reported. The solid‐state structure of 1 is similar to that of [TcH3(PPh3)4] having a capped‐octahedral coordination sphere. The PPh3 ligands surround the Re atom in a trigonal‐pyramidal mode with a short apical Re−P bond (2.300(2) Å) and three longer basal bonds (2.429(2)–2.449(2) Å). Reactions of 1 with monodentate phosphines such as PMe3 or PBu3 give the mono‐substituted complexes [ReH3(PPh3)3(PMe3)] (2) and [ReH3(PPh3)3(PBu3)] (3) under retention of the apical PPh3 ligand and substitution of one of the basal PPh3 ligands. The stability of the phosphine trihydride complexes decreases in the order PPh3>PMe3>PBu3. Treatment of [ReH3(PPh3)4] with trityl hexafluorophosphate in CH3CN does not result in a hydride abstraction, but gives the tetrahydrido cation [ReH4(NCCH3)(PPh3)3]+ (4), while reactions with nitriles give unstable azavinylidene complexes of the composition [ReH2(PPh3)3(NC(H)R)] (5). They are formed by an insertion of the nitrile into a Re−H bond. The solid‐state structure of the methyl derivative [ReH2(PPh3)3(NC(H)CH3)] (5 a) was determined showing a linear Re−N−C unit with rhenium−nitrogen and nitrogen−carbon double bonds, while the N=CH−C bond is clearly bent with an angle of 124°. Two previously unknown polymorphs of [ReH5(PPh3)3] were isolated from reactions of 1 with HOC6H3(CH3)2 and thiourea after prolonged heating in toluene and characterized by IR spectroscopy and X‐ray diffraction.
Enzyme‐Assisted Extraction of Alginate from Beach Wrack Fucus vesiculosus
Authors: Malvis Romero Ana , Brozio Felix , Kammler Sinah , Burkhardt Christin , Baruth Leon , Kaltschmitt Martin , Antranikian Garabed , Liese Andreas
Published: January 2023

Beach wrack constitutes an unutilized, abundant renewable source of marine macro algae being rich in valuable biopolymers. This work investigates the revalorization of the brown algae Fucus vesiculosus collected from beach wrack as a source of alginate, the main polysaccharide in brown algae which constitutes a potential ingredient for the development of biopolymer films. Enzyme‐assisted extraction has been investigated for cell disruption with commercial cellulase blends and proteases. The effect of enzyme type, enzyme activity, and extraction time on alginate yields, molecular weight distribution, functional groups, and purity has been studied.
Ethnic disparities in the immune microenvironment of triple negative breast cancer and its role in therapeutic outcomes
Authors: Zajac Kelsee K. , Malla Saloni , Babu Ramapuram Jayachandra , Raman Dayanidhi , Tiwari Amit K.
Published: January 2023

In 2020, newly diagnosed breast cancer (BC) cases surpassed that of lung cancer among women, making it the most common female cancer globally. In spite of recent increases in incidence rates, mortality due to BC has declined since 1989. These declines have been attributed to advancements in treatment modalities as well as increased mammography surveillance. Despite these advances, African American (AA) women are 40% more likely to die from BC than Caucasian women. Multifactorial etiology has been implicated in the disparity of BC mortality rates among AA women. As an example, AA women have a disproportionate incidence of triple negative breast cancer (TNBC), which has a poor prognosis and marginal treatment options. Increasingly, the tumor microenvironment (TME) has gained relevance as it relates to primary tumor progression, metastasis and treatment possibilities. The treatment outcomes or pathological complete response (pCR) in TNBC among AA women are affected by differences in TME. The TME of AA women exhibit several variances in acellular and cellular components associated with pro‐tumorigenic effects. For example, increased levels of the adipocyte‐related hormone, resistin, the pro‐inflammatory cytokine, IL‐6, and the CC chemokine, CCL2, within the TME of AA women gives rise to an increased density of M2 macrophages, also known as tumor‐associated macrophages. Elevated levels of vascular endothelial growth factor in the TME of AA women increase the vascular density or vascularity, which facilitate aggressive tumor growth and metastasis. Furthermore, a pro‐tumorigenic TME is supported by increased levels of the CXC chemokine, CXCL12 that results in the recruitment of regulatory T lymphocytes (Tregs). Due to these and other differences in the TME of AA women, precision oncology can target specific aspects of the TME that may contribute to a poorer prognosis. In addition to the discrepancies in the TME, AA women face socio‐economic barriers that limit their ability to access state‐of‐the‐art, novel therapies against metastatic TNBC. In this review, we will provide a brief overview of the tumor immune microenvironment, immune‐based treatment options for TNBC and their potential to decrease health disparities due to ethnicity.
Physicochemical Analytical Studies on Yttrium‐Doped Triglycine Sulfate Single Crystals
Authors: Rafi Ahamed S. , Suppuraj P. , Balakrishnan C. , Kalpana S.
Published: January 2023

Single crystals of pure triglycine sulfate (TGS) and yttrium‐acetate (0.5 mol%)‐doped triglycine sulfate (YTGS) crystals are synthesized and the crystals are grown from aqueous solution by slow evaporation solution growth method. The grown crystals are subjected to single crystal and powder X‐ray diffraction studies to identify the morphology and structure. Both the grown crystals are packed in a monoclinic crystal system and the lattice parameters of YTGS crystal are a = 9.138 Å, b = 12.72 Å, and c = 5.728 Å, whereas the doped TGS are, a = 9.134 Å, b = 12.61 Å, and c = 5.723 Å. The lattice parameters are slightly distorted due to the incorporation of yttrium ion into the lattice sites of the TGS crystal. The thermal stability of the grown crystals is investigated by differential thermal analysis (DTA) and thermogravimetric studies. DTA curve shows a lower decomposition temperature for YTGS crystal than for pure TGS crystal. The functional groups of the grown crystals are identified by Fourier transform infrared spectral studies. The surface morphology of the crystals is examined by scanning electron microscopy. Dielectric studies are carried out to identify the phase transition temperature and to find the dielectric constant of the YTGS crystals.
Tailoring the Chemical Structure of Nitrogen‐Doped Carbon Dots for Nano‐Aminocatalysis in Aqueous Media
Authors: Gentile Giuseppe , Mamone Martina , Rosso Cristian , Amato Francesco , Lanfrit Chiara , Filippini Giacomo , Prato Maurizio
Published: January 2023

Amine‐rich carbon dots (NCDs) have become promising nano‐aminocatalytic platforms in organic synthesis. These nanomaterials can be effectively produced through straightforward bottom‐up approaches using inexpensive nitrogen‐containing molecular precursors as a starting material. However, to date, there is still a limited understanding of how the molecular features of these precursors affect the catalytic activity of the resulting nanoparticles. This study concerns the production of a new family of NCDs, which use l‐arginine and different alkyl diamines as starting materials. The surface amines of all these NCDs were comprehensively characterized, thus allowing us to provide a correlation between the structural features of the nanoparticles and their catalytic performance with a selected amino‐catalyzed organic transformation. Importantly, the most active nano‐aminocatalysts, namely, NCDs‐3, were then used as a basis for the formation of a wide variety of functionalized organic compounds in water under mild reaction conditions.
Optimization of the “in‐silico” mate‐pair method improves contiguity and accuracy of genome assembly
Authors: Zhou Tao , Lu Liang , Li Chenhong
Published: January 2023

A combination of short‐insert paired‐ended and mate‐pair libraries of large insert sizes is used as a standard method to generate genome assemblies with high contiguity. The third‐generation sequencing techniques also are used to improve the quality of assembled genomes. However, both mate‐pair libraries and the third‐generation libraries require high‐molecular‐weight DNA, making the use of these libraries inappropriate for samples with only degraded DNA. An in silico method that generates mate‐pair libraries using a reference genome was devised for the task of assembling target genomes. Although the contiguity and completeness of assembled genomes were significantly improved by this method, a high level of errors manifested in the assembly, further to which the methods for using reference genomes, was not optimized. Here, we tested different strategies for using reference genomes to generate in silico mate‐pairs. The results showed that using a closely related reference genome from the same genus was more effective than using divergent references. Conservation of in silico mate‐pairs by comparing two references and using those to guide genome assembly reduced the number of misassemblies (18.6%–46.1%) and increased the contiguity of assembled genomes (9.7%–70.7%), while maintaining gene completeness at a level that was either similar or marginally lower than that obtained via the current method. Finally, we developed a pipeline of the optimized in silico method and compared it with another reference‐guided assembler, RagTag. We found that RagTag produced longer scaffolds (17.8 Mbp vs 3.0 Mbp), but resulted in a much higher misassembly rate (85.68%) than our optimized in silico mate‐pair method. This optimized in silico pipeline developed in this study should facilitate further studies on genomics, population genetics, and conservation of endangered species.
Dynamic disequilibrium: Recent widespread increases in vegetation cover on subarctic floodplains of Interior Alaska
Authors: Frost Gerald V. , Roland Carl A. , Schmidt Joshua H.
Published: January 2023

Boreal forest and tundra ecosystems are undergoing rapid climatic and environmental changes with consequences for ecosystem structure, function, and services. Although riparian zones occupy a small footprint within subarctic landscapes, they have disproportionately high value as foci of hydrological processes, biogeochemical cycling, ecological disturbance, biodiversity, and wildlife activity. Recent observations of increased winter discharge, reduced peak flows, and increased connectivity between catchments, streams, and groundwater in subarctic riparian zones have prompted predictions of altered riverine disturbance regimes, increased channelization, and a decline in the extent of active floodplains. However, few observational data exist concerning the spatiotemporal dynamics of subarctic floodplain vegetation, which can serve as a bioindicator to corroborate such predictions. We analyzed the distribution and extent of riparian ecotypes across a network of streams in 12 Interior Alaska watersheds using high‐resolution image pairs from circa 1981–2010. All stream reaches encompassed pronounced elevational gradients and included elevational forest–tundra ecotones. We classified riparian ecotypes using an image‐based point‐intercept sampling approach, calculated the probability of ecotype transitions, and evaluated relationships between ecotype transitions and environmental covariates. Our results reveal widespread increases in the stature, density, and extent of riparian vegetation spanning gradients of elevation, floodplain morphology, and climate. Ecotype transitions occurred at >20% of sample points, and there was a strong imbalance toward forward successional transitions (16.5%) versus backward transitions (4.0%). That is, we observed a strong tendency toward increasing cover, stature, and density of vegetation communities across our extensive sampling domain across our approximately 30‐year sample period. This relatively rapid riparian “greening” signal tended to be most pronounced in our glaciated watersheds. Although the streams we studied displayed high local variability in ecotype transitions, our results support hypotheses of increasing channelization and reduced extent of unvegetated surfaces on subarctic floodplains. They also likely reflect a trend toward more rapid and extensive plant recruitment and growth due to processes associated with conspicuous warming in northern ecosystems, consistent with greening documented in other subarctic landscape segments along gradients of elevation and latitude.
Simple Access to 2‐Arylbenzo[b]tellurophenes
Authors: Paegle Edgars , Arsenyan Pavel
Published: January 2023

Arguably, the simplest way for the preparation of benzo[b]tellurophenes has been elaborated. Cyclization of o‐haloarylalkynes in the presence of Te‐NaOH‐DMSO triad occurs by simple mixing of starting materials and heating overnight without the need for dry and inert atmosphere and provides the corresponding benzo[b]tellurophenes in up to 90 % GC‐yield. Catalytic telluration of aryl iodide substrates extends the applicability of the developed cyclization cascade to substrates that are not suitable for the direct SNAr/5‐endo‐dig cyclization approach. Successful SEAr in the third position of benzo[b]tellurophene provides a synthetic intermediate for the preparation of Te analogues of selective estrogen receptor modulator (SERM) raloxifene.
Densified mixture design algorithm: A novel mix design concept and its application for green concretes incorporating industrial by‐products
Authors: Nguyen Tan‐Hung , Limongan Andrian H. , Nguyen May Huu , Hwang Chao‐Lung , Huynh Trong‐Phuoc
Published: January 2023

Despite the fact that densified mixture design algorithm (DMDA) has been identified as a promising tool for green concrete mix design, its use in real practice has still been minimal worldwide. Due to the lack of precise information on DMDA computation in earlier studies, this work proposes DMDA including fly ash and ground granulated blast‐furnace slag as a viable way to improve the long‐term performance of green concrete. To encourage the use of DMDA, this study offers a detailed description of the DMDA mix design, as well as a step‐by‐step standard operating procedure and an empirical example of the computation. Assessments of the long‐term performance of green mixtures (self‐consolidating concrete and high‐performance concrete) and ordinary Portland cement concrete (designed using the conventional method of American Concrete Institute, ACI) were made. Performances of the ACI (O6000 mixture) and DMDA concretes (S6000 and H6000 mixtures) were then compared in terms of compressive strength, elastic modulus, shrinkage, and creep strain. As a result, all of the concrete samples attained the target strength of above 41 MPa (6000 psi) after only 28 days. Moreover, compressive strength, elastic modulus, shrinkage, and creep strain increased significantly in all of the concretes over curing time. Importantly, the experimental results confirmed that both types of DMDA concrete exhibited higher compressive strength and better long‐term performance than the ACI concrete under elastic modulus, creep, and shrinkage aspects.
Analysis on temporal variation law of ozone pollution and meteorological driving factors in Pudong New Area of Shanghai
Authors: Guan Jie , Geng Zhixin , Yang Fan , Zhang Xiaojiao , Chen Shuai , Guo Yaoguang
Published: January 2023

In order to deeply understand the influence of meteorological drivers on ozone (O3) pollution during the high season and explore O3 pollution control options, we analyzed the temporal variation characteristics of O3 pollution based on the ambient air observation data of Pudong New Area, Shanghai from 2020 to 2021, studied the influence of meteorological drivers on O3 pollution, and explored seasonal emission reduction options based on the results of EKMA (Empirical Kinetics Modeling Approach) curves. The results show that the seasonal O3 concentration variation is spring > summer > autumn > winter; relative humidity, temperature and wind speed are the main meteorological drivers of O3 pollution; the cross‐regional transport of high O3 concentrations and precursors from the south and southwest has a strong influence on the local O3 concentration; Pudong New Area is in the “VOCs control zone” during the O3 pollution period in May. Therefore, it is important to control the production and emission of local VOCs and to strengthen the synergistic control of O3 and its precursors between regions for the control of spring O3 in Pudong New Area.
Potential application of domestic solar dryers for coriander leaves: Drying kinetics, thermal efficiency, and quality assessment
Authors: Kaur Sukhanjot , Singh Manpreet , Zalpouri Ruchika , Kaur Kulwinder
Published: January 2023

Coriander (Coriandrum sativum L.) is a highly perishable crop with a shelf‐life of a few days under refrigerated conditions. Solar drying is one of the economical, hygienic and eco‐friendly methods of food preservation. During this study, fresh coriander was pre‐treated in a solution of 0.1% magnesium chloride, 0.1% sodium bicarbonate and 2.0% KMS for 15 min before solar or open sun drying. There were two types of solar dryers used, namely: PAU advanced domestic solar dryer and PAU domestic solar dryer. Solar dryers were evaluated and compared with open sun drying for drying kinetics, thermal efficiency, and product quality. The quality parameters determined were total color difference, total flavonoid content, total chlorophyll content, and ascorbic acid content. For drying of coriander, ADSD achieved the maximum thermal efficiency (18.56%) and minimum solar energy input (12.56 MJ/kg) out of the various drying systems under consideration. Additionally, ADSD samples had the highest quality retention in terms of the highest total flavonoid content (1.23 mg/100 g), total chlorophyll content (24.14 mg/100 g) and ascorbic acid content (24.29 mg/100 g).
Analysis and prediction of plastic waste composite construction material properties using machine learning techniques
Authors: Jain Devansh , Bhadauria Sudhir Singh , Kushwah Suresh Singh
Published: January 2023

The use of plastic‐based composites as building materials may be one method of recycling plastic waste. Plastic pollution has emerged as a global issue since our planet is becoming increasingly engulfed in plastic waste. In order to preserve a long‐term sustainable ecosystem, alternative methods of recycling this plastic trash would be extremely beneficial. In this study, the six attributes, which are ingredients used to make plastic composite construction material, are used to predict five target variables or properties of plastic composite construction material, such as compressive strength, flexural strength, split tensile strength, density, and water absorption. Five machine learning techniques random forest, Decision Tree, Ridge, Lasso, and Linear regression have been used to get the best prediction model for the properties of plastic composite construction material. The correlation method has been used to analyze the relationships among the properties and ingredients of plastic composite construction material. Analytical results for K‐fold cross‐validation show that random forest and decision tree form the best predictive models, having greater prediction accuracy than the rest of the machine learning algorithms. This pioneering work provides a simple and convenient method for predicting various properties of plastic‐based composite construction material and finding the impact of each composition mix on various properties.
Developing smart city services using intent‐aware recommendation systems: A survey
Authors: Rafique Wajid , Hafid Abdelhakim Senhaji , Qadir Junaid
Published: January 2023

Smart cities could be defined as urban areas that use Information and Communication Technology (ICT) to solve city problems in efficient and sustainable ways. Intent‐aware Recommender Systems (IARS) within ICT play a crucial role in filtering useless information according to user demands and assist in decision‐making in various smart city platforms. In smart cities, the user traces on IoT, RFIDs, mobiles, and smart sensors capture actual user intent of performing an activity and enhance user satisfaction by proposing optimal services. This paper presents a detailed literature survey of the field of IARS and how it can be used for developing smart city services. First, we present the evolution of IARS with the development of computing technology. Then, we present case studies, synergies, advances, and a reference implementation architecture of IARS for smart cities. We discuss requirements for developing smart city services using IARS. Furthermore, we devise a comprehensive taxonomy of applications and techniques of IARS using different performance parameters. Finally, we elaborate on current issues, challenges, and future research directions in IARS; these directions we believe will pave the way for autonomous service provisioning in smart cities.
Life‐space mobility among home‐living older adults with care needs and clinical depression—A cross‐sectional analysis
Authors: Lech Sonia , Mümken Sandra , Kessler Eva‐Marie , Gellert Paul
Published: January 2023

Objectives

While life‐space mobility is key for wellbeing, social participation and access to health care, vulnerable older adults face physical and mental barriers that may restrict mobility. The present exploratory study examined associations between physical functional limitations, depressive symptoms, life‐space mobility and outpatient health care utilization.

Methods

Cross‐sectional data from 197 community‐dwelling older adults with care needs and clinical depression was collected. Life‐space assessment composite score (LS‐C), instrumental activities of daily living scale (iADL), Geriatric Depression Scale (GDS‐12) and outpatient health care utilization have been assessed. Multiple regression analyses were conducted.

Results

Mean LS‐C score was 31.8 (SD = 17.7, range: 0–92), indicating low mobility levels. Depressive symptoms (β = −0.21, p = 0.001) and iADL (β = 0.54, p < 0.001) were significantly related with life‐space mobility, over and above age and living alone. An interaction effect between depressive symptoms and iADL was not significant (β = −0.07, 0.17, p = 0.26). Moreover, life‐space mobility was positively associated with primary care (β = 0.19, p = 0.02) and mental health care utilization (β = 0.33, p < 0.001).

Conclusions

Life‐space mobility appears to be largely restricted in home‐living vulnerable older adults with clinically significant depression; and factors associated with these restrictions appear to be physical and mental. The interplay of depression, mobility and health care utilization and its potential for interventional approaches need further investigations. Present findings underline an urgent need for new health care services that allow mobility‐impaired older patients to receive mental health outpatient treatment in their own home.

Clinical trial registration

The trial was prospectively registered with the ISRCTN registry (Trial registration number: ISRCTN55646265, registered February 15, 2019).
Using insights from personality dynamics to move developmental metatheory forward: Integrating insights from relational developmental systems metatheory and whole trait theory
Authors: Dykhuis Elise M. , Warren Michael T. , Meindl Peter , Jayawickreme Eranda
Published: January 2023

Developmental science benefits from a rich tradition of conceptual frameworks, such as Relational Developmental Systems metatheory, that seek to understand the individual ⇔ context relations that promote thriving across the lifespan. However, there are substantive methodological challenges associated with capturing individual‐level and contextual variables, let alone the dynamics between them. These challenges have encouraged the perpetuation of simple models that focus on either individuals or their contexts alone, or as parallel processes with little attention to the dynamics of the relations. In this paper, we engage in cross‐disciplinary dialogue between developmental and personality science (adding to recent work being done by those in personality development) and highlight the benefits that developmental science can reap by adopting several recent advancements in dynamic personality theory and the methods used to test them. In addition, we discuss what personality science might gain from applying a developmental lens to their research questions. Such integration may also help personality scientists better understand how developmental theory can complement their methods for understanding the development of individual differences over time. Ultimately, the two fields can use their similar missions of understanding the development of individual differences in order to support one another in pursuing good science.
Exploration of immunotherapy in advanced pulmonary lymphoepithelioma‐like carcinoma
Authors: Pang Lan‐Lan , Liao Jun , Huang Yi‐Hua , Gan Jia‐Di , Zhuang Wei‐Tao , Lv Yi , Liang Wei‐Ting , Zhang Li , Fang Wen‐Feng
Published: January 2023

Pulmonary lymphoepithelioma‐like carcinoma (PLELC) is a rare and histologically distinctive subtype of nonsmall cell lung cancer (NSCLC). High expression of programmed death ligand 1 (PD‐L1) and scarcity of druggable driver mutations raise the potential of immunotherapy for advanced PELEC. However, evidence on the clinical impact of immune‐checkpoint inhibitors (ICIs) remained limited and unconvincing. The present study retrospectively enrolled advanced PLELC patients who received ICIs either as up‐front or salvage therapy in SYSUCC between March 15, 2017 and March 15, 2022. The comparative efficacy of chemoimmunotherapy vs chemotherapy in the first‐line setting and chemoimmunotherapy vs ICIs monotherapy in the ≥2 line setting was investigated. A total of 96 patients were finally enrolled; 49 PLELC patients received immunotherapy plus platinum‐based chemotherapy, while 45 patients received platinum‐based chemotherapy as first‐line treatment. Patients with chemoimmunotherapy significantly obtain more survival benefits than those receiving chemotherapy (median progression‐free survival [PFS]: 15.6 vs 8.6 months, P = .0015). Additionally, patients with chemoimmunotherapy obtained more PFS benefits than those with ICIs monotherapy in the ≥2 line of therapy (median PFS: 21.7 months vs 7.8 months, P = .094). A significant correlation was observed between prognostic nutritional index (PNI) and favorable treatment outcomes in patients receiving first‐line chemoimmunotherapy (median PFS: 17.8 months vs 7.6 months, P < .0001). Likewise, patients in the monocyte‐to‐lymphocyte ratio (MLR)‐high group had significantly shorter PFS than the MLR‐low group (median PFS: 11.2 months vs not reached, P = .0009). Our study elucidated the superior efficacy of ICIs therapy, especially chemoimmunotherapy in advanced PLELC, which may provide new insight into the role of immunotherapy in advanced PLELC.
A study of the role of multiple layer‐by‐layer assembled bionic extracellular matrix in promoting wound healing via activation of the Wnt signaling pathway
Authors: Wang Zehui , Cao Kun , Yan Di , Ge Yangjing , Li Ruiyuan , Liu Yanwen , Ma Ting , Sun Xiaojuan
Published: January 2023

Wound healing is a multicellular collaborative process in which the adhesion and proliferation of fibroblasts in the wound is the basis for ensuring rapid wound healing, and in this process, it can promote the regeneration and remodeling of tissue and extracellular matrix. Studies have shown that Arg‐Gly‐Asp adhesive peptide (RGD) and basic fibroblast growth factor (bFGF) can stimulate the adhesion and proliferation of fibroblasts by activating the Wnt/β‐catenin signaling pathway, respectively. This study adopts the principle of layer‐by‐layer self‐assembly, and the binding force formed by electrostatic attraction and Schiff base was used to combine bFGF and RGD with collagen membrane to form a biomimetic membrane that is non‐cytotoxic with strong biocompatibility that could promote soft tissue healing. The surface characteristics of MLCM and the sustained release concentration of bFGF in vitro were measured, and the effects of MLCM on cell viability, proliferation, migration, and wound healing by means of Wnt/catenin pathways were studied through cell experiments and animal experiments under the comparison of negative control groups and positive control groups. The results showed that MLCM could stimulate wound healing more actively and had a positive effect on cell activity, proliferation, and migration. During wound healing, MLCM activates the Wnt/β‐catenin signaling pathway and inhibition of Wnt/β‐catenin signaling pathway significantly reduces the positive effects of MLCM on wound healing.
Inhibition of autophagic flux by the curcumin analog EF‐24 and its antiproliferative effect on MCF‐7 cancer cells
Authors: Li Jun , Wang Song‐He , Liu Yang‐Ting , Zhang Qin , Zhou Guang‐Zhou
Published: January 2023

5‐Bis[(2‐fluorophenyl)methylene]‐4‐piperidinone (EF‐24) is a curcumin analog, which was identified for its physiochemical stability and diverse pharmacological functions. In the present study, EF‐24 was added to the breast cancer cell line MCF‐7 and its cellular effects were characterized. The results indicated that EF‐24 possessed antiproliferative and antimigratory activities on MCF‐7 cells as determined by MTT assay, wound healing, and transwell assay, respectively. In addition, the autophagosomal vesicles could be detected by acridine orange staining and electron microscope analysis in EF‐24‐treated cells. Conversion of LC3‐I to LC3‐II was also investigated following EF‐24 treatment of the cells. However, the expression analysis of p62 and LC3 revealed that EF‐24 could inhibit autophagic flux in MCF‐7 cells. Confocal microscopy suggested that EF‐24 could inhibit the degradation of autophagic vesicles by blocking the fusion of autophagosomes with lysosomes. EF‐24 could also induce apoptosis of MCF‐7 cells as determined by Hoechst 33342 staining, flow cytometry analysis, and western blot analysis. Moreover, treatment of the cells with the autophagy inhibitor 3‐MA enhanced the PARP1 cleavage of EF‐24‐treated MCF‐7 cells, which indicated the crosstalk between autophagy and apoptosis in breast cancer cells. Additional investigation of EF‐24 should be performed in future studies to assess its antiproliferation and antimigratory effects on MCF‐7 cells. However, the current results provide a solid foundation for the potential in vivo anticancer activity of this compound.