bluuebunny/crossref_metadata_2025 huggingface dataset:
Modulating Emission of Boric Acid into Highly Efficient and Color‐Tunable Afterglow via Dehydration‐Induced Through‐Space Conjugation
Authors: Zhang Zhen , Wang Zhenguang , Liu Xiao , Shi Yu‐e , Li Zhiqiang , Zhao Yanli
Published: March 2023

Inorganic boric acid (BA) is generally not considered an efficient afterglow material, and several groups have reported its extremely weak room‐temperature phosphorescence (RTP) in the blue spectral region. It is discovered that heat treatment of BA results in increased afterglow intensity (27‐fold increase) and prolonged emission lifetime (from 0.83 to 1.59 s), attributed to enhanced through‐space conjugation (TSC) of BA. The afterglow intensity of BA can be increased further (≈415 folds) by introducing p‐hydroxybenzoic acid (PHA), which contains a conjugated molecular motif, to further promote the TSC of the BA system. This combination results in the production of afterglow materials with a photoluminescence quantum yield of 83.8% and an emission lifetime of 2.01 s. In addition, a tunable multicolor afterglow in the 420–490 nm range is achieved owing to the enhancement of the RTP and thermally activated delayed fluorescence of PHA, where BA exerts a confinement effect on the guest molecules. Thus, this study demonstrates promising afterglow materials produced from extremely abundant and simple precursor materials for various applications.
Electronic Coupling of Metal‐to‐Insulator Transitions in Nickelate‐Based Heterostructures
Authors: Varbaro Lucia , Mundet Bernat , Domínguez Claribel , Fowlie Jennifer , Georgescu Alexandru B. , Korosec Lukas , Alexander Duncan T.L. , Triscone Jean‐Marc
Published: March 2023

In rare earth nickelates, the metal‐to‐insulator transition observed as a function of temperature can be described using an electronic and a structural order parameter. The electronic one is linked to the electronic disproportionation observed below the transition temperature and the structural one characterizes the breathing mode that develops in the low temperature phase. Here SmNiO3/NdNiO3 superlattices are grown with insulating LaAlO3 spacer layers to study the unusual coupling of metal‐to‐ insulator transitions observed at SmNiO3/NdNiO3 interfaces and determine the role of the two order parameters. Temperature‐dependent transport measurements reveal that a single unit cell of LaAlO3 inserted between SmNiO3 and NdNiO3 leads to a complete decoupling of the metal‐to‐insulator transitions suggesting that the order parameter controlling the coupling is the electronic one.
Development of a Triboelectric Nanogenerator for Joining of Silver Nanorods
Authors: Jalili Mohammad Amin , Karimzadeh Fathallah , Enayati Mohammad Hossein , Kalali Ehsan Naderi , Kheirabadi Noushin Raeisi
Published: March 2023

On account of their excellent properties, 2D nanostructures beyond graphene, such as MoS2, have extensive applications. Given their quantum confinement effects, MoS2 monolayers could efficiently trap electrons as an intermediate layer between friction and electrode in triboelectric nanogenerators (TENGs) and successfully hinder their recombination and air breakdown, increasing their output. With the help of this phenomenon, a TENG called PS+PS/MoS2‐AHSG (PPMA) TENG is fabricated with an open‐circuit voltage of ≈1200 V and a short‐circuit current of 0.74 mA, and a maximum power of 11.27 mW. PPMA TENG consists of transparent polystyrene (PS) and PS/MoS2 as negative contact and storage layers. Also, the positive layer is a novel Alyssum homolocarpum seed gum (AHSG) layer, which is a natural polymer. This TENG could successfully light up 115 commercial light‐emitting diodes. PPMA TENG exhibits exceptional mechanical robustness so that after a decrease in its outputs, heating would activate the self‐healing mechanism, and the surface charge density could reach from 0.428 to 0.874 µC m−2, which is 82% of the initial value. To demonstrate the practical applications of PPMA TENG as a high‐voltage sustainable power source, it is successfully employed to perform a dielectrophoretic assisted welding of silver nanorods.
Tailoring Active Cu2O/Copper Interface Sites for N‐Formylation of Aliphatic Primary Amines with CO2/H2
Authors: Dai Xingchao , Li Teng , Wang Bin , Kreyenschulte Carsten , Bartling Stephan , Liu Shujuan , He Dongcheng , Yuan Hangkong , Brückner Angelika , Shi Feng , Rabeah Jabor , Cui Xinjiang
Published: March 2023

Heterogeneously catalyzed N‐formylation of amines to formamide with CO2/H2 is highly attractive for the valorization of CO2. However, the relationship of the catalytic performance with the catalyst structure is still elusive. Herein, mixed valence catalysts containing Cu2O/Cu interface sites were constructed for this transformation. Both aliphatic primary and secondary amines with diverse structures were efficiently converted into the desired formamides with good to excellent yields. Combined ex and in situ catalyst characterization revealed that the presence of Cu2O/Cu interface sites was vital for the excellent catalytic activity. Density functional theory (DFT) calculations demonstrated that better catalytic activity of Cu2O/Cu(111) than Cu(111) is attributed to the assistance of oxygen at the Cu2O/Cu interface (Ointer) in formation of Ointer‐H moieties, which not only reduce the apparent barrier of HCOOH formation but also benefit the desorption of the desired N‐formylated amine, leading to high activity and selectivity.
A Dissipative Reaction Network Drives Transient Solid–Liquid and Liquid–Liquid Phase Cycling of Nanoparticles
Authors: Roy Soumendu , Gravener Laura , Philp Douglas , Kay Euan R.
Published: March 2023

Transient states maintained by energy dissipation are an essential feature of dynamic systems where structures and functions are regulated by fluxes of energy and matter through chemical reaction networks. Perfected in biology, chemically fueled dissipative networks incorporating nanoscale components allow the unique properties of nanomaterials to be bestowed with spatiotemporal adaptability and chemical responsiveness. We report the transient dispersion of gold nanoparticles in water, powered by dissipation of a chemical fuel. A dispersed state that is generated under non‐equilibrium conditions permits fully reversible solid–liquid or liquid–liquid phase transfer. The molecular basis of the out‐of‐equilibrium process is reversible covalent modification of nanoparticle‐bound ligands by a simple inorganic activator. Activator consumption by a coupled dissipative reaction network leads to autonomous cycling between phases. The out‐of‐equilibrium lifetime is tunable by adjusting the pH value, and reversible phase cycling is reproducible over several cycles.
Enhanced Carrier Diffusion Enables Efficient Back‐Contact Perovskite Photovoltaics
Authors: Zhao Boya , Gillan Lara V. , Scully Andrew D. , Chesman Anthony S. R. , Tan Boer , Lin Xiongfeng , Liu Jingying , Rietwyk Kevin J. , Deng Siqi , Bailey Christopher , Cheng Yi‐Bing , McCamey Dane R. , Bach Udo
Published: March 2023

Back‐contact architectures offer a promising route to improve the record efficiencies of perovskite solar cells (PSCs) by eliminating parasitic light absorption. However, the performance of back‐contact PSCs is limited by inadequate carrier diffusion in perovskite. Here, we report that perovskite films with a preferred out‐of‐plane orientation show improved carrier dynamic properties. With the addition of guanidine thiocyanate, the films exhibit carrier lifetimes and mobilities increased by 3–5 times, leading to diffusion lengths exceeding 7 μm. The enhanced carrier diffusion results from substantial suppression of nonradiative recombination and improves charge collection. Devices using such films achieve reproducible efficiencies reaching 11.2 %, among the best performances for back‐contact PSCs. Our findings demonstrate the impact of carrier dynamics on back‐contact PSCs and provide the basis for a new route to high‐performance back‐contact perovskite optoelectronic devices at low cost.
Influence of Composition of Nickel‐Iron Nanoparticles for Abiotic CO2 Conversion to Early Prebiotic Organics
Authors: Beyazay Tuğçe , Ochoa‐Hernández Cristina , Song Youngdong , Belthle Kendra S. , Martin William F. , Tüysüz Harun
Published: March 2023

Abiotic synthesis of formate and short hydrocarbons takes place in serpentinizing vents where some members of vent microbial communities live on abiotic formate as their main carbon source. To better understand the catalytic properties of Ni−Fe minerals that naturally exist in hydrothermal vents, we have investigated the ability of synthetic Ni−Fe based nanoparticular solids to catalyze the H2‐dependent reduction of CO2, the first step required for the beginning of pre‐biotic chemistry. Mono and bimetallic Ni−Fe nanoparticles with varied Ni‐to‐Fe ratios transform CO2 and H2 into intermediates and products of the acetyl‐coenzyme A pathway—formate, acetate, and pyruvate—in mM range under mild hydrothermal conditions. Furthermore, Ni−Fe catalysts converted CO2 to similar products without molecular H2 by using water as a hydrogen source. Both CO2 chemisorption analysis and post‐reaction characterization of materials indicate that Ni and Fe metals play complementary roles for CO2 fixation.
Small Data Can Play a Big Role in Chemical Discovery
Authors: Shalit Peleg Hadas , Milo Anat
Published: March 2023

The chemistry community is currently witnessing a surge of scientific discoveries in organic chemistry supported by machine learning (ML) techniques. Whereas many of these techniques were developed forbig dataapplications, the nature of experimental organic chemistry often confines practitioners to small datasets. Herein, we touch upon the limitations associated withsmall datain ML and emphasize the impact of bias and variance on constructing reliable predictive models. We aim to raise awareness to these possible pitfalls, and thus, provide an introductory guideline for good practice. Ultimately, we stress the great value associated with statistical analysis ofsmall data, which can be further boosted by adopting a holistic data‐centric approach in chemistry.
A Facile Strategy for the Development of Recyclable Multifunctional Liquid Crystal Polymers via Post‐Polymerization Modification and Ring‐Opening Metathesis Polymerization
Authors: Zhao Xin , Chen Yan , Peng Bo , Wei Jia , Yu Yanlei
Published: March 2023

Post‐polymerization modification (PPM) offers a versatile approach for engineering multifunctional polymers, but this advantage has not been fully exploited to fabricate multifunctional liquid crystal polymers (LCPs). Here, we design a facile synthetic approach towards multifunctional LCP by combining the ring‐opening metathesis polymerization (ROMP) with PPM, in which ROMP helps to prepare a reactive LCP precursor with high molecular weight, and PPM provides a facilitation to introduce functional groups into the precursor. Consequently, a photo‐ and humidity‐responsive linear LCP (LLCP) is demonstrated to show the potential of this synthetic strategy to diversify functions of the LCPs. Under light irradiation and humidity changes, the deformation modes of the LLCP films are converted to complex shapes (bending, twisting, and curling). The obtained dual‐responsive LLCP with high molecular weight possesses excellent processability and recyclability, making it possible to construct 3D shape actuators with programmable deformation behaviors under light/humidity.
Cyclopentylmethyl Ether, a Non‐Fluorinated, Weakly Solvating and Wide Temperature Solvent for High‐Performance Lithium Metal Battery
Authors: Zhang Han , Zeng Ziqi , Ma Fenfen , Wu Qiang , Wang Xinlan , Cheng Shijie , Xie Jia
Published: March 2023

While recent work demonstrates the advantages of weakly solvating solvents in enhancing the cyclability of LMBs, both new designs and design strategies for high performance weakly solvating solvent, especially physicochemical properties, are still lacking. Here, we propose a molecular design to tune the solvating power and physicochemical properties of non‐fluorinated ether solvent. The resulting cyclopentylmethyl ether (CPME) have a weak solvating power and wide liquid‐phase temperature range. By optimizing the salt concentration, the CE is further promoted to 99.4 %. Besides, the improved electrochemical performance of Li−S battery in CPME‐based electrolytes is obtained at −20 °C. The Li||LFP (17.6 mg cm−2) battery with developed electrolyte maintains >90 % of the original capacity over 400 cycles. Our design concept for solvent molecule provides a promising pathway to non‐fluorinated electrolytes with weakly solvating power and wide temperature window for high‐energy‐density LMBs.
Carbazole‐Dendronized Luminescent Radicals
Authors: Xiaotian Rui , Ota Wataru , Sato Tohru , Furukori Minori , Nakayama Yasuo , Hosokai Takuya , Hisamura Eri , Nakamura Kazuhiro , Matsuda Kenshiro , Nakao Kohei , Monkman Andrew P. , Albrecht Ken
Published: March 2023

A series of carbazole‐dendronized tris(2,4,6‐trichlorophenyl)methyl (TTM) radicals have been synthesized. The photophysical properties of dendronized radicals up to the fourth generation were compared systematically to understand how structure–property relationships evolve with generation. The photoluminescence quantum yield (PLQY) was found to increase with the increasing generation, and the fourth generation (G4TTM) in cyclohexane solution showed a PLQY as high as 63 % at a wavelength of 627 nm (in the deep‐red region) from the doublet state. The dendron modification strategy also showed a blue‐shift of the emission on increasing the generation number, and the photostability was also increased compared to the bare TTM radical.
Organic pH Buffer for Dendrite‐Free and Shuttle‐Free Zn‐I2 Batteries
Authors: Lyu Yanqiu , Yuwono Jodie A. , Wang Pengtang , Wang Yanyan , Yang Fuhua , Liu Sailin , Zhang Shilin , Wang Baofeng , Davey Kenneth , Mao Jianfeng , Guo Zaiping
Published: March 2023

Aqueous Zn‐Iodine (I2) batteries are attractive for large‐scale energy storage. However, drawbacks include, Zn dendrites, hydrogen evolution reaction (HER), corrosion and, cathode “shuttle” of polyiodines. Here we report a class of N‐containing heterocyclic compounds as organic pH buffers to obviate these. We evidence that addition of pyridine /imidazole regulates electrolyte pH, and inhibits HER and anode corrosion. In addition, pyridine and imidazole preferentially absorb on Zn metal, regulating non‐dendritic Zn plating /stripping, and achieving a high Coulombic efficiency of 99.6 % and long‐term cycling stability of 3200 h at 2 mA cm−2, 2 mAh cm−2. It is also confirmed that pyridine inhibits polyiodines shuttling and boosts conversion kinetics for I−/I2. As a result, the Zn‐I2 full battery exhibits long cycle stability of >25 000 cycles and high specific capacity of 105.5 mAh g−1 at 10 A g−1. We conclude organic pH buffer engineering is practical for dendrite‐free and shuttle‐free Zn‐I2 batteries.
Alkali‐Metal‐Alkoxide Powered Zincation of Fluoroarenes Employing Zinc Bis‐Amide Zn(TMP)2
Authors: Judge Neil R. , Hevia Eva
Published: March 2023

Reminiscent of Lochmann‐Schlosser superbase recipes, the addition of two molar equivalents of KOtBu to Zn(TMP)2 (TMP=2,2,6,6‐tetramethylpiperidide) transforms this mild zinc bis‐amide base to a powerful metalating agent able to perform facile regioselective zincation of a wide range of sensitive fluoroarenes. Structural authentication of the intermediates post Zn−H exchange demonstrates activation of both TMP groups to form a range of higher order bis‐aryl potassium zincates, isolable as solids and further functionalized in electrophilic interception reactions. Studies assessing the role of KOtBu reveal that the first equivalent undergoes co‐complexation with Zn(TMP)2, enabling kinetic activation of the amide groups; whereas the second equivalent stabilizes the metalated intermediate preventing ligand redistribution. Showcasing its metalating power, this bimetallic KOtBu/Zn(TMP)2 partnership, can effect zincation of toluene and benzene at room temperature.
Hydrogen‐Atom‐Transfer‐Initiated Radical/Polar Crossover Annulation Cascade for Expedient Access to Complex Tetralins
Authors: Johnson Lucas K. , Barnes Griffin L. , Fernandez Sebastian A. , Vanderwal Christopher D.
Published: March 2023

A radical/polar crossover annulation between allyl‐substituted arenes and electron‐deficient alkenes is described. Cobalt‐catalyzed hydrogen atom transfer (HAT) facilitates tandem radical C−C bond formation that generates functionalized tetralin products in the face of potentially problematic hydrofluorination, hydroalkoxylation, hydrogenation, alkene isomerization, and radical polymerization reactions. The reactions proceed under mild conditions that tolerate many functional groups, leading to a broad substrate scope. This powerful ring‐forming reaction very quickly assembles complex tetralins that are the formal products of the largely infeasible Diels–Alder cycloadditions of styrenes.
Identification of Turkish extra virgin olive oils produced in different regions by using NMR (1H and 13C) and IRMS (13C/12C)
Authors: Sevim Didar , Köseoğlu Oya , Ertaş Hasan , Özdemir Durmuş , Ulaş Mehmet , Günnaz Salih , Çelenk Veysel Umut
Published: March 2023

Isotope ratio mass spectroscopy (IRMS) and nuclear magnetic resonance (NMR) spectroscopy techniques are two of the analytical methods that are used to characterize food products. The aim of this study is to classify extra virgin olive oil (EVOO) samples collected from different regions of Turkey based on 1H and 13C NMR spectra along with IRMS δ13C carbon isotope ratio data by using chemometrics multivariate data analysis methods. A total of 175 EVOO samples were analyzed in 2014/15 and 2015/16 harvest seasons. Multivariate classification and clustering models were used to identify geographical and botanical origins of the EVOOs. IRMS results showed that there was no significant difference in terms of δ13C values between the years in terms of harvest year (p > 0.05), only extraction phase and variety were statistically significant factors (p < 0.05). The interactions of the factors showed that the harvest year × variety interaction is important. The outcomes of this research clearly indicated that considering the partial least squares discriminant analysis result with NMR spectra, the percent success of the model in the South Marmara, North Aegean, and South Aegean region samples were 95%, 95.7%, and 96.4% in the model set, respectively. The results showed that by using classification and clustering models, geographic marking and labeling of these oils can be carried out regardless of differences in year and production systems (2 and 3 phase extraction system) according the NMR analysis.
Why are coauthored academic articles more cited: Higher quality or larger audience?
Authors: Thelwall Mike , Kousha Kayvan , Abdoli Mahshid , Stuart Emma , Makita Meiko , Wilson Paul , Levitt Jonathan
Published: March 2023

Collaboration is encouraged because it is believed to improve academic research, supported by indirect evidence in the form of more coauthored articles being more cited. Nevertheless, this might not reflect quality but increased self‐citations or the “audience effect”: citations from increased awareness through multiple author networks. We address this with the first science wide investigation into whether author numbers associate with journal article quality, using expert peer quality judgments for 122,331 articles from the 2014–20 UK national assessment. Spearman correlations between author numbers and quality scores show moderately strong positive associations (0.2–0.4) in the health, life, and physical sciences, but weak or no positive associations in engineering and social sciences, with weak negative/positive or no associations in various arts and humanities, and a possible negative association for decision sciences. This gives the first systematic evidence that greater numbers of authors associates with higher quality journal articles in the majority of academia outside the arts and humanities, at least for the UK. Positive associations between team size and citation counts in areas with little association between team size and quality also show that audience effects or other nonquality factors account for the higher citation rates of coauthored articles in some fields.
Exploring in vitro solubility of lamotrigine in physiologically mimetic conditions to prospect the in vivo dissolution in pediatric population
Authors: Caleffi‐Marchesini Edilainy Rizzieri , Borghi‐Pangoni Fernanda Belincanta , Macente Julia , Chiamulera‐Mantovani Priscila , Mazucheli Josmar , Cristofoletti Rodrigo , Diniz Andréa
Published: March 2023

Pediatric drugs knowledge still leaves several gaps to be filled, all the while many biopharmaceutic properties applied to adults do not work in pediatrics. The solubility in many cases is extrapolated to pediatrics; however, sometimes it may not represent the real scenario. In this context, the aim of this study was to assess the possibility of the extrapolation of the solubility data assumed for adults to children aged 2–12 years using lamotrigine (LTG) as a model. LTG showed that its solubility is dependent on the pH of the medium, no precipitate formation was seen, and biomimetic media showed a greater capacity to solubilize it. Based on the dose number (D0) in adults, the LTG was soluble in acidic pH media and poorly soluble in neutral to basic. Similar behavior was found in conditions which mimic children aged 10–12 years at a dose of 5 and 15 mg/kg. The D0 for 5‐year‐old children at a dose of 15 mg/kg showed different behaviors between biorelevant and pharmacopeial buffers media. For children aged 2–3 years, LTG appeared to be poorly soluble under both gastric and intestinal conditions. Solubility was dependent on the volume of fluid calculated for each age group, and this may impact the development of better pharmaceutical formulations for this population, better pharmacokinetic predictions in tools as PBPK, and physiologically‐based biopharmaceutics modeling, greater accuracy in the justifications for biowaiver, and many other possibilities.
Mobilization of hematopoietic stem cells with lenograstim in multiple myeloma patients: Prospective multicenter observational study (KMM122)
Authors: Jung Eun Hee , Byun Ja Min , Shin Dong‐Yeop , Do Young Rok , Jo Jae‐Cheol , Lee Sang Min , Yoon Sung‐Soo
Published: March 2023

Background

Current guidelines recommend using filgrastim or tbo‐filgrastim to mobilize hematopoietic progenitor cells in an autologous setting. However, previous studies have suggested other forms of granulocyte colony‐stimulating factor (G‐CSF) are equally efficacious, possibly with fewer leukaphereses required. Thus, we prospectively studied the efficacy of lenograstim, a glycosylated recombinant form of G‐CSF, in multiple myeloma (MM) patients.

Methods

From November 2011 to January 2020, 98 MM patients undergoing autologous stem cell transplant (ASCT) from five academic centers in Korea were enrolled. Patients were mobilized with subcutaneous lenograstim (Neutrogin®) with fixed doses of 10 μg/kg for 4 days.

Results

Most of the patients ( N  = 90, 91.8%) achieved at least the targets of 2 × 106 CD34+ cells/kg body weight, and more than half of MM patients ( N  = 57, 58.2%) reached a target of 5 × 106 CD34+ cells/kg body weight. The mobilization failure rate was 8.2% ( N  = 8). The median number of CD34 + cell/kg using G‐CSF only was 5.25 × 106/kg (range 0.49–13.47). Adverse events included transfusion (TF, N  = 53, 54.1%), bone pain ( N  = 6, 6.1%), fever ( N  = 2, 2.0%), and gastrointestinal troubles ( N  = 2, 2.0%). There were no grade 3 or 4 adverse events during mobilization. Body surface area (BSA) at mobilization and platelet TF were factors associated with CD34+ collection. Most patients achieved neutrophil ( N  = 93, 98.9%) and platelet ( N  = 89, 95.7%) engraftment.

Conclusion

Lenograstim can safely and effectively mobilize stem cells in MM autologous settings.
Is tumor necrosis a clinical prognostic factor in hepato‐biliary‐pancreatic cancers? A systematic review and meta‐analysis
Authors: Yang Siqi , Hu Haijie , Hu Yafei , Dai Yushi , Zou Ruiqi , Lv Tianrun , Li Fuyu
Published: March 2023

Background

It has been proven that tumor necrosis is associated with poor prognoses in various solid malignant tumors. However, the prognostic effect of tumor necrosis in hepato‐biliary‐pancreatic cancers is still unclear. Therefore, this study was performed to evaluate the associations of tumor necrosis with survival outcomes and clinicopathological features in patients with hepato‐biliary‐pancreatic cancers.

Methods

Based on the PRISMA statement, eligible studies were identified from PubMed, Embase, Cochrane Library, and Web of Science from inception until January 2023. The pooled hazard ratios (HRs) and 95% confidence intervals (95%CIs) were calculated to assess the connection between tumor necrosis and hepato‐biliary‐pancreatic cancers. We then choose which effects model to use to generate pooled HRs and 95% CIs, depending on data heterogeneity.

Results

In total, 6497 articles were identified, 10 of which were included in this meta‐analysis. Our results suggested that the presence of tumor necrosis predicted a poorer outcome for overall survival (HR = 1.54, 95% CI = 1.35–1.77, p < 0.001) and recurrence‐free survival (HR = 1.69, 95% CI = 1.37–2.08, p < 0.001). In addition, tumor necrosis was correlated with larger tumor size, a higher frequency of lymph node metastasis, poorer histologic differentiation, and higher recurrence and metastasis rates.

Conclusion

Our meta‐analysis suggests that hepato‐biliary‐pancreatic cancer patients with tumor necrosis have dismal survival outcomes, and that their tumors have aggressive biological behaviors. Tumor necrosis has the potential to be a promising biomarker for forecasting poor prognosis in these patients.
Burden of cancers attributable to high fasting plasma glucose in the Middle East and North Africa region, 1990–2019
Authors: Tondro Anamag Farhad , Noori Maryam , Nejadghaderi Seyed Aria , Sullman Mark J. M. , Grieger Jessica A. , Kolahi Ali‐Asghar , Safiri Saeid
Published: March 2023

Background

The present study reported the cancer deaths and disability‐adjusted life years (DALYs) that were attributable to high fasting plasma glucose (HFPG) in the Middle East and North Africa (MENA) region by country, age, sex, cancer type and Socio‐demographic Index (SDI), from 1990 to 2019.

Methods

Global Burden of Disease (GBD) 2019 data were used to report the cancer‐related deaths and DALYs that were attributable to HFPG, for all MENA countries over the period 1990–2019. The results were presented as numbers, population attributable fractions (PAFs) and rates (per 100,000) with 95% uncertainty intervals.

Results

In 2019, there were an estimated 19.8 thousand (5.5–40.2) cancer deaths attributable to HFPG in MENA, which represents 4.7% (1.3–9.3) of all cancer‐related deaths. The number of regional DALYs due to HFPG‐related cancers was 462.2 thousand (127.3–959.5), which represents 3.8% (1.1–7.6) of all cancer‐related DALYs in 2019. From 1990 to 2019, the age‐standardized DALY rate of cancers attributable to HFPG (per 100,000) grew from 56.3 (14.6–121.1) to 107.0 (29.8–220.8), which was a 90.1% (64.4–127.8) increase. In 2019, the highest age‐standardized DALY rate of cancers attributable to HFPG was in Qatar (270.4) and the lowest was in Sudan (75.3). The DALY rate of cancers attributable to HFPG increased with age, peaking for males in the 70–74 age group and for females in the 75–79 age group, and then decreased for both sexes. A broadly positive relationship was found between the national SDI and the national age‐standardized DALY rate of all cancers attributable to FPG over the measurement period.

Conclusions

The burden of HFPG‐related cancers has increased over the past three decades in MENA, and was higher than the global average in multiple age groups. Implementing a battery of preventive measures and therapeutic interventions is suggested to address the adverse effects of this modifiable risk factor.
Impact of age, antiretroviral therapy, and cancer on epigenetic aging in people living with HIV
Authors: Qing Yulan , Chan Ricky , Fu Pingfu , Cullen Jennifer , Miron Alexander , Jacobson Jeffrey M. , Pink John , Gerson Stanton L.
Published: March 2023

Background

Premature aging has been identified as a global risk factor for cancer. Causes of premature aging are multifactorial, including inflammation, infection, chronic stress, and lifestyle factors.

Method

We evaluated whether premature aging in people living with HIV (PLWH) was associated with antiretroviral therapy (ART) or the diagnosis of cancer. We used well‐established DNA methylation patterns to assess premature aging, using Horvath et al., in individuals with HIV located in Cleveland, Ohio and compared these to standardized datasets of US historical blood samples. Some of the PLWH developed cancer over time.

Results

We found that DNA methylation analysis identified accelerated aging in PLWH whereas ART therapy mitigated the advancement of DNA methylation age. A variety of cancers were observed in this population, but a cancer diagnosis was not significantly associated with more advanced DNA methylation age.

Conclusion

We find that the age acceleration detected in PLWH is mitigated by ART therapy and is not further accelerated by a diagnosis of cancer.
Long‐term survivors with desmoplastic small round cell tumor (DSRCT): Results from a retrospective single‐institution case series analysis
Authors: Giani Claudia , Radaelli Stefano , Miceli Rosalba , Gandola Lorenza , Sangalli Claudia , Frezza Anna Maria , Provenzano Salvatore , Pasquali Sandro , Bertulli Rossella , Fiore Marco , Callegaro Dario , Casanova Michela , Chiaravalli Stefano , Collini Paola , Dagrada Gian Paolo , Morosi Carlo , Zaffaroni Nadia , Casali Paolo G. , Ferrari Andrea , Gronchi Alessandro , Stacchiotti Silvia
Published: March 2023

Objective

To report on a retrospective study of primary DSRCT aiming at characterizing long‐term survivors (LTS).

Methods

All consecutive patients treated at our institution for a primary DSRCT between 2000 and 2021 were retrospectively identified. Patients received multiagent chemotherapy ± surgery ± hyperthermic intraperitoneal chemotherapy (HIPEC) ± whole abdomino‐pelvic radiotherapy (WAP‐RT) ± high‐dose chemotherapy ± maintenance chemotherapy (MC). Event‐free survival (EFS) and overall survival (OS) were estimated by Kaplan–Meier method. Patients alive, without evidence of disease at ≥36 months from diagnosis, were defined as LTS.

Results

Thirty‐eight patients were identified. All received multiagent chemotherapy; 27/38 (71%) surgery (7/27 [26%] plus HIPEC), 9/38 (24%) WAP‐RT, 12/38 (32%) MC. At a median‐follow‐up of 37 months (IQR 18–63), overall median‐EFS and median‐OS were 15 and 37 months, respectively. All events occurred within 35 months. In patients who underwent surgery, median‐EFS and median‐OS were 19 and 37 months (23 and 43 months after R0/R1, and 10 and 19 months after R2 resection), respectively. LTS were 5/38 (13%), alive at 37, 39, 53, 64, 209 months. None had liver or extra‐abdominal metastasis at diagnosis, they all received R0/R1 resection, 3/5 had WAP‐RT, 2/5 MC, 1/5 received high‐dose chemotherapy, none HIPEC.

Conclusions

In our series cure was likely achieved in 13% of DSRCT. LTS had no liver/extra‐abdominal disease, were treated with complete surgery, and possibly WAP‐RT/MC.
Effect of local treatment in patients with oligo‐recurrence after surgery of distal bile duct cancer: A bi‐institutional study
Authors: Yoon So Jeong , Hong Seung Soo , Gwon Min Jae , Shin Sang Hyun , Heo Jin Seok , Kang Chang Moo , Kim Kyung Sik , Hwang Ho Kyoung , Han In Woong
Published: March 2023

Background

Distal extrahepatic bile duct (EHBD) cancer is highly recurrent. More than 50% of patients suffer from disease relapse after curative resection. Some patients present with oligo‐recurrence which could be a single loco‐regional mass or lesions limited to a single solid organ. The aim of this study was to examine the effect of local control (surgical resection or radiofrequency ablation) on survival outcomes in patients with oligo‐recurrent distal EHBD cancer.

Methods

Data of 1219 patients who underwent surgery for distal EHBD cancer from 2000 to 2018 were retrospectively reviewed. Clinicopathological characteristics and survival outcomes of patients with recurrence were investigated. Post‐recurrence survival (PRS) was analyzed according to modalities of re‐treatment (local treatment or systemic therapy alone).

Results

Among 654 patients with recurrence, 90 patients who had oligo‐recurrence showed better recurrence‐free and overall survival than patients with non‐oligo‐recurrent disease. Lymph node ratio and perineural invasion at initial pathology, timing of recurrence, and platelet‐to‐lymphocyte ratio at recurrence were independent risk factors for PRS in the oligo‐recurrent group. Patients with local treatment for oligo‐recurrence had better 3‐ and 5‐year PRS than those with systemic treatment alone (38.3% vs. 14.1%, p = 0.04; 28.3% vs. 7.1%, p = 0.04, respectively). Recurrence within 24 months after initial surgery was the only significant factor for PRS in the local treatment group.

Conclusion

In patients with oligo‐recurrence after resection of distal EHBD cancer, post‐recurrence local treatment could improve survival outcomes, particularly for those with recurrence more than 2 years after initial resection.
Who is willing to help Ukrainian refugees and why? The role of individual prosocial dispositions and superordinate European identity
Authors: Politi Emanuele , Gale Jessica , Roblain Antoine , Bobowik Magdalena , Green Eva G.T.
Published: March 2023

In 2022, Europe experienced unprecedented citizen mobilizations to help Ukrainian refugees. Based on two parallel lines of scholarship, we examined individual prosocial dispositions and superordinate identities related to intentions to help Ukrainians. Employing a French‐speaking student sample in Belgium (N = 374), in Study 1, we showed that dispositional prosociality and European identification were both positively related to intentions to help Ukrainians. An interaction qualified these main effects, so that highly prosocial European identifiers were particularly willing to help. With a nationwide quota sample of the French‐speaking population in Belgium (N = 371), in Study 2, we identified two processes mediating the relationship of dispositional prosociality and European identification with intentions to help Ukrainians. On the one hand, dispositional prosociality was positively related to empathy with Ukrainians, which in turn predicted participants' helping intentions. On the other hand, European identification was positively related to both empathy and identity fusion with Ukrainians, which further predicted participants' helping intentions. Overall, these findings suggest that individual prosocial dispositions and superordinate identities represent two cumulative pathways to intergroup helping. Concluding, we discuss common and specific processes related to intentions to help Ukrainians, compared with other refugee groups.
Chemoproteomics Reveals That Quaternary Protoberberine Alkaloids Inhibit Telomerase Activity Oncologically by Binding to PES1
Authors: Xu Ling‐Wen , Zhang Xue‐Qian , Yan Zheng , Li Zhi‐Hong , Deng An‐Jun , Qin Hai‐Lin
Published: March 2023

Natural QPAs have anti‐cancer property. The prodrugs of QPAs synthesized in our work with significantly improved solubility showed significantly stronger activity in animal experiments. Nevertheless, the mechanism of action of QPAs for treating cancers remains poorly understood. Here, a chemoproteomic study reveals that QPAs non‐covalently and multivalently bind to PES1 in CRC cells, which impinges on the direct interaction between hTERT and hTR in the assembly of the telomerase complex, downregulates telomerase activity, and so promotes the aging process of CRC cells. This study is beneficial for us to conduct extensively the pharmaceutical chemistry research of QPAs.
HIF‐1α‐induced upregulated miR‐322 forms a feedback loop by targeting Smurf2 and Smad7 to activate Smad3/β‐catenin/HIF‐1α, thereby improving myocardial ischemia‐reperfusion injury
Authors: Dong Wei , Dong Chen , Zhu Jianbing , Zheng Yaofu , Weng Junfei , Liu Leilei , Ruan Yang , Fang Xu , Chen Jin , Liu Wenyu , Peng Xiaoping , Chen Xuanying
Published: March 2023

Myocardial ischemia/reperfusion injury (MIRI) is a major cause of heart failure after myocardial infarction. It has been reported that miR‐322 is involved in MIRI progression, while the molecular mechanism of miR‐322 in regulating MIRI progression needs to be further probed. MIRI cell model was established by oxygen‐glucose deprivation/reoxygenation (OGD/R). Cell viability was assessed using MTS assay. Flow cytometry and terminal deoxynucleotidyl transferase‐mediated dUTP nick‐end labeling staining were employed to analyze cell apoptosis. In addition, the interactions between miR‐322, Smad7/Smurf2, hypoxia‐inducible factor alpha (HIF‐1α), and β‐catenin were verified by dual‐luciferase reporter gene assay. Our results displayed that miR‐322 was significantly downregulated in OGD/R‐treated H9c2 cells, and its overexpression resulted in increased cell viability and reduced the apoptosis. Smurf2 and Smad7 were identified as the direct targets of miR‐322. Smad7 knockdown or Smurf2 knockdown increased OGD/R‐treated H9c2 cell viability and suppressed the apoptosis. Meanwhile, miR‐322 mimics abolished the mitigating effect of Smad7 or Smurf2 overexpression on MIRI. In addition, the Smad3/β‐catenin pathway was identified as the downstream pathway of Smurf2/Smad7. Moreover, it was found that HIF‐1α interacted with the miR‐322 promoter, and β‐catenin interacted with the HIF‐1α promoter to form a loop. HIF‐1α‐induced upregulated miR‐322 activated the Smad3/β‐catenin pathway by targeting Smurf2 and Smad7 to improve MIRI; meanwhile, β‐catenin/HIF‐1α formed a positive feedback loop to continuously improve MIRI.
Ormeloxifene, a nonsteroidal antifertility drug promotes megakaryocyte differentiation in leukemia cell line K562
Authors: Mishra Mukul , Singh Anil Kumar , Thacker Gatha , Upadhyay Vishal , Sanyal Sabyasachi , Trivedi Arun Kumar
Published: March 2023

Ormeloxifene (ORM) (3,4‐trans‐2,2‐dimethyl‐3‐phenyl‐4‐p‐(β‐pyrrolidinoethoxy) phenyl‐7‐methoxychroman), world's first nonsteroidal selective estrogen receptor modulator approved for contraception in India has been shown to have potential anticancer activities. Here, we show that ORM can induce megakaryocyte and myeloid (granulocytic) but not erythroid differentiation in multipotent human myeloid leukemia cell line K562. We show that ORM at an IC50 of 7.5 µM can induce morphological changes similar to megakaryocytes in K562 cells. ORM led to increase in levels of megakaryocytic differentiation markers (CD41 and CD61) as well as key transcription factors GATA1 and AML1. We further show that ORM induces megakaryocytic differentiation in K562 cells through ERK activation and induction of autophagy in a fashion similar to other known inducers of megakaryocytic differentiation such as phorbol esters. In addition, as shown earlier, we yet again observed that ORM led to activation of caspases since their inhibition through pan‐caspase inhibitor mitigated megakaryocytic differentiation as they led to significant decrease in CD41 and CD61. Because induction of megakaryocytic differentiation in K562 involves growth arrest and exit from cell cycle, we also observed an increase in levels of p21 and p27 with decrease in c‐Myc protein levels in K562 cells treated with 7.5 µM ORM for 24 and 48 h, respectively. Taken together, these findings indicate that ORM can markedly induce megakaryocytic differentiation in K562 cells.
Vascular closure after transfemoral transcatheter aortic valve replacement: Further randomized trials are justified
Authors: Hillegass William B.
Published: March 2023

Key Points

Major vascular complications (MVCs) occur in approximately 4% of contemporary transcatheter aortic valve replacements (TAVR) often related to large bore transfemoral access and vascular closure.

Plug‐based vascular closure appears to have non‐significantly lower risk of MVCs in 8 observational studies while suture‐based devices have non‐significantly lower MVCs in the 2 randomized trials.

Given the frequency of TAVR and the consequences of MVCs, larger randomized trials may better inform patient, procedural, and operator/institutional specific choice of vascular closure device.
Bioplastic film making properties of quality protein maize (QPM) zein
Authors: Baloyi Julia T. , Taylor Janet , Taylor John R. N.
Published: March 2023

Background and Objective

Quality protein maize (QPM) has abundant γ‐zein, which crosslinks itself and other zeins through disulfide bonding. The work aims to develop zein bioplastics with better functionality by using QPM zein. Physical properties of cast QPM zein films from QPM maize were compared with zein films from regular maize types and commercial zein, all without added plasticizers.

Findings

QPM zein contained 3.8% cysteine compared with 1.8%–2.7% in regular maize zeins and 1% in commercial zein and the QPM zein had a much higher proportion of γ‐zein. QPM zein films cast from glacial acetic acid (GAA) were opaque but absorbed the least liquid (≈16%) and swelled less (≈11%) after buffer immersion than the other zein films and aqueous ethanol‐cast films. Notably, the GAA‐cast QPM zein films became highly flexible after ambient storage, whereas the other zein films remained brittle.

Conclusions

The low buffer uptake and swelling of QPM zein films is attributed to crosslinking involving the cysteine‐rich γ‐zein polypeptides. Their flexibility is attributed to better solubilization of the zein in GAA and water molecules bound to the γ‐zein polypeptides acting as a plasticizer.

Significance and Novelty

QPM zein can enable the formation of flexible zein bioplastics without added plasticizers.
Exploring Zr‐Based Metal‐Organic Frameworks as Smart Electrochromic Sensors by Coordination‐Driven Surface Engineering
Authors: Huang Shan , Liu Ying , Huang Pengcheng , Wu Fang‐Ying , Mao Lanqun
Published: March 2023

As emerging stimuli‐responsive materials, electrochromic metal‐organic frameworks (MOFs) are still not utilized in sensing applications due to difficulties in water stability, facile synthesis and functionalization, and efficient translation of specific recognition events. Here, we firstly find that a Zr‐based MOF furnished with postsynthetically created viologen‐like electron‐deficient moiety was electrochromic active. With a coordination‐driven surface engineering strategy where phosphate‐containing biomolecules are tethered to Zr nodes of the MOF, fine tuning the interface electron transfer was readily achieved, thus benefitting for constructing smart electrochromic sensors through the combination of the sensitivity of electrochemistry with the visuality of colorimetry. Particularly, MOF‐coated conductive films enabled label‐free detection of phosphoproteins, and aptamer‐functionalized ones responded specifically to the target. In two cases distinct color changes allow for visual quantification. This study represents the first example of MOF‐based electrochromic sensors developed by an efficient strategy, indicating the generality to electrochromic counterparts for various sensing applications.
Stereochemical Control of Secondary Benzamide‐based BODIPY Emitters
Authors: Waly Sara M. A. , Benniston Andrew C. , Karlsson Joshua K. G. , Dixon Casey M. , Wills Corinne , Waddell Paul G. , Harriman Anthony
Published: March 2023

Aromatic amides can be used to construct light‐harvesting materials with valuable optical properties. The amide bond is formed using well‐known coupling agents in near quantitative yield, as illustrated here through the synthesis of two boron dipyrromethene derivatives bearing an amide linkage. The primary concern with acyl amides is rotation around the C−N bond, leading to cis and trans isomers. Using NMR spectroscopy, quantum chemical calculations and critical comparison to simpler benzamides, the stereochemistry of the target compounds has been addressed. The N‐cyclohexyl derivative gave diffraction quality crystals that established a trans geometry for the amide bond. Quantum chemical calculations support the trans geometry as being the lowest‐energy structure in solution but indicate that inversion of the aryl ring is an important structural feature. Indeed, rotation around the C(sp2)−C(aryl) bond has a strong influence on the solution‐phase NMR spectra. The amide connection has minimal effect on the photophysical properties.
A Template‐Free Pd2L4Cage with up to Nanomolar Affinity for Chloride in Aqueous Solutions**
Authors: Sivalingam Vellaiyadevan , Krishnaswamy Shobhana , Chand Dillip Kumar
Published: March 2023

Selective binding of chloride over the other most abundant anions in living organisms is pivotal due to its essential role in physiological functions. Herein, we report a template‐free Pd2L4cage exhibiting high selectivity for medium‐sized halides (i. e., Cl−, Br−) in water owing to the size‐discriminatory nature of the cage cavity. In pure water, this cage displays high selectivity and micromolar affinity for chloride. The cage shows no binding towards other biologically more abundant essential anions such as phosphates, carboxylates, or bicarbonate. This cage shows an unprecedented nanomolar affinity with 1 : 1 binding stoichiometry for chloride in aqueous‐DMSO media. This high affinity was achieved with the best use of traditional hydrogen bonding and electrostatic interactions, as confirmed by single‐crystal X‐ray diffraction analysis. This well‐defined cage sequestrates F−by cleaving a B−F bond in BF4−in a facile manner in a nonpolar solvent or in the presence of excess ligand. This cage also demonstrates capture of the sub‐ppm chloride level that is present in commercial D2O samples.
Chemotherapy response in low‐grade serous ovarian carcinoma at a comprehensive cancer center: Readdressing the roles of platinum and cytotoxic therapies
Authors: Manning‐Geist Beryl L. , Kahn Ryan M. , Nemirovsky David , Girshman Jeffrey , Laibangyang Anya , Gordhandas Sushmita , Iasonos Alexia , Chui M. Herman , Long Roche Kara , Zivanovic Oliver , Chi Dennis S. , Aghajanian Carol , Grisham Rachel N.
Published: March 2023

Background

Data on platinum sensitivity of low‐grade serous ovarian carcinoma (LGSOC) in the upfront setting is lacking, and there is limited and contradictory information on chemotherapy responses in recurrent disease.

Methods

Patients with LGSOC seen at a comprehensive cancer center from January 1, 1998 to September 30, 2021 were identified from institutional databases. Response to neoadjuvant chemotherapy (NACT) or adjuvant platinum‐based chemotherapy and to second‐ to fifth‐line regimens was retrospectively characterized by Response Evaluation Criteria in Solid Tumors (RECIST) v1.1. Wilcoxon rank‐sum and two‐tailed Fisher exact tests were employed.

Results

Of 50 patients, 12 received platinum doublets for suboptimal residual disease and 11 as NACT. Of 12 patients with suboptimal residual disease, seven (58%) achieved objective responses (five partial responses [PRs] and two complete responses); of the 11 patients who underwent NACT, one (9%) achieved a PR (p = .027). The 15 remaining patients had stable disease on first‐line platinum chemotherapy. Of 44 patients who recurred, 20 had RECIST‐evaluable responses to second‐line and 27 to third‐line chemotherapy. Objective response rates to platinum‐based chemotherapy were 22% (two of nine) in the second line and 10% (one of 10) in the third. In second and third lines, highest response rates were observed with nonplatinum chemotherapy with bevacizumab, at 100% (two of two) and 30% (three of 10), respectively.

Conclusions

Primary platinum‐based chemotherapy has moderate activity in LGSOC and minimal activity in the recurrent setting, suggesting standard definitions of platinum sensitivity may not apply in LGSOC. In the second and third lines, nonplatinum chemotherapy/bevacizumab elicited the highest response rates.