bluuebunny/crossref_metadata_2025_split huggingface dataset:
Optical Humidity Sensor Based on CdSe/ZnS Quantum Dots Modified by Porous Silica
Authors: Yuan Baozhen , Zhang Xuanyu , Yu Jiahao , Zhou Leiqing , Luo Bingshen , Liu Yanjun , Chen Rui 
Published: September 2022

AbstractUltra‐sensitive optical humidity sensors based on nanomaterials play important roles in the fields of science and industry. The related research has been reported, however, the underlying physical mechanism is still unclear. In order to clarify this point, and further improve the sensing performance, herein, optical humidity sensor based on porous silica/quantum dots (PS/QDs) hybrid nanoarchitecture has been developed. PS is selected to enhance emission of QDs due to its large surface roughness, which can improve light utilization. Under optimized conditions, the emission from the hybrid PS/QDs can be enhanced 6.5 times compared with the as‐grown QDs. With the increase of relative humidity from 20% to 80%, the hybrid PS/QDs demonstrate excellent response, wide sensing range, fast response time (22–40 s), good selectivity, and repeatability. Based on laser spectroscopy, the sensing mechanism is ascribed to the passivation of the surface defects by water molecules, which results in enhanced emission. This work provides a simple and low‐cost method to fabricate humidity sensors and shows promising applications in environmental detection.
Interface‐Tailored Relaxor Ferroelectric Nanocomposites with Ultrahigh‐Insulation Shell of Fluorinated Aromatic Polythiourea for High‐Capacitance Energy Storage Applications
Authors: Zhu Ning , Liu Jiahao , Zhou Jingtao , Zhang Lei , Yao Ni , Liu Xiaolian , Chen Yingxin , Zhang Jian , Zhang Xuefeng 
Published: September 2022

AbstractThe strategy of interface engineering plays a prominent role in obtaining desirable dielectric performance of polymer nanocomposites. In this study, ultrahigh‐insulation BaTiO3@fluorinated aromatic polythiourea (BT@ArPFTU) nanoparticles (NPs), which are successfully synthesized via microwave‐initiated polymerization, are served as novel nanofillers to prepare poly(vinylidenefluoride‐trifluoroethylenechlorotrifuoroethylene)‐based (P(VDF‐TrFE‐CTFE)‐based) nanocomposites for capacitor applications. The ArPFTU coating shell forms a strong interface with 30‐nm thickness between BT and the matrix. It not only contributes to the suppression of current density at the interfaces, the regulation of interfacial charge distribution and tolerating high electric‐field strength, but also favors the improvement in dielectric constant and electric polarization due to interfacial polarization, as confirmed by finite element simulations and experimental results. In addition, the direct observation of electric‐polarization enhancement at the interfaces in the P(VDF‐TrFE‐CTFE)/BT@ArPFTU nanocomposites is well probed by piezoelectric force microscopy. Remarkably, with small loading of BT@ArPFTU NPs, relaxor ferroelectric nanocomposites display an unprecedented discharged energy density of 23.1 J cm−3 and the charge–discharge efficiency of 65%, which is much larger than that of other types of BT‐based polymer nanocomposites and commercial biaxially oriented polypropylene of 0.71 J cm−3. This systematic study further paves a new avenue to design high‐performance polymer nanocomposites by interfacial architecture for capacitor application.
The forgotten survivor: A comprehensive review on Non‐Hodgkin lymphoma survivorship
Authors: Alabdaljabar Mohamad S. , Durani Urshila , Thompson Carrie A. , Constine Louis S. , Hashmi Shahrukh K. 
Published: September 2022

AbstractThe number of non‐Hodgkin lymphoma (NHL) survivors is increasing. With the advancement of NHL therapies, it is crucial to focus on the challenges these survivors may face. Three main categories are to be considered in NHL survivorship, including quality of life and uncertainty about the future, possible physical health complications (including cardiovascular disease, infertility, and subsequent neoplasms), and the impact of novel NHL treatments and their potential complications. The latter includes CAR T‐cell therapy, monoclonal antibodies, checkpoint inhibitors, and hematopoietic stem cell transplantation. In this report, we aim to shed the light on these aspects and to discuss survivorship care plan for NHL.
How Subtle Changes Can Make a Difference: Reproducibility in Complex Supramolecular Systems
Authors: Schnitzer Tobias , Preuss Marco D. , van Basten Jule , Schoenmakers Sandra M. C. , Spiering A. J. H. , Vantomme Ghislaine , Meijer E. W. 
Published: September 2022

AbstractThe desire to construct complex molecular systems is driven by the need for technological (r)evolution and our intrinsic curiosity to comprehend the origin of life. Supramolecular chemists tackle this challenge by combining covalent and noncovalent reactions leading to multicomponent systems with emerging complexity. However, this synthetic strategy often coincides with difficult preparation protocols and a narrow window of suitable conditions. Here, we report on unsuspected observations of our group that highlight the impact of subtle “irregularities” on supramolecular systems. Based on the effects of pathway complexity, minute amounts of water in organic solvents or small impurities in the supramolecular building block, we discuss potential pitfalls in the study of complex systems. This article is intended to draw attention to often overlooked details and to initiate an open discussion on the importance of reporting experimental details to increase reproducibility in supramolecular chemistry.
A Reactivity‐Tunable Self‐Immolative Design Enables Histone Deacetylase‐Targeted Imaging and Prodrug Activation
Authors: Liu Feng , Ding Xu , Xu Xiaobo , Wang Fenglin , Chu Xia , Jiang Jian‐Hui 
Published: September 2022

AbstractHistone deacetylase (HDAC)‐targeted probes and prodrugs are crucial for cancer theranostics. We developed a self‐immolative design that enables in vivo activatable near‐infrared fluorescence (NIRF) and photoacoustic (PA) imaging and prodrug release in response to HDAC. This design comprises a phenyl ester linker with tunable reactivity, facilitating efficient release of caged fluorophores/drugs upon deacetylation. We engineered a new fluorophore using a spirocyclic xanthene scaffold with ring‐open property, affording NIRF/PA detection with high contrast. We showed that a nitro‐substituted self‐immolative linker allows sensitive NIRF/PA in vivo imaging of HDAC with minimal interference. A highly efficient prodrug system was further developed for targeted therapy in HDAC‐overexpressed triple negative breast tumors in mice. Our study provides a valuable paradigm for HDAC‐targeted NIRF/PA imaging and prodrug release in vivo, highlighting its potential for bioimaging and drug development.
Conservation of Nickel Ion Single‐Active Site Character in a Bottom‐Up Constructed π‐Conjugated Molecular Network
Authors: Baranowski Daniel , Cojocariu Iulia , Sala Alessandro , Africh Cristina , Comelli Giovanni , Schio Luca , Tormen Massimo , Floreano Luca , Feyer Vitaliy , Schneider Claus M. 
Published: September 2022

AbstractOn‐surface chemistry holds the potential for ultimate miniaturization of functional devices. Porphyrins are promising building‐blocks in exploring advanced nanoarchitecture concepts. More stable molecular materials of practical interest with improved charge transfer properties can be achieved by covalently interconnecting molecular units. On‐surface synthesis allows to construct extended covalent nanostructures at interfaces not conventionally available. Here, we address the synthesis and properties of covalent molecular network composed of interconnected constituents derived from halogenated nickel tetraphenylporphyrin on Au(111). We report that the π‐extended two‐dimensional material exhibits dispersive electronic features. Concomitantly, the functional Ni cores retain the same single‐active site character of their single‐molecule counterparts. This opens new pathways when exploiting the high robustness of transition metal cores provided by bottom‐up constructed covalent nanomeshes.
The Growth Mechanism of a Conductive MOF Thin Film in Spray‐based Layer‐by‐layer Liquid Phase Epitaxy
Authors: Zheng Rui , Fu Zhi‐Hua , Deng Wei‐Hua , Wen Yingyi , Wu Ai‐Qian , Ye Xiao‐Liang , Xu Gang 
Published: September 2022

AbstractThe layer‐by‐layer liquid‐phase epitaxy (LBL‐LPE) method is widely used in preparing metal–organic framework (MOF) thin films with the merits of controlling thickness and out‐of‐plane orientation for superior performances in applications. The LBL‐LPE growth mechanism related to the grain boundary, structure defect, and orientation is critical but very challenging to study. In this work, a novel “in‐plane self‐limiting and self‐repairing” thin‐film growth mechanism is demonstrated by the combination study of the grain boundary, structure defect, and orientation ofCu3(HHTP)2‐xCthin film via microscopic analysis techniques and electrical measurements. This mechanism results a desired high‐quality MOF thin film with preferred in‐plane orientations at its bottom for the first time and is very helpful for optimizing the LBL‐LPE method, understanding the growth cycle‐dependent properties of MOF thin film, and inspiring the investigations of the biomimetic self‐repairing materials.
Mouse dendritic cells in the steady state: Hypoxia, autophagy, and stem cell factor
Authors: Barroeta Seijas Amairelys Belen , Simonetti Sonia , Filippi Irene , Naldini Antonella , Favaretto Gabriele , Colombo Teresa , Natalini Ambra , Antonangeli Fabrizio , Laffranchi Mattia , Sozzani Silvano , Santoni Angela , Di Rosa Francesca 
Published: September 2022

AbstractDendritic cells (DCs) are innate immune cells with a central role in immunity and tolerance. Under steady‐state, DCs are scattered in tissues as resting cells. Upon infection or injury, DCs get activated and acquire the full capacity to prime antigen‐specific CD4+ and CD8+ T cells, thus bridging innate and adaptive immunity. By secreting different sets of cytokines and chemokines, DCs orchestrate diverse types of immune responses, from a classical proinflammatory to an alternative pro‐repair one. DCs are highly heterogeneous, and physiological differences in tissue microenvironments greatly contribute to variations in DC phenotype. Oxygen tension is normally low in some lymphoid areas, including bone marrow (BM) hematopoietic niches; nevertheless, the possible impact of tissue hypoxia on DC physiology has been poorly investigated. We assessed whether DCs are hypoxic in BM and spleen, by staining for hypoxia‐inducible‐factor‐1α subunit (HIF‐1α), the master regulator of hypoxia‐induced response, and pimonidazole (PIM), a hypoxic marker, and by flow cytometric analysis. Indeed, we observed that mouse DCs have a hypoxic phenotype in spleen and BM, and showed some remarkable differences between DC subsets. Notably, DCs expressing membrane c‐kit, the receptor for stem cell factor (SCF), had a higher PIM median fluorescence intensity (MFI) than c‐kit− DCs, both in the spleen and in the BM. To determine whether SCF (a.k.a. kit ligand) has a role in DC hypoxia, we evaluated molecular pathways activated by SCF in c‐kit+ BM‐derived DCs cultured in hypoxic conditions. Gene expression microarrays and gene set enrichment analysis supported the hypothesis that SCF had an impact on hypoxia response and inhibited autophagy‐related gene sets. Our results suggest that hypoxic response and autophagy, and their modulation by SCF, can play a role in DC homeostasis at the steady state, in agreement with our previous findings on SCF's role in DC survival.
Bicyclic Caged Morpholino Oligonucleotides for Optical Gene Silencing**
Authors: Pattanayak Sankha , Sarode Bhagyesh R. , Deiters Alexander , Chen James K. 
Published: September 2022

AbstractCaged morpholino oligonucleotides (cMOs) are synthetic tools that allow light‐inducible gene silencing in live organisms. Previously reported cMOs have utilized hairpin, duplex, and cyclic structures, as well as caged nucleobases. While these antisense technologies enable efficient optical control of RNA splicing and translation, they can have limited dynamic range. A new caging strategy was developed where the two MO termini are conjugated to an internal position through a self‐immolative trifunctional linker, thereby generating a bicyclic cMO that is conformationally resistant to RNA binding. The efficacy of this alternative cMO design has been demonstrated in zebrafish embryos and compared to linear MOs and monocyclic constructs.
Treatment of Reactive Dyes Using Amberlite Resin Functionalized with Amine‐Based Solvent – Batch and Continuous Studies
Authors: Awasthi Anjali , Datta Dipaloy 
Published: September 2022

AbstractThe azo dyes Reactive Orange‐16 and Reactive Green‐19 were removed using Aliquat‐336‐incorporated Amberlite XAD7HP resin in batch and in a continuous stirrer vessel. The prepared resin was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, Brunauer‐Emmett‐Teller method, and X‐ray photoelectron spectroscopy. The effect of dosage, initial dye concentration, time, pH, and temperature on the removal efficiency of both dyes was evaluated. Equilibrium, kinetic, and diffusion models were fitted to the batch data. Design calculations for single‐stage batch adsorption were done to scale up the process industrially. The resin was regenerated using ethanol. To intensify the process further, continuous studies were performed in a recirculating stirred vessel at different flow rates and stirring speeds.
Alkyne Activation in the Diversity Oriented Synthesis of sp2‐Rich Scaffolds: A Biased Library Approach for Targeting Polynucleotides (DNA/RNA)
Authors: Chen Shuqi , Priebbenow Daniel L. , Somkhit Julie , Scullino Carmen V. , Agama Keli , Pommier Yves , Flynn Bernard L. 
Published: September 2022

AbstractPolynucleotides, DNA and RNA (mRNA and non‐coding RNAs) are critically involved in the molecular pathways of disease. Small molecule binding interactions with polynucleotides can modify functional polynucleotide topologies and/or their interactions with proteins. Current approaches to library design (lead‐like or fragment‐like libraries) are based on protein‐ligand interactions and often include careful consideration of the 3‐dimensional orientation of binding motifs and exclude π‐rich compounds (polyfused aromatics) to avoid off‐target R/DNA interactions. In contrast to proteins, where π,π‐interactions are weak, polynucleotides can form strong π,π‐interactions with suitable π‐rich ligands. To assist in designing a polynucleotide‐biased library, a scaffold‐divergent synthesis approach to polyfused aromatic scaffolds has been undertaken. Initial screening hits that form moderately stable polynucleotide‐ligand‐protein ternary complexes can be further optimized through judicious incorporation of substituents on the scaffold to increase protein‐ligand interactions. An example of this approach is given for topoisomerase‐1 (TOP1), generating a novel TOP1 inhibitory chemotype.
Bismuth Gadolinium Oxychloride with a Remarkable Visible‐Light‐Responsive O2 Evolution Activity Promoted by Iodine Doping
Authors: Zhao Conghui , Sun Liwei , Xu Yang , Dong Beibei , Luo Yuhong , Li Jingde , Chen Jianxin , Zhang Zisheng 
Published: September 2022

AbstractVisible‐light‐responsive bismuth‐based oxyhalide has recently attracted extensive attention, however, the promotion of its charge separation is still challenging. Herein, we introduce iodine into Bi2GdO4Cl to synthetize I‐doped Bi2GdO4Cl (denoted as yI−Bi2GdO4Cl, 0≤y≤2). The incorporation of I− ions is found to enhance light absorption and to accelerate charge separation by combining various characterizations such as density functional theory calculation, photoelectrochemical test, electrochemical impedance spectroscopy, photoluminescence spectrum, and open‐circuit voltage decay. The O2‐evolving performances of 1I−Bi2GdO4Cl with optimized dopant concentration of I− ion and IrO2 loaded 1I−Bi2GdO4Cl are tremendously enhanced by ca. 4 and 45 times compared to pristine Bi2GdO4Cl. Notably, The O2 evolution rate reaches as high as 154.8 μmol ⋅ h−1 with an apparent quantum efficiency of ∼1.1 % at 420 nm. The synthetic iodine‐doped photocatalyst remains stable after long‐term photoreaction, demonstrating its potential in the field of photocatalysis.
Non‐Covalent Integration of a [FeFe]‐Hydrogenase Mimic to Multiwalled Carbon Nanotubes for Electrocatalytic Hydrogen Evolution
Authors: Zamader Afridi , Reuillard Bertrand , Pécaut Jacques , Billon Laurent , Bousquet Antoine , Berggren Gustav , Artero Vincent 
Published: September 2022

AbstractSurface integration of molecular catalysts inspired from the active sites of hydrogenase enzymes represents a promising route towards developing noble metal‐free and sustainable technologies for H2 production. Efficient and stable catalyst anchoring is a key aspect to enable this approach. Herein, we report the preparation and electrochemical characterization of an original diironhexacarbonyl complex including two pyrene groups per catalytic unit in order to allow for its smooth integration, through π‐interactions, onto multiwalled carbon nanotube‐based electrodes. In this configuration, the grafted catalyst could reach turnover numbers for H2 production (TONH2) of up to 4±2×103 within 20 h of bulk electrolysis, operating at neutral pH. Post operando analysis of catalyst functionalized electrodes revealed the degradation of the catalytic unit occurred via loss of the iron carbonyl units, while the anchoring groups and most part of the ligand remained attached onto multiwalled carbon nanotubes.
Efficacy of neoadjuvant chemotherapy in male breast cancer compared with female breast cancer
Authors: Leone José Pablo , Hassett Michael J. , Leone Julieta , Tolaney Sara M. , Vallejo Carlos T. , Leone Bernardo A. , Winer Eric P. , Lin Nancy U. 
Published: September 2022

BackgroundNeoadjuvant chemotherapy (NAC) is standard for many females with breast cancer (FBC). The efficacy of NAC in male breast cancer (MaBC) is unclear. The aim of this study was to compare proportions of pathologic complete response (pCR) between MaBC and FBC by tumor subtype (TS).MethodsMaBC and FBC treated with NAC between 2010 and 2016, with known TS, were evaluated from the National Cancer Database. Proportions of pCR (ypT0/Tis ypN0) were compared between sexes within TS by Fisher test. Multivariable logistic regression assessed the independent association of sex with pCR. Overall survival (OS) was estimated by Kaplan–Meier.ResultsA total of 385 MaBC and 68,065 FBC were included. Median time from initiation of NAC to surgery was 143 days in MaBC and 148 days in FBC. Proportions of pCR in MaBC and FBC by TS were: hormone receptor–positive/human epidermal growth factor receptor 2–negative (HR+/HER2–): 4.9% vs 9.7%, p = .01; HR+/HER2+: 16.1% vs 33.6%, p < .001; HR–/HER2+: 44.0% vs 53.2%, p = .42; and HR–/HER2–: 21.4% vs 32.1%, p = .18, respectively. FBC had twice the odds of pCR than MaBC (adjusted odds ratio, 2.0; 95% CI, 1.5–2.8; p < .001). Five‐year OS for MaBC with pCR vs not was 90% vs 64.7%; p = .02. Five‐year OS for FBC with pCR vs not was 91.9% vs 75.3%; p < .01.ConclusionsProportions and odds of pCR to NAC were numerically lower in MaBC compared with FBC for each TS and statistically significant for HR+/HER2– and HR+/HER2+. The independent association of sex with pCR was confirmed in multivariable analysis. pCR is prognostic in both MaBC and FBC.
Cost effectiveness of treatment strategies for high risk prostate cancer
Authors: Kowalchuk Roman O. , Kim Hayeon , Harmsen William S. , Jeans Elizabeth B. , Morris Lindsay K. , Mullikin Trey C. , Miller Robert C. , Wong William W. , Vargas Carlos E. , Trifiletti Daniel M. , Phillips Ryan M. , Choo C. R. , Davis Brian J. , Beriwal Sushil , Tendulkar Rahul D. , Stish Bradley J. , Breen William G. , Waddle Mark R. 
Published: September 2022

BackgroundPatients with high‐risk prostate cancer (HRPC) have multiple accepted treatment options. Because there is no overall survival benefit of one option over another, appropriate treatment must consider patient life expectancy, quality of life, and cost.MethodsThe authors compared quality‐adjusted life years (QALYs) and cost effectiveness among treatment options for HRPC using a Markov model with three treatment arms: (1) external‐beam radiotherapy (EBRT) delivered with 20 fractions, (2) EBRT with 23 fractions followed by low‐dose‐rate (LDR) brachytherapy boost, or (3) radical prostatectomy alone. An exploratory analysis considered a simultaneous integrated boost according to the FLAME trial (ClinicalTrials.gov identifier NCT01168479).ResultsTreatment strategies were compared using the incremental cost‐effectiveness ratio (ICER). EBRT with LDR brachytherapy boost was a cost‐effective strategy (ICER, $20,929 per QALY gained). These results were most sensitive to variations in the biochemical failure rate. However, the results still demonstrated cost effectiveness for the brachytherapy boost paradigm, regardless of any tested parameter ranges. Probabilistic sensitivity analysis demonstrated that EBRT with LDR brachytherapy was favored in 52% of 100,000 Monte Carlo iterations. In an exploratory analysis, EBRT with a simultaneous integrated boost was also a cost‐effective strategy, resulting in an ICER of $62,607 per QALY gained; however, it was not cost effective compared with EBRT plus LDR brachytherapy boost.ConclusionsEBRT with LDR brachytherapy boost may be a cost‐effective treatment strategy compared with EBRT alone and radical prostatectomy for HRPC, demonstrating high‐value care. The current analysis suggests that a reduction in biochemical failure alone can result in cost‐effective care, despite no change in overall survival.
Understanding the Behaviour of Real Metaborates in Solution
Authors: Pope Frances , Watson Noë I. , Deblais Antoine , Rothenberg Gadi 
Published: September 2022

AbstractAlkali metal borohydrides are promising candidates for large‐scale hydrogen storage. They react spontaneously with water, generating dihydrogen and metaborate salts. While sodium borohydride is the most studied, potassium has the best chance of commercial application. Here we examine the physical and chemical properties of such self‐hydrolysis solutions. We do this by following the hydrogen evolution, the pH changes, and monitoring the reaction intermediates using NMR. Most studies on such systems are done using dilute solutions, but real‐life applications require high concentrations. We show that increasing the borohydride concentration radically changes the system's microstructure and rheology. The changes are seen already at concentrations as low as 5 w/w%, and are critical above 10 w/w%. While dilute solutions are Newtonian, concentrated reaction solutions display non‐Newtonian behaviour, that we attribute to the formation and (dis)entanglement of metaborate oligomers. The implications of these findings towards using borohydride salts for hydrogen storage are discussed.
Unfurling Anion‐π Interactions Involving Graphynes
Authors: Parameswaran Aiswarya M. , James Anto , Aboobacker Adil , Srinivasamurthy Swathi Rotti 
Published: September 2022

AbstractEver since the inception of anion‐π interactions, their nature and functional relevance have intrigued researchers. We address the twin challenge of elucidation of the role of extended conjugation and design of all‐carbon neutral anion receptors by computations on the anion‐π complexes of the halide ions with graphynes. Leveraging on the extended π‐conjugation effects, we unfurl the functional relevance of graphynes as anion receptors using descriptors such as electrostatic potential, quadrupole moments, molecular polarizabilities and binding energies. Further, employing natural energy decomposition analysis, we assert that anion‐π interactions are not merely dominated by electrostatic interactions. The polarization components do indeed play a crucial role in governing the binding of the anions to the graphynes.