bluuebunny/crossref_metadata_2025_split huggingface dataset:
Programmable Assembly of Multivalent DNA‐Protein Superstructures for Tumor Imaging and Targeted Therapy
Authors: Xu Zhen , Shi Tianhui , Mo Fengye , Yu Wenqian , Shen Yu , Jiang Qunying , Wang Fuan , Liu Xiaoqing 
Published: September 2022

AbstractProgrammable DNA materials hold great potential in biochemical and biomedical researches, yet the complicated synthesis, and the low stability and targeting efficacy in complex biological milieu limit their clinical translations. Here we show a one‐pot assembly of DNA‐protein superstructures as drug vehicles with specifically high affinity and stability for targeted therapy. This is achieved by biomimetic assembly of programmable polymer DNA wire into densely packed DNA nanosphere with an alkaline protein, protamine. Multivalent DNA nanostructures encoded with different types and densities of aptamers exhibit high affinity to targeted cells through polyvalent interaction. Our results show high cancer cell selectivity, reduced side effect, excellent therapeutic efficacy, and sensitive tumor imaging in both subcutaneous and orthotopic non‐small‐cell lung cancer murine models. This biomimetic assembly approach provides practical DNA nanomaterials for further clinical trials and may advance oligonucleotide drug delivery.
Pt Atoms/Clusters on Ni‐phytate‐sensitized Carbon Nitride for Enhanced NIR‐light‐driven Overall Water Splitting beyond 800 nm
Authors: Huang Yuanyong , Li Di , Feng Shuo , Jia Yujing , Guo Shuhui , Wu Xiaojie , Chen Min , Shi Weidong 
Published: September 2022

AbstractNear‐infrared (NIR) light‐driven overall water splitting beyond 800 nm remains a high‐priority target yet great challenge. Here we report that efficient utilization of photogenerated electrons in a photosensitized system prepared by site‐selective photodeposition of platinum single atoms/clusters (Pt‐SACs) on Ni‐phytate (PA‐Ni)‐sensitized polymeric carbon nitride (PCN). The optimal catalyst presents simultaneous hydrogen (H2) and oxygen (O2) evolution with an H2evolution amount of 1.4 μmol at λ>800 nm for 24 hours, which its activity was approximately 140 times higher than that of a system without Pt‐SAC modification (PA‐Ni1.1@PCN). This work represents the first NIR‐light responsive photosensitized system for overall water splitting, and may open an avenue for precisely manipulating cocatalyst positions at the atomic level to improve NIR‐light‐driven overall water splitting via photosensitization.
Toxicity of Ocimum americanum L. extracts against Aedes aegypti larvae (Diptera: Culicidae) and their impact on insecticide resistance
Authors: Ramachandran Maduraiveeran , Deepika Nagabushanam , Jayakumar Manickkam 
Published: September 2022

AbstractMosquitoes are a key threat to millions of people worldwide. They spread the pathogens that cause deadly diseases among humans and animals. Synthetic pesticides are the best agents to control mosquitoes, but they cause several problems for the environment as well as public health. Continuous usage of commonly available insecticides develops multiple resistances among pests. In search of alternatives to synthetic pesticides, botanicals could be one of the best alternatives to control mosquitoes. The present study explores the insecticidal activity of Ocimum americanum against Aedes aegypti larvae and their effect on detoxification enzymes. Leaves of O. americanum were sequentially extracted using hexane, chloroform, and methanol. Among these, hexane extract showed 100% larvicidal activity at 1 g/L concentration for 24 h and the LC50 value was 0.3 g/L. The phytochemical screening of hexane extract was performed through gas chromatography‐mass spectrometry analysis, which showed 27 compounds. The major compounds are squalene (13.03%), camphor (9.77%), and 1‐Iodohexadecane (8.02%). The toxicity of active hexane extract was tested against third instar larvae of Chironomus costatus (nontarget organism). Results revealed less toxicity (12.2%) at 1 g/L concentration on the nontarget organism. The enzyme activity of acetylcholinesterase and β‐carboxylesterase was significantly inhibited by the hexane extract. The present study reveals the insecticidal potential of O. americanum with minimum effects on nontarget organisms. The O. americanum extract inhibited the activity of A. aegypti's major insecticide‐resistant enzymes. O. americanum could be one of the best alternatives to controlling mosquitoes.
Vanadium Redox Flow Battery Using Activated Carbon Catalyst Produced from Low‐Density Polyethylene
Authors: Lim Hyeonsoo , Shin Mingyu , Phae Chae‐Gun , Kwon Yongchai 
Published: September 2022

AbstractCarbonized and activated low‐density polyethylene (LDPE) is suggested as a carbon catalyst for vanadium redox flow battery (VRFB). This carbon catalyst has many surface oxygen functional groups and a large surface area, while such benefits are achieved through activation of carbonized LDPE. According to electrochemical analysis, this carbon catalyst doped graphite felt (GF) enhances the redox reactivity of vanadium ions. More specifically, peak current density and peak potential separation for redox reaction of vanadium ions are 96.0 and 22.1% more improved than those measured by bare GF, while charge transfer resistance for the redox reactions is also improved by use of the catalyst doped GF. When performance of VRFB using this catalyst doped GF is measured, energy efficiency is 39% more improved than that measured without the catalyst. Based on that, this is revealed that new LDPE‐based carbon catalyst is effective for performance improvement of VRFB.
A rapid and sensitive UPLC–MS/MS method for the determination of zanubrutinib in beagle plasma and its application in pharmacokinetics
Authors: Zhu Yong‐liang , Ding Hao‐zhe , Gou Kai‐feng , Sun Bo , Chen Ye , Zhang He‐wei 
Published: September 2022

AbstractA reliable and sensitive ultra‐performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) method was developed for the determination of zanubrutinib in the plasma of beagle dogs. The column used was an Acquity BEH C18 column (2.1 mm × 50 mm, 1.7 μm), maintained at 40°C with an injection volume of 2 μl. The gradient elution program was as follows: 0–1 min, 10–10% A; 1–1.1 min, 10–90% A; 1.1–2.1 min, 90–90% A; 2.1–2.2 min, 90–10% A; 2.2–3.0 min, 10–10% A. Mobile phase A was 0.1% formic acid, B was acetonitrile, and the total analysis time was 3 min. The mass spectrometry was performed in positive ion mode, and the scanning mode was multi‐reaction monitoring mode with electrospray ionization as the ion source; m/z 472.2 → 455.01 for zanubrutinib and m/z 441.03 → 137.99 for ibrutinib (internal standard). The plasma samples were processed by protein precipitation. The standard curve showed good linearity (r2 = 0.999 8) in the range of 1.0–1,000 ng/ml (zanubrutinib) with a low limit of quantification of 1 ng/ml. Also, the intra‐day and inter‐day precision (RSD) was <5.88% and the accuracy (RE) ranged from −1.56 to 1.08%; the recoveries of zanubrutinib in beagle plasma ranged from 90.12 to 93.53% (RSD 1.67–6.42%) and the ME values of zanubrutinib were 98.70–101.06% (RSD 5.37–8.49%, n = 6). All values meet US Food and Drug Administration requirements. A rapid, highly selective and sensitive method for the determination of zanubrutinib concentration in plasma by UPLC–MS/MS was successfully developed. This method is suitable for pharmacokinetic studies in beagle dogs by following oral administration of zanubrutinib.
Analysis of serum metabolism in premature infants before and after feeding using GC–MS and the relationship with necrotizing enterocolitis
Authors: Wang Fusheng , Wang Guanghuan , Li Weizhong , Xu Chenbin , Zeng Zailin , Zhou Yongcui 
Published: September 2022

AbstractPreterm birth and enteral feeding are two main factors leading to necrotizing enterocolitis (NEC). The metabolomics of preterm infants before and after feeding can provide a basis for the prediction of NEC. Using the method of cross‐sectional study, the mode was established with the serum samples of 19 premature infants at birth and after feeding as the control group. The serum was analyzed using GC–MS. Chemometric analysis includes principal component analysis, partial least squares‐discriminant analysis, and orthogonal partial least squares‐discriminant analysis. Spectral separation of serum metabolites occurred in premature infants before and after feeding. The levels of xylose, d‐talose, phosphoglycolic acid, maleimide, l‐gulonolactone, maleic acid, β‐hydroxypyruvate, itaconic acid, and pantothenic acid in the serum of premature infants after feeding were significant in both multidimensional and single‐dimensional modes (variable importance in projection >2, P < 0.01). There was a moderate correlation between total bilirubin and l‐gulonolactone and β‐hydroxypyruvate (0.8 > r > 0.5). Maleimide, maleic acid, and itaconic acid have diagnostic value (area under the curve >0.9). The results indicated that serum metabolism of preterm infants changes significantly after feeding. Some metabolites have potential value in predicting NEC.
Knowledge and innovation management in agribusiness: A study in the Dominican Republic
Authors: Ureña‐Espaillat Hayrold José , Briones‐Peñalver Antonio Juan , Bernal‐Conesa Juan Andrés , Córdoba‐Pachón José Rodrigo 
Published: September 2022

AbstractTo date and worldwide, most business activities in the agribusiness sectors have focused on increasing productive efficiency to the detriment of the environmental impact of these activities, despite close connection that exist between agribusinesses and natural resources. This paper argues that knowledge and innovation management (KIM) can play a key role in fostering and managing creativity in the agribusiness sector. To test this assumption, an empirical model linking KIM with employee creativity, responsible green innovation, and performance in the agribusiness sector of the Dominican Republic is proposed and tested with data from 110 agribusiness companies. We found that strengthening the relationships between the above constructs is needed, with a view to readjusting the meaning of firm performance in the light of emerging (post‐pandemic) circumstances for agribusinesses. The statistical analyses yield important implications and recommendations for practice, management, and policy making in these areas in this country and elsewhere.
Does children’s fear matter? Evaluating children’s positions in Finnish court decisions on stalking
Authors: Koulu Sanna , Nikupeteri Anna , Laitinen Merja , Lohiniva‐Kerkelä Mirva 
Published: September 2022

AbstractChildren are at particular risk when one parent is targeted by the other parent's stalking behaviors post‐separation. In this article, we explore how court decisions position children when assessing fear, distress, and unlawfulness in cases of parental stalking. The data comprised 127 court decisions on stalking that involved a relationship (dating, cohabitation, or marriage), separation/divorce, and one or more children. Using discourse analysis, we identified four categories in how children were positioned: (1) children relegated to the background, (2) children’s involvement recounted as part of the facts, (3) children’s involvement assessed as relevant because it affected the parent, and (4) children as agents or victims in their own right. The findings highlight a significant risk of losing sight of children when the focus is on parents, and our concern is that this may also contribute to children not receiving the support they need.
Superoxide Dismutase 1 Folding Stability as a Target for Molecular Tweezers in SOD1‐Related Amyotrophic Lateral Sclerosis
Authors: Samanta Nirnay , Ruiz‐Blanco Yasser B. , Fetahaj Zamira , Gnutt David , Lantz Carter , Loo Joseph A. , Sanchez‐Garcia Elsa , Ebbinghaus Simon 
Published: September 2022

AbstractProtein misfolding and aggregation are hallmarks of many severe neurodegenerative diseases including Alzheimer's, Parkinson's and Huntington's disease. As a supramolecular ligand that binds to lysine and arginine residues, the molecular tweezer CLR01 was found to modify the aggregation pathway of disease‐relevant proteins in vitro and in vivo with beneficial effects on toxicity. However, the molecular mechanisms of how tweezers exert these effects remain mainly unknown, hampering further drug development. Here, we investigate the modulation mechanism of unfolding and aggregation pathways of SOD1, which are involved in amyotrophic lateral sclerosis (ALS), by CLR01. Using a truncated version of the wildtype SOD1 protein, SOD1bar, we show that CLR01 acts on the first step of the aggregation pathway, the unfolding of the SOD1 monomer. CLR01 increases, by ∼10 °C, the melting temperatures of the A4V and G41D SOD1 mutants, which are commonly observed mutations in familial ALS. Molecular dynamics simulations and binding free energy calculations as well as native mass spectrometry and mutational studies allowed us to identify K61 and K92 as binding sites for the tweezers to mediate the stability increase. The data suggest that the modulation of SOD1 conformational stability is a promising target for future developments of supramolecular ligands against neurodegenerative diseases.
Exploiting the Innate Plasticity of the Programmed Cell Death‐1 (PD1) Receptor to Design Pembrolizumab H3 Loop Mimics**
Authors: Richaud Alexis D. , Zaghouani Mehdi , Zhao Guangkuan , Wangpaichitr Medhi , Savaraj Niramol , Roche Stéphane P. 
Published: September 2022

AbstractCheckpoint blockade of the immunoreceptor programmed cell death‐1 (PD1) with its ligand‐1 (PDL1) by monoclonal antibodies such as pembrolizumab provided compelling clinical results in various cancer types, yet the molecular mechanism by which this drug blocks the PD1/PDL1 interface remains unclear. To address this question, we examined the conformational motion of PD1 associated with the binding of pembrolizumab. Our results revealed that the innate plasticity of both C'D and FG loops is crucial to form a deep binding groove (371 Å3) across several distant epitopes of PD1. This analysis ultimately provided a rational‐design to create pembrolizumab H3 loop mimics [RDYRFDMGFD] into β‐hairpin scaffolds. As a result, a 20‐residue long β‐hairpin peptide 1 e was identified as a first‐in‐class potent PD1‐inhibitor (EC50 of 0.29 μM; Ki of 41 nM).
Pseudoxanthomatous salpingitis: An uncommon lesion of the fallopian tube
Authors: Limaiem Faten , Halouani Ahmed , Dimassi Kaouther 
Published: September 2022

AbstractPseudoxanthomatous salpingitis (PXS) is an uncommon condition characterized by the presence of pigment‐laden histiocytes within the lamina propria of the fallopian tube. Less than 30 cases of PXS have been reported in the literature. We herein report a case of PXS associated with an endometriotic cyst.
Imine Reductases: Multifunctional Biocatalysts with Varying Active Sites and Catalytic Mechanisms
Authors: Wu Kai , Huang Junhai , Shao Lei 
Published: September 2022

AbstractThe synthesis of chiral amines is significant in the pharmaceutical industry. Imine reductase (IRED), a promising biocatalyst that was previously known to only catalyze asymmetric imine reduction (IR), was revealed to achieve direct asymmetric reductive amination (RA) of ketones with excess amines, producing secondary and tertiary amines. Moreover, conjugate reduction (CR) and RA activity by a single IRED has been reported for the preparation of valuable amine diastereomers. IREDs catalyzing these different reactions share the same standard quaternary structure, but possess varying active sites, indicating correlations and differences between their catalytic mechanisms. In this review, we trace the catalytic mechanisms reported for IRED‐catalyzed IR, RA, and CR‐RA. Insights obtained from structural and protein engineering in understanding the IRED‐catalyzed asymmetric synthesis are also included. This review will help readers acquire comprehensive insights into the catalytic mechanism of IREDs and ultimately inspire the engineering of IREDs for industrial applications.
Effect of Steaming on Waste‐Derived Zeolite ZSM‐5 as Methanol‐To‐Hydrocarbons Catalyst
Authors: Nikolopoulos Nikolaos , van Veenhuizen Oscar , Weckhuysen Bert Marc 
Published: September 2022

AbstractThe valorization of low‐grade industrial residues into valuable materials has been a way to reduce the impact of the industry on planetary boundaries. Silicon‐rich wastes have been used for zeolite synthesis while the impurities originating from wastes have a vital role in the physicochemical properties and the catalytic performance of waste‐derived zeolites. Here, the effect of steaming and the impact of impurities on waste‐derived zeolites were investigated. Steamed waste‐derived zeolite ZSM‐5 maintained their structure while their Brønsted acidity was decreased significantly due to dealumination. Electron paramagnetic resonance revealed that steaming of the samples resulted in the re‐dispersion of Fe impurities phases. The waste‐derived zeolites exhibited a high amount of weak and intermediate acidity upon steaming. Interestingly, the waste‐derived sample with a higher amount of impurities had an increase in Lewis acidity upon steaming, while catalytic testing in the Methanol‐to‐Hydrocarbons reaction exhibited 10 % higher conversion and 4 % in propylene yield.
Unprecedented Combination of Polyketide Natural Product Fragments Identifies the New Hedgehog Signaling Pathway Inhibitor Grismonone
Authors: Grigalunas Michael , Patil Sohan , Krzyzanowski Adrian , Pahl Axel , Flegel Jana , Schölermann Beate , Xie Jianing , Sievers Sonja , Ziegler Slava , Waldmann Herbert 
Published: September 2022

AbstractPseudo‐natural products (pseudo‐NPs) are de novo combinations of natural product (NP) fragments that define novel bioactive chemotypes. For their discovery, new design principles are being sought. Previously, pseudo‐NPs were synthesized by the combination of fragments originating from biosynthetically unrelated NPs to guarantee structural novelty and novel bioactivity. We report the combination of fragments from biosynthetically related NPs in novel arrangements to yield a novel chemotype with activity not shared by the guiding fragments. We describe the synthesis of the polyketide pseudo‐NP grismonone and identify it as a structurally novel and potent inhibitor of Hedgehog signaling. The insight that the de novo combination of fragments derived from biosynthetically related NPs may also yield new biologically relevant compound classes with unexpected bioactivity may be considered a chemical extension or diversion of existing biosynthetic pathways and greatly expands the opportunities for exploration of biologically relevant chemical space by means of the pseudo‐NP principle.
Trianionic 1,3,2‐Dioxaborine‐Containing Polymethines: Bright Near‐Infrared Fluorophores
Authors: Polishchuk Vladyslav , Filatova Mariia , Rusanov Eduard , Shandura Mykola 
Published: September 2022

AbstractTrianionic polymethines of the A′‐π‐A‐π‐A‐π‐A′ type comprising dioxaborine rings (A) and different electron‐accepting end groups (A′) have been synthesized. The obtained dyes absorb and emit light in the near‐infrared region with remarkably high molar attenuation coefficients (ϵ up to 495 000 M−1 cm−1 in DMF) and fluorescence quantum yields (Φf up to 0.73 in DMF). Thus, the novel trianionic dyes stand among the brightest individual fluorophores known to date – with a magnitude of fluorescence brightness (ϵ⋅Φf) of 313 000 M−1 cm−1 in DMF. The synthesized dyes demonstrate a minor negative solvatochromism and small Stokes shifts. X‐ray data reveal the nearly planar geometry of the trianionic chromophore. All the obtained compounds are stable in the solid state and in a solution, although the relative stability is much higher in polar aprotic than in protic solvents.
Chemical Strategies for Dendritic Magneto‐plasmonic Nanostructures Applied to Surface‐Enhanced Raman Spectroscopy
Authors: Fernandes Tiago , Nogueira Helena I. S. , Amorim Carlos O. , Amaral João S. , Daniel‐da‐Silva Ana L. , Trindade Tito 
Published: September 2022

AbstractChemical analyses in the field using surface‐enhanced Raman scattering (SERS) protocols are expected to be part of several analytical procedures applied to water quality monitoring. To date, these endeavors have been supported by developments in SERS substrate nanofabrication, instrumentation portability, and the internet of things. Here, we report distinct chemical strategies for preparing magneto‐plasmonic (Fe3O4 : Au) colloids, which are relevant in the context of trace‐level detection of water contaminants due to their inherent multifunctionality. The main objective of this research is to investigate the role of poly(amidoamine) dendrimers (PAMAMs) in the preparation of SERS substrates integrating both functionalities into single nanostructures. Three chemical routes were investigated to design magneto‐plasmonic nanostructures that translate into different ways for assessing SERS detection by using distinct interfaces. Hence, a series of magneto‐plasmonic colloids have been characterized and then assessed for their SERS activity by using a model pesticide (thiram) dissolved in aqueous samples.
Highly Active La(III)‐Based Metal‐Organic Framework as a Heterogeneous Lewis Acid Catalyst for Friedel‐Crafts Alkylation
Authors: Wu Jia‐Qi , Wu Xin‐Yuan , Lu Jian‐Mei , Shi Qian , Shao Li‐Xiong 
Published: September 2022

AbstractIn this study, a novel La(III)‐based two‐dimensional (2D) metal‐organic framework, [La2/3(qptca)1/2] (referred to as SLX‐2), from LaCl3 and 1,1′ : 4′,1′′ : 4′′,1′′′ : 4′′′,1′′′′‐quinquephenyl]‐2,2′′,2′′′′,5′′‐tetracarboxylic acid (H4qptca) was synthesized by conventional solvothermal method and thoroughly characterized by using X‐ray single‐crystal diffraction, powder X‐ray diffraction, and thermogravimetric analyses. The 2D SLX‐2 features a unique lanthanum center exposed to the skeleton and was used as an efficient Lewis acid catalyst for the Friedel‐Crafts alkylation of indole and pyrrole with β‐nitrostyrene along with a wide substrate scope, giving the desired products in good‐to‐high yields under the optimal reaction conditions. Furthermore, the catalyst was used for twenty cycles, with nearly no effect on its activity, and the reaction was heterogeneous in nature. Moreover, compared to the previous hydrogen‐bond‐donating MOF catalysts for such alkylation reactions, SLX‐2 showed an excellent stability toward harsh acidic and basic environment, and gave comparable catalytic activities.
Synthesis of Cyclic and Acyclicortho‐Aryloxy Diaryliodonium Salts for Chemoselective Functionalizations
Authors: Linde Erika , Knippenberg Niels , Olofsson Berit 
Published: September 2022

AbstractTwo regioselective, high‐yielding one‐pot routes to oxygen‐bridged cyclic diaryliodonium salts andortho‐aryloxy‐substituted acyclic diaryliodonium salts are presented. Starting from easily availableortho‐iodo diaryl ethers, complete selectivity in formation of either the cyclic or acyclic product could be achieved by varying the reaction conditions. The complimentary reactivities of these novel ortho‐oxygenated iodonium salts were demonstrated through a series of chemoselective arylations under metal‐catalyzed and metal‐free conditions, to deliver a range of novel,ortho‐functionalized diaryl ether derivatives.