bluuebunny/crossref_metadata_2025 huggingface dataset:
A Bifunctional Liquid Fuel Cell Coupling Power Generation and V3.5+ Electrolytes Production for All Vanadium Flow Batteries
Authors: Sun Shibo , Fang Liwei , Guo Hui , Sun Liping , Liu Yong , Cheng Yuanhui
Published: April 2023

All vanadium flow batteries (VFBs) are considered one of the most promising large‐scale energy storage technology, but restricts by the high manufacturing cost of V3.5+ electrolytes using the current electrolysis method. Here, a bifunctional liquid fuel cell is designed and proposed to produce V3.5+ electrolytes and generate power energy by using formic acid as fuels and V4+ as oxidants. Compared with the traditional electrolysis method, this method not only does not consume additional electric energy, but also can output electric energy. Therefore, the process cost of producing V3.5+ electrolytes is reduced by 16.3%. This fuel cell has a maximum power of 0.276 mW cm−2 at an operating current of 1.75 mA cm−2. Ultraviolet–visible spectrum and potentiometric titration identify the oxidation state of prepared vanadium electrolytes is 3.48 ± 0.06, close to the ideal 3.5. VFBs with prepared V3.5+ electrolytes deliver similar energy conversion efficiency and superior capacity retention to that with commercial V3.5+ electrolytes. This work proposes a simple and practical strategy to prepare V3.5+ electrolytes.
Thermometry of AlGaN/GaN 2D Channels at High Electric Fields Using Electrical and Optical Methods
Authors: Vitusevich S. , Nasieka I.M. , Naumov A. V. , Kalyuzhnyi V. V. , Liubchenko O. I. , Antypov I. O. , Boyko M. I. , Belyaev A. E.
Published: April 2023

The active channels in AlGaN/GaN‐based heterostructures are studied under different applied electrical fields to identify the Joule heating factors affecting the temperature values in the channels. The temperature in active channels of two different lengths (30 and 180 µm) is characterized using optical methods, and electrical methods are used as a reference. The technique of optical thermometry is based on the data of micro‐photoluminescence and micro‐Raman experiments. The electrical method is based on the measurements of current–voltage characteristics for comparison. It is shown that photoluminescence‐ and electrical‐based temperature values demonstrate similar behavior and good correlation. The Raman‐based method, exploiting the temperature dependence of the frequency position of E2high vibrational band in GaN, shows a significant deviation compared with electrical‐ and luminescence‐based methods. This deviation is shown to be related to the residual mechanical strain in the layered structure and the formation of hot phonons. The influence of hot phonons and mechanical strain effects increases at high electrical load (>5 kV cm−1) and at high temperatures (>400 °C), respectively.
Ion Bridging by Carbon Dioxide Facilitates Electrochemical Energy Storage at Charged Carbon–Ionic–Liquid Interfaces
Authors: Liu Mingren , Wang Yong‐Lei , Schutjajew Konstantin , Chai Liyuan , Oschatz Martin
Published: April 2023

Solvent free ionic liquid (IL) electrolytes facilitate high‐voltage supercapacitors with enhanced energy density, but their complex ion arrangement and through that the electrochemical properties, are limited by strong Coulombic ordering in the bulk state and like‐charged ion repulsion at electrified interfaces. Herein, a unique interfacial phenomenon resulting from the presence of carbon dioxide loaded in 1‐Ethyl‐3‐methylimidazoliumtetrafluorborate electrolyte that simultaneously couples to IL ions and nitrogen‐doped carbonaceous electrode is reported. The adsorbed CO2 molecule polarizes and mitigates the electrostatic repulsion among like‐charged ions near the electrified interface, leading to an ion “bridge effect” with increased interfacial ionic density and significantly enhanced charge storage capability. The unpolarized CO2 possessing a large quadrupole moment further reduces ion coupling, resulting in higher conductivity of the bulk IL and improved rate capability of the supercapacitor. This work demonstrates polarization‐controlled like‐charge attraction at IL–electrode–gas three‐phase boundaries, providing insights into manipulating complex interfacial ion ordering with small polar molecule mediators.
Elder‐led cultural identity program as counterspace at a public university: Narratives on sense of community, empowering settings, and empowerment
Authors: Buckingham Sara L. , Schroeder Tiera Uqiilaq , Hutchinson Jacy R.
Published: April 2023

Higher education institutions present unique settings in which identities and life paths are distinctively shaped. While at their best universities should serve as empowering settings that support their members to grow and develop, to raise awareness of injustice, and to catalyze change, too often systems of higher education in the United States serve to marginalize Indigenous cultures and promote assimilation to White, Euro‐American cultures. Counterspaces offer an important response, spaces developed by and for people experiencing oppression that allow for solidarity‐building, social support, healing, resource attainment, skill‐building, resistance, counter‐storytelling, and ideally, empowerment. The Alaska Native (AN) Cultural Identity Project (CIP) is based at an urban U.S.‐based university and was rolled out during the COVID‐19 pandemic. Developed from the best available scientific and practice literature, local data from AN students, and traditional wisdom from Elders, CIP incorporated storytelling, experiential learning, connection, exploration, and sharing of identity and cultural strengths with the aim of helping AN students understand who they are and who they are becoming. In all, 44 students, 5 Elders, and 3 additional staff participated in the space. In this paper, we sought to understand how CIP was experienced by these unique members who co‐created and engaged in this space through 10 focus groups with 36 of the CIP members. We found that the counterspace promoted a sense of community, served as an empowering setting, and set the stage for empowering actions and ripple effects beyond its impact on individuals.
Reactive Superhydrophobic Surfaces for Interlayer Electrical Connectivity in Three‐dimensional Electronics
Authors: Xie Xinjian , Feng Wenqian
Published: April 2023

This study describes the development of a new type of amine‐reactive superhydrophobic (RSH) film that is facilely coated on various substrates using a single‐step process, while the versatility of this RSH film offers a reliable solution for efficient formation of complex and robust interlayer electrical connectivity (IEC) in 3D electronic systems. The excellent spatial controllability of surface amine modification enables the generation of vertical circuits in situ, providing a distinct way to connect circuits located on different layers. Moreover, the inherent superhydrophobicity and porosity exhibit the required anti‐fouling and breathability properties, making the RSH‐based IEC well‐suited for applications where exposure to environmental gas and liquid contaminants is likely. This approach provides another avenue towards the development of IEC in 3D flexible integrated electronics, opening up new possibilities for the advancement of this field.
Selective In Situ Analysis of Mature microRNAs in Extracellular Vesicles Using a DNA Cage‐Based Thermophoretic Assay
Authors: Zhao Shuai , Zhang Shaohua , Hu Huijun , Cheng Yangchang , Zou Kexuan , Song Jie , Deng Jinqi , Li Lele , Zhang Xiao‐Bing , Ke Guoliang , Sun Jiashu
Published: April 2023

Mature microRNAs (miRNAs) in extracellular vesicles (EVs) are involved in different stages of cancer progression, yet it remains challenging to precisely detect mature miRNAs in EVs due to the presence of interfering RNAs (such as longer precursor miRNAs, pre‐miRNAs) and the low abundance of tumor‐associated miRNAs. By leveraging the size‐selective ability of DNA cages and polyethylene glycol (PEG)‐enhanced thermophoretic accumulation of EVs, we devised a DNA cage‐based thermophoretic assay for highly sensitive, selective, and in situ detection of mature miRNAs in EVs with a low limit of detection (LoD) of 2.05 fM. Our assay can profile EV mature miRNAs directly in serum samples without the interference of pre‐miRNAs and the need for ultracentrifugation. A clinical study showed that EV miR‐21 or miR‐155 had an overall accuracy of 90 % for discrimination between breast cancer patients and healthy donors, which outperformed conventional molecular probes detecting both mature miRNAs and pre‐miRNAs. We envision that our assay can advance EV miRNA‐based diagnosis of cancer.
Photocatalytic degradation of Rhodamine B dye using low‐cost pyrofabricated titanium dioxide quantum dots‐kaolinite nanocomposite
Authors: Awad Mahmoud E. , Farrag Amr M. , El‐Bindary Ashraf A. , El‐Bindary Mohamed A. , Kiwaan Hala A.
Published: April 2023

In this study, we report a simple technique for the pyrofabrication of a novel photocatalyst of titanium dioxide quantum dots‐kaolinite nanocomposite (TiO2‐QDs‐Kao) used for rhodamine B (RhB) dye degradation. The photocatalyst was characterized by using different analytical techniques, including XRD, XRF, XPS, FTIR, DTA/TGA, SEM–EDX, TEM, BET, BJH, ZP and UV–Vis DRS. The photocatalytic degradation of RhB was performed in aqueous solutions using the sustainable sunlight energy under atmospheric conditions and fixed neutral medium (pH = 7). The produced photocatalyst exhibited optical band gap energy of 2.85 eV, an improved large specific surface area of 107.724 m2/g with pore radius of 1.45 nm and total pore volume of 0.123 cm3/g. The study indicated a maximum 91% degradation efficiency of RhB after 120 min using the optimum dose 1,400 mg/l of the TiO2‐QDs‐Kao photocatalyst. The degradation of RhB dye fitted the Langmuir first‐order kinetics with rate constant 0.0151 min−1. The radical trapping experiments based on scavengers confirmed that the mechanism of photocatalytic degradation activity was potentially based on electron (e−) and hole (h+) conduction band. The potential energy of the valence and conduction bands EVB and ECB were calculated 2.73 and −0.12 eV, respectively. A triple reusability study confirmed a high stability of TiO2‐QDs‐Kao photocatalyst with detected degradation efficiencies of 91.0, 89.9, 88.8 and 87.5%, respectively.
A new organic zinc thermal stabilizer containing two kinds of anions with excellent thermal stability on polyvinyl chloride by multistep substitution
Authors: Shi Yanqin , Chen Lukai , Lu Songyan , Yao Yuchen , Chen Si , He Huiwen , Ma Meng , Wang Xu
Published: April 2023

A new kind of highly efficient organic zinc thermal stabilizer for polyvinyl chloride (PVC), zinc arginine stearate [Zn(Arg)(St)], is designed by introducing the arginine and stearate to the same zinc atoms to regulate the binding energy between anions and cation. Gaussian soft is used to calculate the binding energy. The results of Fourier transform infrared spectra, elemental analysis, thermogravimetric analysis, and differential scanning calorimetry show that Zn(Arg)(St) has been successfully synthesized. Zn(Arg)(St) stabilized PVC displays excellent Congo red, static and dynamic thermal stability time, especially the excellent initial whiteness and whiteness retention time. The thermal stability mechanism of Zn(Arg)(St) attributes to the different binding energy between the two anions and zinc cation, which results in Zn(Arg)(St) continuously replacing the unstable chlorine atoms step by step by Arg and St anions. Moreover, the amino group in Arg could complex ZnCl2 to inhibit the “zinc burning” effect, and the guanidine group could absorb HCl to inhibit the “autocatalytic effect” of HCl. In addition, Zn(Arg)(St) has a remarkable lubrication effect, which also enhances the thermal stability of PVC. Thus, Zn(Arg)(St) is an environmentally friendly thermal stabilizer for PVC with an excellent thermal stability effect. Importantly, this work also proposes a new method to design highly efficient thermal stabilizers for PVC.
Cyclic carbonates as building blocks for non‐isocyanate polyurethanes
Authors: Kotanen Soilikki , Wirtanen Tom , Mahlberg Riitta , Anghelescu‐Hakala Adina , Harjunalanen Tapani , Willberg‐Keyrilainen Pia , Laaksonen Timo , Sarlin Essi
Published: April 2023

Three different cyclic carbonates (ethylene, propylene, and butylene carbonate) that can be derived from CO2 were successfully polymerized with hexamethylenediamine to form non‐isocyanate polyurethanes (NIPUs) via self‐polycondensation route without the use of harmful di‐isocyanates. Three different catalysts were compared for their performance in self‐polycondensation. Increasing the side chain length in cyclic carbonate increased the amount of urea side reaction and decreased the solubility of the final product. The increased amount of urea lead to a more thermoset behavior as the melting and decomposition took place simultaneously. Furthermore, the extent of urea side reaction and melting behavior were adjustable with the selection of the catalyst or polymerization parameters. With ethylene and propylene carbonate based precursors, it was possible to obtain promising melting temperatures and lap shear strength for the NIPUs when optimized polymerization parameters and catalyst were used.
Synthesis of fluorinated copolymers and their applications as pressure‐responsive materials
Authors: Shi Jiayan , Wei Chunhua , Deng Mengyu , Liang Lei , Tian Yanqing
Published: April 2023

Pressure‐sensitive paints (PSPs) have been demonstrated to be very important for aerodynamics research. In order to improve the pressure sensitivity and adhesion ability of PSP, herein, a series of fluorine‐containing copolymers compositing of an oxygen and pressure‐responsive probe derived from platinum(II)‐5,10,15,20‐tetrakis‐(2,3,4,5,6‐pentafluorophenyl)‐porphyrin (PtTFPP) named as poly[(tBs)a‐co‐(TFEM)b‐co‐(PtTFPP‐1MA)c] were synthesized and investigated as PSPs. These PSPs were constructed with different fluorine ratios for the investigation of the effect of fluorine contents on PSPs. Especially, PSP (F0.33) with the trifluoroethyl methacrylate (TFEM) molar ratio of 33% in the copolymers could adhere well to the surface of an aircraft model. F0.33 showed high oxygen sensitivity (I0/I100 = 32.87), reasonable response time to oxygen (44 s), high pressure sensitivity (SP = 0.75%/kPa at 20°C) and low temperature response (ST = −0.77%/°C at 100 kPa). F0.33 was further sprayed on the surface of a delta wing of an aircraft model and its pressure response was verified in a wind tunnel. The data from F0.33 film at the same wind speed and position were close to the pressure data measured by using traditional method using open pressure holes, showing the potential application of these PSPs.
Emissionsarmes Bauen mit Beton: Perspektiven und Handlungskorridore
Authors: Weidner Stefanie , Bechmann Roland , Mrzigod Alexandra
Published: April 2023

Errichtung, Betrieb und Rückbau von Gebäuden verursachen große Mengen an Treibhausgasen. Insbesondere der Einsatz von Beton führt zu schädlichen Umweltauswirkungen. Die Herstellung von Zement verursacht mehr als 8 % des anthropogenen CO2‐Ausstoßes. In diesem Beitrag werden Lösungsstrategien aufgezeigt, die jede/r Planer/in schon heute mit den verfügbaren Technologien und Werkzeugen anwenden kann, um einen wichtigen Beitrag zur Emissionsreduzierung des Bausektors zu leisten.
Constrained density functional theory calculations for estimation of forward and backward intermolecular charge transfer energy
Authors: Kim Junseok , Kim Hyungjun
Published: April 2023

Charge transfer (CT) in donor–acceptor complexes can occur in two directions: from donor to acceptor (forward CT, CTF) and from acceptor to donor (backward CT, CTB). For an ethylene and tetrafluoroethylene model system, coupled cluster calculations predict that CTF is more stable than CTB. Meanwhile, density functional theory (DFT) and time‐dependent DFT (TDDFT) employing B3LYP functional show a different CT state order depending on the Hartree–Fock exchange (HFX) contribution. The impact of basis sets as a possible cause to induce such unreasonable CT state reverse along with the increase of HFX was investigated. The physical origin of CT state reversal is examined in terms of molecular orbital energy. We analyzed two additional molecular pairs that feature CT state reversal along with the amount of HFX in B3LYP functional. Despite the reduced gap, we suggest constrained DFT using M06‐HF functional as an effective approach to estimate two CT state energies on equal footing.
Hepatocellular carcinoma in patients cured of chronic hepatitis C: Minimal steatosis
Authors: Rocha Chiara , Doyle Erin H. , Bowman Chip A. , Fiel M‐Isabel , Stueck Ashley E. , Goossens Nicolas , Bichoupan Kian , Patel Neal , Crismale James F. , Makkar Jasnit , Lewis Sara , Perumalswami Ponni V. , Schiano Thomas D. , Hoshida Yujin , Schwartz Myron , Branch Andrea D.
Published: April 2023

Background

Successful treatment of hepatitis C reduces liver inflammation and fibrosis; however, patients remain at risk of developing hepatocellular carcinoma (HCC).

Aims

To identify risk factors for new‐onset HCC in patients cured of hepatitis C.

Methods

Imaging, histological, and clinical data on patients whose first HCC was diagnosed >12 months of post‐SVR were analyzed. Histology of 20 nontumor tissues was analyzed in a blinded manner using the Knodel/Ishak/HAI system for necroinflammation and fibrosis/cirrhosis stage and the Brunt system for steatosis/steatohepatitis. Factors associated with post‐SVR HCC were identified by comparison with HALT‐C participants who did not develop post‐SVR HCC.

Results

Hepatocellular carcinoma was diagnosed in 54 patients (45 M/9F), a median of 6 years of post‐SVR [interquartile range (IQR) =1.4‐10y] at a median age of 61 years (IQR, 59–67). Approximately one‐third lacked cirrhosis, and only 11% had steatosis on imaging. The majority (60%) had no steatosis/steatohepatitis in histopathology. The median HAI score was 3 (1.25–4), indicating mild necroinflammation. In a multivariable logistic regression model, post‐SVR HCC was positively associated with non‐Caucasian race (p = 0.03), smoking (p = 0.03), age > 60 years at HCC diagnosis (p = 0.03), albumin<3.5 g/dL (p = 0.02), AST/ALT>1 (p = 0.05), and platelets <100 × 103 cells/μL (p < 0.001). Alpha fetoprotein ≥4.75 ng/mL had 90% specificity and 71% sensitivity for HCC occurrence. Noncirrhotic patients had larger tumors (p = 0.002) and a higher prevalence of vascular invasion (p = 0.016) than cirrhotic patients.

Conclusions

One‐third of patients with post‐SVR HCC did not have liver cirrhosis; most had no steatosis/steatohepatitis. Hepatocellular carcinomas were more advanced in noncirrhotic patients. Results support AFP as a promising marker of post‐SVR HCC risk.
Time trends and survival of marginal zone lymphoma over 25 years in Girona, Spain (1994–2018)
Authors: Auñón Carmen , Sanvisens Arantza , Turon Estel , Vidal‐Vila Anna , Puigdemont Montse , Osca‐Gelis Gemma , Eraso Arantxa , Marcos‐Gragera Rafael
Published: April 2023

Objective

To analyze the incidence, incidence trends, and survival of marginal zone lymphomas (MZLs) in Girona and to describe these indicators based on the location in the case of extranodal MZLs.

Methods

Population‐based study of MZL collected in the Girona Cancer Registry, 1994–2018. Sociodemographic data, tumor location, and stage were obtained from clinical records. Crude (CR) and age‐adjusted (ASRE) incidence rates expressed per 100,000 person‐years (p‐y) were calculated. Joinpoint regression models were used for the trend analysis according to the MZL group. Five‐year observed and net survival were analyzed.

Results

A total of 472 MZLs were included, 44 (9.3%) were nodal, 288 (61.0%) extranodal, 122 (25.9%) splenic, and the rest (n = 18) MZL, NOS. The CR for the MZL was 2.89 × 100,000 p‐y (95% CI: 2.63–3.15), the ASRE was 3.26 × 100,000 p‐y (95% CI: 2.97–3.57), and the annual percentage change (APC) was 1.6 (95% CI: 0.5–2.7). The ASRE for nodal MZL was 0.30 × 100,000 p‐y (95% CI: 0.22–0.41) and showed an APC of 2.9% (95% CI: −16.4–26.6). For extranodal MZL, the ASRE was 1.98 × 100,000 p‐y (95% CI: 1.76–2.23) and the APC was −0.4 (95% CI: −2.0–1.2). The most frequent locations of this type of MZL were the gastric (35.4%), skin (13.2%), and respiratory system (11.8%). The ASRE of the splenic MZL was 0.85 (95% CI: 0.71–1.02) with an APC of 12.8 (95% CI: 2.5–24.0). The 5‐year net survival of MZL was 82.1% (95% CI: 76.3–86.5).

Conclusions

This study reveals differences in the incidence and trend of the incidence of MZL according to the subgroup, showing a significant increase in the overall MZL mainly due to splenic MZL type.
Novel predictors of immune checkpoint inhibitor response and prognosis in advanced non‐small‐cell lung cancer with bone metastasis
Authors: Asano Yohei , Yamamoto Norio , Demura Satoru , Hayashi Katsuhiro , Takeuchi Akihiko , Kato Satoshi , Miwa Shinji , Igarashi Kentaro , Higuchi Takashi , Taniguchi Yuta , Morinaga Sei , Sone Takashi , Okuda Miho , Matsumoto Isao , Yano Seiji , Tsuchiya Hiroyuki
Published: April 2023

Backgrounds

Immune checkpoint inhibitors (ICIs) can significantly prolong the survival of patients with advanced non‐small‐cell lung cancer (NSCLC); however, few studies on the therapeutic effects of ICIs on bone metastases were performed.

Methods

This retrospective study aimed to investigate the therapeutic effects of ICIs and determine predictors of favorable ICI response and prognosis in 55 advanced NSCLC patients with bone metastases who initiated ICI treatment between 2016 and 2019, with a mean follow‐up period of 23.2 months. Patients were classified into responders (complete or partial response) and non‐responders (stable or progressive disease) according to the MD Anderson Cancer Center (MDA) criteria, and the predictors of therapeutic response were identified using multivariate logistic regression analysis. Furthermore, overall survival from the time of ICI administration to the final follow‐up or death was evaluated, and prognostic predictors were identified using Cox proportional hazards regression analysis.

Results

ICI response rate was 30.9% (complete in three cases, partial in 14). Median survival time was 9.3 months, with 1‐year and 2‐year survival rates of 40.6% and 19.3%, respectively. Responders survived significantly longer than non‐responders (p = 0.03). Based on the receiver operating characteristic curve, the predictive cutoff value of the pretreatment neutrophil‐to‐lymphocyte ratio (NLR) was 2.1. Multivariate analysis identified female sex (p = 0.03), use of ICIs as first‐line therapy (p < 0.01), and NLR <2.1 (p = 0.03) as significant predictors of therapeutic response, whereas concomitant use of a bone‐modifying agent (p < 0.01), Katagiri score ≤6 points (p < 0.01), and NLR <2.1 (p = 0.02) were identified as significant predictors of good prognosis.

Conclusions

This study identified some novel predictors for favorable therapeutic response and prognosis in advanced NSCLC patients with bone metastases undergoing ICI treatment. Pretreatment NLR less than 2.1 can be considered the most important predictor.
Matched Ligands for Small, Stable Colloidal Nanoparticles of Copper, Cuprous Oxide and Cuprous Sulfide
Authors: Cowie Bradley E. , Häfele Lisa , Phanopoulos Andreas , Said Said A. , Lee Ja Kyung , Regoutz Anna , Shaffer Milo S. P. , Williams Charlotte K.
Published: April 2023

This work applies organometallic routes to copper(0/I) nanoparticles and describes how to match ligand chemistries with different material compositions. The syntheses involve reacting an organo‐copper precursor, mesitylcopper(I) [CuMes]z (z=4, 5), at low temperatures and in organic solvents, with hydrogen, air or hydrogen sulfide to deliver Cu, Cu2O or Cu2S nanoparticles. Use of sub‐stoichiometric quantities of protonated ligand (pro‐ligand; 0.1–0.2 equivalents vs. [CuMes]z) allows saturation of surface coordination sites but avoids excess pro‐ligand contaminating the nanoparticle solutions. The pro‐ligands are nonanoic acid (HO2CR1), 2‐[2‐(2‐methoxyethoxy)ethoxy]acetic acid (HO2CR2) or di(thio)nonanoic acid, (HS2CR1), and are matched to the metallic, oxide or sulfide nanoparticles. Ligand exchange reactions reveal that copper(0) nanoparticles may be coordinated by carboxylate or di(thio)carboxylate ligands, but Cu2O is preferentially coordinated by carboxylate ligands and Cu2S by di(thio)carboxylate ligands. This work highlights the opportunities for organometallic routes to well‐defined nanoparticles and the need for appropriate ligand selection.
De‐Novo Design of pre‐miR‐21 Maturation Inhibitors: Synthesis and Activity Assessment
Authors: Shcheholeva Iryna , Fernández‐Remacha Daniel , Estrada‐Tejedor Roger , Duca Maria , Michelet Véronique
Published: April 2023

Targeting RNA with small molecules is a major challenge of current medicinal chemistry, and the identification and design of original scaffolds able to selectively interact with an RNA target remains difficult. Various approaches have been developed based on classical medicinal chemistry strategies (fragment‐based drug design, dynamic combinatorial chemistry, HTS or DNA‐encoded libraries) as well as on advanced structural biology and biochemistry methodologies (such as X‐ray, cryo‐EM, NMR, or SHAPE). Here, we report the de novo design, synthesis, and biological evaluation of RNA ligands by using a straightforward and sustainable chemistry combined with molecular docking and biochemical and biophysical studies that allowed us to identify a novel pharmacophore for RNA binding. Specifically, we focused on targeting the biogenesis of microRNA‐21, the well‐known oncogene. This led us not only to promising inhibitors but also to a better understanding of the interactions between the small‐molecule compounds and the RNA target paving the way for the rational design of efficient inhibitors with potential anticancer activity.
From Proton to Boron: The Lewis Analogs of Protonated Brønsted Super Acids
Authors: Osi Arnaud , Tumanov Nikolay , Fusaro Luca , Wouters Johan , Berionni Guillaume , Chardon Aurélien
Published: April 2023

Isolation and characterization of highly reactive intermediates are crucial to understand the nature of chemical reactivity. Accordingly, the reactivity of weakly coordinating anions (WCA), usually used to stabilized cationic super electrophiles are of fundamental interest. When a variety of WCA are known to form stable σ‐complexes with a proton, inducing Brønsted super acidity, bis‐coordinated weak‐coordinated anions are much more elusive and considered as long‐sought reactive species. In this work, the chemistry of borylated sulfate, triflimidate and triflate anions were scouted in details with the aim of synthetizing the unique analogs of protonated Brønsted superacids. Those complexes were formed by successive borylation with a 9‐boratriptycene derived Lewis super acid paired with a weak coordinated anion, characterized in solution and in the solid state and exhibit unique structures and reactivities.
The Origin of Catalysis and Regioselectivity of Lewis Acid‐Catalyzed Diels‐Alder Reactions with Tropone**
Authors: Tiekink Eveline H. , Vermeeren Pascal , Hamlin Trevor A.
Published: April 2023

We have studied the uncatalyzed and Lewis acid (LA)‐catalyzed cycloaddition reaction between tropone and 1,1‐dimethoxyethene using dispersion‐corrected relativistic density functional theory (DFT). The LA catalysts BF3, B(C6H5)3, and B(C6F5)3efficiently accelerate both the competing [4+2] and [8+2] cycloaddition reactions by lowering the activation barrier up to 12 kcal mol−1compared to the uncatalyzed reaction. Our study reveals that the LA catalyst promotes both cycloaddition reaction pathways byLUMO‐lowering catalysisand demonstrates thatPauli‐lowering catalysisis not always the operative catalytic mechanism in cycloaddition reactions. Judicious choice of the LA catalyst can effectively impart regiocontrol of the cycloaddition: B(C6H5)3furnishes the [8+2] adduct while B(C6F5)3yields the [4+2] adduct. We discovered that the regioselectivity shift finds its origin in the ability of the LA to absorb distortion by adopting a trigonal pyramidal geometry around the boron atom.
Exposure‐Response Analysis to Assess the Concentration‐QTc Relationship of Iberdomide
Authors: Cheng Yiming , Gaudy Allison , Liu Liangang , Ye Ying , Thomas Michael , Xue Yongjun , Zhou Simon , Li Yan
Published: April 2023

Iberdomide is an orally available cereblon‐modulating agent being developed for the treatment of hematologic malignancies and autoimmune‐mediated diseases. To assess the potential concentration‐QTc relationship in humans and to ascertain or exclude a potential QT effect by iberdomide, a plasma concentration and ΔQTcF (change from baseline of corrected QT interval using the Fridericia formula) model of iberdomide was developed. Iberdomide concentration and paired high‐quality, intensive electrocardiogram signal from a single‐ascending‐dose study in healthy subjects (N = 56) were included in the analysis. The primary analysis was based on a linear mixed‐effect model with ΔQTcF as the dependent variable; iberdomide plasma concentration and baseline QTcF as continuous covariates; treatment (active or placebo) and time as a categorical factor; and a random intercept per subject. The predicted change from baseline and placebo corrected (ΔΔQTcF) at the observed geometric mean maximum plasma concentration and 2‐sided 90% confidence intervals at different dose levels were calculated. The upper bound of the 90% confidence interval of the model‐predicted ΔΔQTcF effect at maximum concentration from the supratherapeutic dose of 6 mg (2.54 milliseconds) is <10‐millisecond threshold, suggesting that iberdomide does not have a clinically relevant QT prolongation liability.
An anomaly detection on blockchain infrastructure using artificial intelligence techniques: Challenges and future directions – A review
Authors: Chithanuru Vasavi , Ramaiah Mangayarkarasi
Published: April 2023

Recently, Blockchain cryptographic distributed transaction ledger technology finds its usage in many applications. The application's ledgers implemented through Blockchain, ensures tamper‐proof transactions, and in turn the applications became robust enough against cyber‐attack But still adversaries put forward their efforts in detecting the vulnerabilities in the infrastructure to execute their ill intent. In the literature, many counter measures techniques are presented to address the security breaches on the Blockchain. Detecting as well mitigating from the possible anomalies against on blockchain infrastructure through AI techniques is the greatest attempt of this article, and which is much needed now. Hence, this review article enlightens the readers with the essence of cyber security, the security aspects of Blockchain, its infrastructure vulnerabilities, various Blockchain‐enabled use cases along with the their challenges. Primarily, anomaly detection on Blockchain infrastructure through Artificial Intelligence Techniques is focused. A detailed analysis of Artificial Intelligence Techniques in detecting the anomalies with the help of Blockchain and also how these two technologies complement each other was demonstrated with the help of suitable use cases. The merits, challenges along with the possible future directions, while integrating Blockchain with Artificial Intelligence Techniques are presented for the benefit of research community.
g‐B3C2N3: A Potential Two Dimensional Metal‐free Photocatalyst for Overall Water Splitting**
Authors: Karmakar Sreejani , Adhikary Souren , Dutta Sudipta
Published: April 2023

Based on hybrid density functional theory (DFT) calculations, we propose a new two‐dimensional (2D) B‐C‐N material, graphitic‐
(g‐
), with the promising prospect of metal‐free photocatalysis. We find it to be a near ultraviolet (UV) absorbing direct band gap (3.69 eV) semiconductor with robust dynamical and mechanical stability. Estimating the band positions with respect to water oxidation and hydrogen reduction potential levels along with a detailed analysis of reaction mechanism of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), we observe that g‐
monolayer can be efficiently used for hydrogen fuel generation over entire pH range as well as for spontaneous water splitting at basic pH range. Upon biaxial strain application, band positions get realigned along with the free energy change that is involved in HER and OER. Consequently, operational range of pH for OER gets broadened and the proposed material exhibits the ability to perform spontaneous and simultaneous oxidation and reduction even in neutral pH. The combination of pH variation and applied strain can be used as a key to control the reducing and/or oxidizing abilities precisely for diverse photocatalytic reactions to attain environmental sustainability.
The effectiveness of a day hospital mentalization‐based therapy programme for adolescents with borderline personality traits: Findings from Touchstone—Child and Adolescent Mental Health Service
Authors: Gilbey Dylan , Brealey Georgia , Mateo‐Arriero Irene , Waters Zoe , Ansell Megan , Janse van Rensburg Elmie , De Gouveia Belinelo Patricia , Milroy Helen , Pace Giulia , Runions Kevin , Salmin Ivan , Woolard Alix
Published: April 2023

Background

Individuals with borderline personality disorder (BPD) are at a substantial risk of harm to themselves and others, experience high levels of functional impairment and typically are high users of tertiary healthcare to address their mental health concerns. As indicators for BPD typically emerge in adolescence, a day therapy service in Bentley, Western Australia, Touchstone Child and Adolescent Mental Health Service (CAMHS), was developed as an intensive intervention for adolescents with indicators for BPD and its associated symptomology. Touchstone utilizes mentalization‐based therapy (MBT) in a therapeutic community setting, where the current study sought to document the anecdotal outcomes using the data provided at Touchstone, to enable a greater understanding of this treatment approach for adolescents with indicators for BPD.

Method

Forty‐six participants attended the Touchstone programme between 2015 and 2020. The programme involved 6 months of MBT (group and individual), occupational therapy, education and creative therapies. Measures of self‐injury, mood and emergency department presentations were collected pre‐ and post‐programme.

Results

Results indicate that participants show a reduction in non‐suicidal acts and thoughts, as well as a reduction in negative moods and feelings from pre‐Touchstone to post‐Touchstone. There is also a decrease in participant presentation to tertiary emergency departments for mental health concerns.

Conclusions

The current study shows evidence for the efficacy of Touchstone as an MBT therapeutic community intervention to reduce symptoms of emerging BPD and effectively reduce presentations to emergency departments for mental health presentations, alleviating pressure on tertiary hospitals and reducing economic impact of adolescents within this demographic.
Intraindividual variability and emotional change as predictors of sudden gains in imagery rescripting and EMDR for PTSD in adult survivors of childhood abuse
Authors: Kuck Sascha , Arntz Arnoud , Rameckers Sophie A. , Lee Christopher W. , Boterhoven de Haan Katrina L. , Fassbinder Eva , Morina Nexhmedin
Published: April 2023

Sudden gains, defined as large and stable improvements in symptom severity during psychological treatment, have consistently been found to be associated with better outcomes across treatments and diagnoses. Yet, insights on coherent predictors of sudden gains and on emotional changes around sudden gains in post‐traumatic stress disorder (PTSD) are lacking. We aimed at replicating a measure of intraindividual variability as a predictor for sudden gains and testing its independence from change during treatment. Furthermore, we expected changes in emotions of guilt, shame and disgust prior to sudden gains to predict sudden gains. Data from a pre‐registered randomized controlled trial (RCT) of eye‐movement desensitization and reprocessing (emdr) and Imagery Rescripting (ImRs) for PTSD in 155 adult survivors of childhood abuse were used. Intraindividual variability of PTSD symptoms in both treatments did not predict sudden gains status and was not independent of change during treatment. In the EMDR condition, levels of shame during treatment predicted sudden gains and shame decreased shortly before a sudden gain in both treatments. Reductions in all emotions during sudden gains were significantly higher for participants with sudden gains than for comparable intervals in non‐sudden gainers. Our findings do not support the predictive validity of intraindividual variability for sudden gains. The decrease of guilt, shame and disgust during sudden gains warrants further research on their role as a mechanism of treatment change for PTSD.
Living through war: An oral history of civilians in Sudan
Authors: Rothbart Daniel , Korostelina Karina , Gjeloshi Beltina
Published: April 2023

Civilians in Sudan have been devastated by wars for decades, including civil wars that occurred from 1956 to 1972 and from 1983 to 2005, and wars continuing to this day in certain regions. With this article, we offer the findings of an oral history project that showcases the testimony of 116 Sudanese from the following three regions: Darfur, the Nuba Mountains and the Blue Nile state. We focused on their experiences of war and their vision of a just future for Sudan. After presenting summaries of the wars in these regions (Section 1), we identify the project's methodology (Section 2). The respondents' testimony is then analyzed thematically as follows: (a) life before war, (b) experiences of war, (c) becoming refugees, (d) war's impact, and (e) vision of justice in Sudan (Section 3). We then interpret the respondents' vision of justice as expressions of their agency in striving to overcome the systemic inequalities that have ravaged this war‐torn nation. Our analysis reveals the complexity of the respondents' notions of justice as inseparable from peace. Long‐term peace necessities the realization of justice that cannot be achieved without long‐term peace.
Mg2+ Ion Pre‐Insertion Boosting Reaction Kinetics and Structural Stability of Ammonium Vanadates for High‐Performance Aqueous Zinc‐Ion Batteries
Authors: Tang Han , Chao Feiyang , Luo Hongyu , Yu Kesong , Wang Juan , Chen Huibiao , Jia Runmin , Xiong Fangyu , Pi Yuqiang , Luo Ping , An Qinyou
Published: April 2023

Aqueous zinc‐ion batteries (AZIBs) attract much attention owing to their high safety, environmentally friendliness and low cost. However, the unsatisfactory performance of cathode materials is one of the unsolved important factors for their widespread application. Herein, we report NH4V4O10 nanorods with Mg2+ ion preinsertion (Mg‐NHVO) as a high‐performance cathode material for AZIBs. The preinserted Mg2+ ions effectively improve the reaction kinetics and structural stability of NH4V4O10 (NHVO), which are confirmed by electrochemical analysis and density functional theory calculations. Compared with pristine NHVO, the intrinsic conductivity of Mg‐NHVO is improved by 5 times based on the test results of a single nanorod device. Besides, Mg‐NHVO could maintain a high specific capacity of 152.3 mAh g−1 after 6000 cycles at the current density of 5 A g−1, which is larger than that of NHVO (only exhibits a low specific capacity of 30.5 mAh g−1 at the same condition). Moreover, the two‐phase crystal structure evolution process of Mg‐NHVO in AZIBs is revealed. This work provides a simple and efficient method to improve the electrochemical performance of ammonium vanadates and enhances the understanding about the reaction mechanism of layered vanadium‐based materials in AZIBs.
Global differences in acute heart failure treatment: analysis of the STRONG‐HF site feasibility questionnaire
Authors: Novosadova Maria , Gianchetti Lauren , Takagi Koji , Morishetty Priyanka , Gaeta Lauren , Edwards Christopher , Davison Beth A. , Picod Adrien , Mebazaa Alexandre , Cotter Gad
Published: April 2023

Aims

Acute heart failure (AHF) has an impact on human health worldwide. Despite guidelines for treatment and management of AHF, mortality rates remain high. The main objective of this study was to compare standard in‐hospital treatment and management of AHF against current clinical guidelines and variations across regions.

Methods

Between February 2018 and May 2021, investigators were approached to participate in the STRONG‐HF study. The lead investigator at 158 sites in 20 countries completed a site feasibility questionnaire. Sites were grouped by country into five different regions: Africa and the Middle East, Eastern Europe, Russia, South America, and Western Europe.

Results

According to the questionnaires, there are large differences in how patients present due to AHF and where in the hospital they are treated. There were significant differences in reported percentage of AHF patients receiving angiotensin converting enzymes inhibitors across the regions (P < 0.001), mostly due to prescription of more angiotensin II receptor blockers and angiotensin receptor‐neprilysin inhibitors in South America and Western Europe. Reported beta‐blocker use was high across all of the regions. Device therapy and percutaneous interventions were more common in Europe. Sites reported a 5 to 8 day length of stay, while in Russia most have a 10 to 12 day length of stay. Regions reported that AHF patients follow up with a community cardiologist or general practitioner post‐discharge, although follow‐up was commonly more than 1 month post discharge, and not all sites had the capability to measure natriuretic peptides post discharge.

Conclusions

In this analysis of feasibility questionnaires, most sites reported general adherence to ESC guidelines for treatment and management of AHF patients although percutaneous and device therapy was less common outside Europe and follow‐up after discharge took place late and was not as extensive as recommended. There were wide variations seen within and across regions in some areas.
Polyamides Derived from Terpenes: Advances in Their Synthesis, Characterization and Applications
Authors: Winnacker Malte
Published: April 2023

Polyamides are very important polymers, with applications from commodities up to high‐performance materials for, for example, fibers or for the biomedical sector. Nowadays, still most of them are synthesized from fossil resources. With regards to sustainability and bioeconomy, and especially regarding the new structures and properties that can thus be achieved, the preparation of polyamides (PAs) from natural precursors is getting more and more important. For this, especially the utilization of terpenes, a large and important group of natural products with different functions in nature (regulators, defense signals, etc.), is important, which is described herein. Similar approaches are interesting from a scientific point of view regarding, for example, structure‐function‐relations, but also with regards to different applications as, for example, high‐performance or biomedical materials.

Practical applications: Terpene‐based polyamides can find many applications, from commodities up to high‐performance fibers and special materials in (bio)medicine, for example, drug delivery, tissue engineering, etc.
Influence of carbon on the dynamic changes in Co oxidation state of Ba0.5Sr0.5Co0.8Fe0.2O3‐δ perovskite catalyst during the oxygen reduction and evolution reactions
Authors: Beall Casey E. , Fabbri Emiliana , Clark Adam H. , Yüzbasi Nur Sena , Graule Thomas , Schmidt Thomas J.
Published: April 2023

Carbon is often used as a conductive additive in catalyst layers to increase conductivity and catalytic activity. However, the effect of carbon addition to perovskites on the oxygen reduction (ORR) and oxygen evolution (OER) reactions is convoluted. In this work, composites of perovskite Ba0.5Sr0.5Co0.8Fe0.2O3‐δ (BSCF) and conductive additives, carbon and indium doped tin oxide are compared. It is found that the conductive additives have differing effects on the ORR and OER activities and cobalt redox behavior, with carbon having a much more significant effect. In order to elucidate further these differences between BSCF and BSCF/carbon, operando X‐ray absorption spectroscopy (XAS) is measured simultaneously with cyclic voltammetry into the ORR and OER regions and the continuous changes in the Co oxidation state are observed with high time resolution. We theorize that carbon is enhancing the Co redox activity and as a result, the ORR and OER activities are likewise improved.

image
Application of response surface approach to optimize CI engine parameters fuelled by newly developed waste cooking biodiesel infused with Al2O3 nanoparticle
Authors: Bhan Suraj , Gautam Raghvendra , Singh Pushpendra
Published: April 2023

In the present study, newly developed waste cooking biodiesel (B20) with nanoparticles (Al2O3) was tested to optimize the response of a CRDI single‐cylinder four‐stroke VCR engine at various input parameters. A response surface methodology (RSM) was used to investigate the impact of various input parameters, such as injection pressure (IP), load, compression ratio (CR), and nanoparticle concentration as fuel additives on engine responses, including brake thermal efficiency (BTE), specific fuel consumption (SFC), carbon dioxide (CO), hydrocarbon (HC), and oxide of nitrogen (NOX) emissions. The RSM found the best suitable value of all input parameters at which the engine produced maximum performance and minimum emissions. Accordingly, the optimal setting of all input parameters was identified as a nano biofuel blend ratio of 1.10, IP of 656 bar, CR of 18.50, and a load of 7.10 kg. At this combination of input parameters, the optimal BTE, SFC, CO, HC, and NOx are 23.6%, 0.3461 kg/kWh, 0.0281%, 25.3756 ppm, and 536.41 ppm respectively. The predicted optimum value from RSM is compared with the experimental value for validity and found a fair agreement.
Energy‐compatible modulating functions for the stochastic generation of fully non‐stationary artificial accelerograms and their effects on seismic site response analysis
Authors: Genovese Federica , Biondi Giovanni , Cascone Ernesto , Muscolino Giuseppe
Published: April 2023

The reliability of non‐linear dynamic analysis aimed to predict the seismic performance of structural and geotechnical systems, as well as their dynamic interaction, is significantly affected by the selection of suitable input motions. Several procedures for selecting actual earthquake records compatible with the seismic hazard at the site of interest and for evaluating synthetic accelerograms consistent with a seismological framework are available in the literature. However, the degree of uncertainty affecting these approaches might lead to unreliable performance predictions especially for strongly non‐linear problems, such as those involving the response of soils to cyclic and dynamic loading. In this vein, the paper presents a procedure for generating fully non‐stationary ground motions ensuring energy compatibility with a target motion. Two different approaches have been introduced: i) the time window method based on the central finite difference approach and ii) the simplified intensity‐compatible approach in which a closed form expression is provided to evaluate a modulating function that depends on the Arias intensity and on the strong motion duration of a target motion. To highlight the reliability and the accuracy of the proposed procedure, several sets of spectrum‐compatible artificial accelerograms, generated starting from a rock outcropping motion, were used as input motions in a series of one‐dimensional site response analyses. The analysis results are presented and discussed in the paper highlighting the influence of the main features of the proposed generation procedure on the variability of the computed site response.