bluuebunny/crossref_metadata_2025_split huggingface dataset:
Investigations on the Synthesis, Reactivity, and Properties of Perfluoro‐α‐Benzo‐Fused BOPHY Fluorophores
Authors: Zhang Guanyu , Wang Maodie , Bobadova‐Parvanova Petia , Fronczek Frank R. , Smith Kevin M. , Vicente M. Graça H. 
Published: April 2022

AbstractThe synthesis and reactivity of 3,8‐dibromo‐dodecafluoro‐benzo‐fused BOPHY 2 are reported, via SNAr with O‐, N‐ S‐ and C‐nucleophiles, and in Pd(0)‐catalyzed cross‐coupling reactions (Suzuki and Stille). The resulting perfluoro‐BOPHY derivatives were investigated for their reactivity in the presence of various nucleophiles. BOPHY 3 displays reversible color change and fluorescence quenching in the presence of bases (Et3N, DBU), whereas BOPHY 7 reacts preferentially at the α‐pyrrolic positions, and BOPHY 8 undergoes regioselective fluorine substitution in the presence of thiols. The structural and electronic features of the fluorinated BOPHYs were studied by TD‐DFT computations. In addition, their spectroscopic and cellular properties were investigated; BOPHY 10 shows the most red‐shifted absorption/emission (λmax 659/699 nm) and 7 the highest fluorescence (Φf=0.95), while all compounds studied showed low cytotoxicity toward human HEp2 cells and were efficiently internalized.
Reversible and Stepwise Single‐Crystal‐to‐Single‐Crystal Transformation of a Platinum(II) Complex with Vapochromic Luminescence
Authors: Saito Daisuke , Galica Tomasz , Nishibori Eiji , Yoshida Masaki , Kobayashi Atsushi , Kato Masako 
Published: April 2022

AbstractThe vapochromic single‐crystal‐to‐single‐crystal (SCSC) transformation of a highly luminescent PtII complex bearing an N‐heterocyclic carbene [Pt(CN)2(tBu‐impy)] (tBu‐impyH+=1‐tert‐butyl‐3‐(2‐pyridyl)‐1H‐imidazolium) is reported. The trihydrate form of the complex, which exhibits blue 3MMLCT emission owing to weak Pt⋅⋅⋅Pt interactions, changed its luminescence color from blue to yellowish‐green upon the desorption of water molecules while keeping the high emission quantum yield of more than 0.45. Variable‐temperature and continuous in‐situ tracking of single‐crystal X‐ray diffraction measurements revealed that the SCSC transformation proceeds reversibly by the release and reabsorption of water molecules, thereby changing the stacked structure slightly. As a result, the dynamics of vapor‐induced SCSC transformation were elucidated: that the anhydrous form returned to the original trihydrate form in a two‐step process under a water vapor atmosphere. In addition, the PtII complex exhibited a similar SCSC response accompanied by a luminescence color change in the presence of methanol vapor, while being inactive toward ethanol vapor.
Consecutive Methylation Catalyzed by TsrM, an Atypical Class B Radical SAM Methylase
Authors: Wu Runze , Ding Wei , Zhang Qi 
Published: April 2022

Comprehensive SummaryTsrM is a cobalamin‐dependent radical S‐adenosylmethionine (SAM) methyltransferase belonging to the Class B radical SAM methylase (RSM) family. This enzyme catalyzes the C‐2 methylation of L‐tryptophan to produce 2‐methyltrytophan (2‐MeTrp), an intermediate involved in the biosynthesis of thiostrepton A. In this work, we report characterization of an unexpected activity of TsrM, which carries out an additional methylation reaction on the product 2‐MeTrp. A series of isotopic labeling studies and assays with different Trp analogs revealed that TsrM is able to transfer a methyl group from SAM to the C4 of 2‐MeTrp to produce 2,4‐dimethyltryptophan. These results reveal the intriguing substrate specificity of TsrM, further expanding the reaction promiscuity of the radical SAM superfamily enzymes.
Expedition Nobel prize chemistry 2021 – experimental insights into the topic of asymmetric organocatalysis
Authors: Reinmold Marco , Fahim Amin , Lühken Arnim 
Published: April 2022

AbstractDie mit dem Nobelpreis ausgezeichneten Forschungsthemen liefern eine wichtige Grundlage zur Konzeption von experimentellen Unterrichtseinheiten und sind nach dem Prinzip der Wissenschaftlichkeit und aufgrund ihrer Aktualität fundamental für die Gestaltung von Chemieunterricht. Auf Basis von Benjamin Lists Arbeiten wird im folgenden Beitrag im Sinne des exemplarischen Prinzips ein experimenteller und theoretischer Zugang zur asymmetrischen Organokatalyse für Schüler:innen vorgestellt. Aufgrund der geringen Gefährdungspotentiale der Edukte und Produkte sowie der Einfachheit der Durchführung kann der Versuch von den Schüler:innen durchgeführt und die Reaktionsmechanismen von ihnen durch die während der Schullaufbahn erworbenen fachlichen Kompetenzen erarbeitet und somit grundlegende Konzepte der asymmetrischen Organokatalyse verstanden werden. Zudem werden klassische Nachweisreaktionen funktioneller Gruppen organischer Moleküle und Analysen zur Charakterisierung der Produkte eingesetzt, welche vergleichend mit der basenkatalysierten Aldolreaktion einen Zugang zum Begriff der Enantioselektivität ermöglichen. Ebenso bietet der Vergleich der basenkatalysierten mit der L‐Prolin‐katalysierten Aldolreaktion Grundlage zur Diskussion ökologischer und ökonomischer Aspekte beider Reaktionsführungen und fördert somit die Kommunikations‐ und Bewertungskompetenz sowie Reflexion im naturwissenschaftlichen Kontext.
Structural Development of Silicon‐Containing Retinoids: Structure–Activity Relationship Study of the Hydrophobic Pharmacophore of Retinobenzoic Acids Using Silyl Functionalities
Authors: Oikawa Tsuyoshi , Fujii Shinya , Mori Shuichi , Masuno Hiroyuki , Kawachi Emiko , Kagechika Hiroyuki 
Published: April 2022

AbstractWe designed and synthesized a series of retinobenzoic acids bearing various silyl functionalities in order to explore in detail the structure‐activity relationship (SAR) at the hydrophobic moiety of retinoids. Among the synthesized compounds, 24 c bearing a t‐butyldimethylsilyl (TBS) group at the hydrophobic site exhibited potent retinoid activity comparable to that of the lead compound Am555S (4). Compound 24 c exhibited transcription‐promoting activity towards all three subtypes of retinoic acid receptor (RAR), but showed the highest activity towards RARγ, in contrast to the high RARα‐selectivity of Am80 (3) and Am555S (4). The SARs presented here should be helpful in the development of subtype‐selective retinoids, and in particular 24 c might be a promising lead compound for new RARγ ligands.
Pneumonitis after immune checkpoint inhibitor therapies in patients with acute myeloid leukemia: A retrospective cohort study
Authors: Sheshadri Ajay , Goizueta Alberto A. , Shannon Vickie R. , London David , Garcia‐Manero Guillermo , Kantarjian Hagop M. , Ravandi‐Kashani Farhad , Kadia Tapan M. , Konopleva Marina Y. , DiNardo Courtney D. , Pierce Sherry , Zarifa Abdulrazzak , Albittar Aya A. , Zhong Linda L. , Akhmedzhanov Fechukwu O. , Arain Muhammad H. , Alfayez Mansour , Alotaibi Ahmad , Altan Mehmet , Naing Aung , Mendoza Tito R. , Godoy Myrna C. B. , Shroff Girish , Kim Sang T. , Faiz Saadia A. , Kontoyiannis Dimitrios P. , Khawaja Fareed , Jennings Kristofer , Daver Naval G. 
Published: April 2022

BackgroundImmune checkpoint inhibitors (ICI), combined with hypomethylating agents, can be used to treat acute myeloid leukemia (AML), but this strategy results in a high rate of pneumonitis. The authors sought to determine risk factors for pneumonitis development and whether pneumonitis increased mortality.MethodsThe authors conducted a retrospective review of 258 AML patients who received ICI‐containing regimens from 2016 to 2018. A multidisciplinary adjudication committee diagnosed pneumonia and pneumonitis by reviewing symptoms, imaging, microbiology, and response to therapies. To measure risk factors for pneumonitis and mortality, multivariate Cox proportional hazards models were constructed. Pneumonia, pneumonitis, and disease progression were modeled as a time‐dependent variable and incorporated a standard risk set modifying variables into the models.ResultsThirty patients developed pneumonitis (12%). Of these, 17 had partial or complete resolution, whereas 13 patients died from pneumonitis. Increasing age (hazard ratio [HR], 1.04 per year; 95% confidence interval [CI], 1.00‐1.08), and baseline shortness of breath increased pneumonitis risk (HR, 2.51; 95% CI, 1.13‐5.55). Female sex (HR, 0.33; 95% CI, 0.15‐0.70) and increasing platelet count (HR, 0.52 per log‐unit increase; 95% CI, 0.30‐0.92) decreased pneumonitis risk. In adjusted models, ICI‐related pneumonitis significantly increased mortality (HR, 2.84; 95% CI, 1.84‐4.37).ConclusionsICI‐related pneumonitis occurs at a high rate in AML patients and increases mortality.Lay Summary

Immune checkpoint inhibitors (ICIs) remove inhibitory signals that reduce T‐cell function and allow T‐cells to better attack cancer cells.

In acute myeloid leukemia (AML), the effectiveness of ICIs is limited in part by inflammation of the lung, called pneumonitis.

This study reviewed 258 patients with AML who received ICIs and identified 30 patients who developed pneumonitis, nearly half of whom died.

Older age and baseline shortness of breath increased pneumonitis risk, whereas female sex and higher baseline platelet counts decreased pneumonitis risk.

Pneumonitis increased mortality by nearly 3‐fold.

This work highlights the significant harm imposed by pneumonitis after ICI therapies.
The promising combination therapy strategy for overcoming resistance to histone deacetylase inhibitors in diffuse large B‐cell lymphoma
Authors: Pei Haixiang , Chen Yihua 
Published: April 2022

AbstractSingle histone deacetylases inhibitors (HDACis) or current combination therapies show limited clinical efficiency in facing the striking heterogeneity of diffuse large B‐cell lymphoma (DLBCL). This commentary reviews the research conducted by Wang et al. to demonstrate the mechanism of the highly efficient HDACi LAQ824 and a promising HDCAi‐based combination therapy approach in DLBCL.
Polycomb‐mediated gene regulation in human brain development and neurodevelopmental disorders
Authors: Bölicke Nora , Albert Mareike 
Published: April 2022

AbstractThe neocortex is considered the seat of higher cognitive function in humans. It develops from a sheet of neural progenitor cells, most of which eventually give rise to neurons. This process of cell fate determination is controlled by precise temporal and spatial gene expression patterns that in turn are affected by epigenetic mechanisms including Polycomb group (PcG) regulation. PcG proteins assemble in multiprotein complexes and catalyze repressive posttranslational histone modifications. Their association with neurodevelopmental disease and various types of cancer of the central nervous system, as well as observations in mouse models, has implicated these epigenetic modifiers in controlling various stages of cortex development. The precise mechanisms conveying PcG‐associated transcriptional repression remain incompletely understood and are an active field of research. PcG activity appears to be highly context‐specific, raising the question of species‐specific differences in the regulation of neural stem and progenitor regulation. In this review, we will discuss our growing understanding of how PcG regulation affects human cortex development, based on studies in murine model systems, but focusing mostly on findings obtained from examining impaired PcG activity in the context of human neurodevelopmental disorders and cancer. Furthermore, we will highlight relevant experimental approaches for functional investigations of PcG regulation in human cortex development.
Increased risk of somatic diseases following anorexia nervosa in a controlled nationwide cohort study
Authors: Steinhausen Hans‐Christoph , Villumsen Martin Dalgaard , Hørder Kirsten , Winkler Laura Al‐Dakhiel , Bilenberg Niels , Støving René Klinkby 
Published: April 2022

AbstractObjectiveTo assess the risk of somatic diseases in connection with anorexia nervosa (AN).MethodThis matched cohort study was based on Danish registries of all patients born 1961–2008 with a first‐time diagnosis of AN in 1994–2018 at age 8–32 and matched controls without an eating disorder. For 13 somatic disease categories, time from inclusion date to time of first somatic diagnosis, accounting for censoring, was studied by use of time‐stratified Cox models.ResultsA total of 9985 AN patients born 1961–2008 and 49,351 controls were followed for a median (interquartile range) of 9.0 (4.4–15.7) years. During the first 2 years after entry there was a 60% higher hazard for any somatic disease among patients with AN than among controls, while the ratio from three to 11 years was reduced to 1.18. Regardless of age at diagnosis, the hazard among patients and controls were no different at approximately a decade after diagnosis of AN and the cumulative risk for patients for 12 of 13 disease categories was always higher or no less that for controls. For all disease categories, the hazard ratio (HR) was higher when close to entry. For most disease categories, age at diagnosis of AN did not modify the effect.DiscussionWhile around 90% of all individuals had any somatic disease at the end of follow‐up, the cumulative incidence over time was higher for patients with AN than for controls. Large HRs were seen in the early years after diagnosis during which patients require extensive medical interventions.Public SignificanceBased on Danish registries, a large sample of almost 10,000 patients with AN born 1961–2008 and almost 50,000 matched controls were followed for a median of 9 years. While around 90% of all individuals had any somatic disease at the end of follow‐up, the cumulative incidence over time was higher for patients with AN than for controls.
Pro‐Pro Dipeptide‐Thiourea Organocatalyst in the Mannich Reaction between α‐Imino Esters and Pyruvates
Authors: Čmelová Patrícia , Šramel Peter , Zahradníková Barbora , Modrocká Viktória , Szabados Henrich , Mečiarová Mária , Šebesta Radovan 
Published: April 2022

AbstractEnantioselective catalytic formation of polyfunctional molecules, such as non‐natural amino acids, is important for the efficient production of many chiral compounds. To this end, we present here the synthesis and evaluation of the catalytic activity of bifunctional peptide–thiourea organocatalysts. These hybrid organocatalysts consist of Pro‐Pro dipeptide and thiourea moiety connected via a 1,2‐diaminocyclohexane unit. These catalysts promoted challenging Mannich reaction between α‐imino esters and pyruvates, providing orthogonally protected oxo‐glutamate derivatives. The N‐tosyl‐protected imino ester, as the most active imine, was required to compensate for the poor reactivity of pyruvates. DFT calculations, NMR, and CD spectroscopy help elucidate the mode of action of these catalysts. Configuration of the dipeptide Pro‐Pro moiety is responsible for the sense of the stereoinduction of the Mannich reaction.
Rhodium‐Catalyzed C−H Activation/Annulation of N‐Aryl‐pyrazolidinones with Vinylene Carbonate
Authors: Huang Gao , Yu Jin‐Tao , Pan Changduo 
Published: April 2022

AbstractA rhodium‐catalyzed C−H activation/annulation of N‐aryl‐pyrazolidinones with vinylene carbonate was developed. The utilization of vinylene carbonate as the acetylene surrogate furnished the successful construction of non‐substituted 5,6‐pyrazolo[1,2‐a]cinnoline derivatives, which are difficult to synthesize through other procedures. In this work, a series of variously substituted pyrazolo[1,2‐a]cinnolines were obtained in yields up to 98 % with broad substrate scope and excellent selectivity. Moreover, external oxidants were not required in this protocol with H2O and CO2 as the clean by‐products.
Computational Design and Application of Molecularly Imprinted/MWCNT Based Electrochemical Sensor for the Determination of Silodosin
Authors: Abo Elalaa Amal Sherif , Abdel‐Hamied Abdel‐Tawab Muhammed , Abdel Ghani Nour. T. , El Nashar Rasha M. 
Published: April 2022

AbstractA novel molecularly imprinted polymer (MIP) based electrochemical sensor was developed for differential pulse voltammetric detection of silodosin (SLD), used for enlarged prostate (benign prostatic hyperplasia; BPH) treatment. A computational design was first applied for optimization of the molar ratio between silodosin (SLD, template): Methacrylic acid (MAA, functional monomer), based on which five polymeric ratios were prepared followed by testing the amount of crosslinker (ethylene glycol dimethacrylate (EGDMA)), imprinting and rebinding efficiency of the polymer. The ratio 1:4:20 was found to have the highest binding capacity for SLD, and thus, was used as a modifier for the development of modified carbon paste electrodes in presence of multiwalled carbon nanotubes (MWCNT). The sensor was electrochemically characterized using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements and morphologically using SEM, TEM and BET and its performance was optimized in terms of amounts of MIP, MWCNT, pH and other electrochemical parameters. A linear response range of 1.0×10−12–1.0×10−3 M SLD with a detection limit (S/N=3) of 1.0×10−13 M was shown. Finally, the MIP‐modified carbon paste sensor was successfully used to determine SLD in pure solutions, pharmaceutical formulations and spiked serum and urine samples.
A systematic overview of electrode configuration in electric‐driven micropumps
Authors: Tavari Tannaz , Nazari Mohsen , Meamardoost Saber , Tamayol Ali , Samandari Mohamadmahdi 
Published: April 2022

AbstractAccurate manipulation of fluids in microfluidic devices is an important factor affecting their functions. Since the emergence of microfluidic technology to transport fluids in microchannels, the electric field has been utilized as an effective dynamic pumping mechanism. This review attempts to provide a fundamental insight of the various electric‐driven flows in microchannels and their working mechanisms as micropumps for microfluidic devices. Different electrokinetic mechanisms implemented in electrohydrodynamic‐, electroosmosis‐, electrothermal, and dielectrophoresis‐based micropumps are discussed. A detailed description of different mechanisms is presented to provide a comprehensive overview on the key parameters used in electric micropumps. Furthermore, electrode configurations and their shapes in different micropumps are explored and categorized to provide conclusive information for the selection of efficient, simple, and affordable strategies to transport fluids in microfluidic devices. In this paper, recent theoretical, numerical and experimental investigations are covered to provide a better insight both on the operational mechanisms and strategies for lab‐on‐chip applications.
Quantifying uncertainties and correlations of engineering demand parameters of building structures for regional seismic loss assessment
Authors: Kang Chulyoung , Kwon Oh‐Sung , Song Junho 
Published: April 2022

AbstractFor an accurate regional seismic loss assessment, it is essential to quantify the uncertainties and correlations of the engineering demand parameters (EDP) of the building structures. Previous studies predicted the mean EDP of each structure by a regression function of the selected intensity measure (IM), while its variability is described by the “EDP residual.” The authors recently proposed a new formulation and Incremental Dynamic Analysis (IDA)‐based methods to evaluate the correlation between EDP residuals. This paper proposes an IM‐invariant method for estimating the variances and correlations of the EDP residuals of building structures. Based on the EDP residuals of various buildings estimated using the proposed method, primary structural characteristics affecting EDP residuals are identified. In addition, this study develops EDP estimation regression equations using predictive variables defined based on the identified structural characteristics to facilitate consideration of the EDP residual correlation in regional seismic loss assessment. Numerical examples verify the regression models and demonstrate that the proposed method can improve the accuracy of a regional loss assessment by considering the building types in the inventory.
Fabrication and characterization of tea polyphenol W/O microemulsion‐based bioactive edible film for sustained release in fish floss preservation
Authors: Zhang Mengna , Zhao Qiaoling , Lin Yanan , Wang Haifeng , Shui Ruofan , Wang Shitong , Ge Lijun , Li Yunyan , Song Gongshuai , Gong Jinyan , Wang Haixing , Chen Xi , Shen Qing 
Published: April 2022

AbstractA coated nanoemulsion (CNE)‐based edible film was fabricated on the surface of fish floss (FF) to extend its shelf life during storage. The antioxidant tea polyphenol (TPP) was embedded into W/O microemulsion, which was further encapsulated into multiple emulsion (Multi‐E) together with functional soluble dietary fiber (SDF). The physicochemical properties indicated that the nanoemulsion‐based edible film (NEF) improved the morphology of FF and reduced the crystallinity of the film by scanning electron microscopy (SEM) and X‐ray diffraction (XRD). The water vapor permeability increased gradually and rose to only 0.99% after 5 h, resulting in the water activity of FF at a low level (≤0.51) during the storage period. The TPP inside was released at a constant rate (≤18.10%) on the surface, and such a rate was accelerated in the simulated gastrointestinal environment, especially in intestine reaching 60.12% after 5 h of digestion. Besides, the effect of NEF on the flavor was also evaluated and the contents of ketones, phenols, and pyrazines increased, which displayed a regulating effect on the overall flavor of FF by blocking the external moisture and suppressing the microorganism activity. In summary, the NEF effectively enhanced the flavor and taste of FF, controlled the release of TPP, and reduced the water activity during the storage, thereby extending the shelf life.
Biochemical indexes and gut microbiota testing as diagnostic methods for Penaeus monodon health and physiological changes during AHPND infection with food safety concerns
Authors: Soo Tze Chiew Christie , Bhassu Subha 
Published: April 2022

AbstractSevere shrimp disease outbreaks have a destructive impact on shrimp aquaculture and its associated downstream food processing industries. Thus, it is essential to develop proper methods for shrimp disease control, which emphasizes the importance of food safety. In this study, we performed biochemical tests and gut microbiome analysis using uninfected control and VpAHPND‐infected Penaeus monodon samples. Biochemical tests were performed to assess the phenoloxidase (PO) activity, respiratory Burst (RB) activity, nitrite concentration, superoxide dismutase (SOD) activity, total hemocyte count (THC), and total protein concentrations. Overall, upregulations were detected in these biochemical tests, which showed the activation of the immune response in P. monodon during acute hepatopancreatic necrosis disease (AHPND) infection, especially at 6 hpi and 12 hpi. Besides that, shrimp gut samples were collected and pooled (n = 3), followed by DNA extraction, PCR amplification targeting the V3/V4 16S ribosomal RNA (rRNA) region, next‐generation sequencing (NGS), and bioinformatics analysis. Proteobacteria was the most abundant phylum in both samples. The Rhodobacteraceae family and Maritimibacter genus were proposed to be vital forshrimp health maintenance. VpAHPND bacterial colonization and secondary Vibrio infections were postulated to have occurred based on the higher abundances of Vibrionaceae family and Vibrio genus in the VpAHPND‐infected sample. Firmicutes phylum together with Photobacterium and Aliiroseovarius genera were inferred to be pathogenic or related factors of AHPND infections. In conclusion, physiology (immune response activation) and gut microbiome changes of disease tolerant P. monodon during AHPND infection were identified. Both biochemical tests and 16S rRNA analysis are proposed as a combined strategy for shrimp health diagnosis for ensuring shrimp health maintenance, disease control, and food safety.