bluuebunny/crossref_metadata_2025 huggingface dataset:
Secular trends in height, weight, and body mass index in the context of economic and political transformations in Russia from 1885 to 2021
Authors: Negasheva Marina A. , Khafizova Ainur A. , Movsesian Alla A.
Published: September 2023

Objectives

To study and analyze the impact of socio‐economic factors on secular changes in height, weight, and body mass index (BMI) among Moscow's youth over the time interval from the late 19th–early 20th century to the present.

Methods

Anthropometric data, including height, weight, and BMI, were collected through surveys conducted on youths aged 17–20 years in Moscow from the 1880s for males and from the 1920s for females to the present. The dataset includes information on 6434 individuals surveyed from 2000 to 2019, as well as previously published mean values. Economic development indicators, such as gross domestic product (GDP) per capita, monthly average income per capita, and the Gini coefficient, were examined to analyze the association between secular trends in body size and socio‐economic conditions.

Results

A positive secular trend in height and weight has been observed among Moscow's youth from the early 20th century to the present. Substantial increases in height occurred during the second half of the previous century, stabilizing in the 2000s. Over the analyzed period, both average body weight and BMI values showed a consistent rise. The pattern for BMI exhibited a U‐shaped trend, with a decline from the 1970s to the mid‐1990s, followed by a subsequent increase. Strong correlations were found between the secular changes in body size among Moscow's youth and temporal fluctuations in key socio‐economic indicators, including GDP per capita, monthly average income per capita, and the Gini coefficient.

Conclusion

The study demonstrates the significant influence of socio‐economic conditions on intergenerational changes in body size, as evidenced by the positive secular trend in physique indicators (height, weight, and BMI) among Moscow's youth.
Factors that predict pursuing sinus surgery in the era of highly effective modulator therapy
Authors: Beswick Daniel M. , Han Ethan J. , Mace Jess C. , Markarian Karolin , Alt Jeremiah A. , Bodner Todd E. , Chowdhury Naweed I. , Eshaghian Patricia H. , Getz Anne E. , Hwang Peter H. , Khanwalkar Ashoke , Kimple Adam J. , Lee Jivianne T. , Li Douglas A. , Norris Meghan , Nayak Jayakar V. , Owens Cameran , Patel Zara , Poch Katie , Schlosser Rodney J. , Smith Kristine A. , Smith Timothy L. , Soler Zachary M. , Suh Jeffrey D. , Turner Grant , Wang Marilene B. , Taylor‐Cousar Jennifer L. , Saavedra Milene
Published: September 2023

Background

Comorbid chronic rhinosinusitis (CRS) remains unresolved for many people with cystic fibrosis (PwCF). While highly effective modulator therapy improves quality‐of‐life and symptom severity, the impact of this intervention and other factors associated with pursuing endoscopic sinus surgery (ESS) remains understudied.

Methods

Adult PwCF + CRS were enrolled into a prospective, observational, multi‐institutional study. Participants completed validated outcome measures to evaluate respiratory symptom severity, depression, headache, and sleep quality, as well as nasal endoscopy, sinus computed tomography (CT), and olfactory testing. Bivariate comparisons and regression modeling evaluated treatment cofactors, disease characteristics, and outcome measures associated with pursuing ESS.

Results

Sixty PwCF were analyzed, including 24 (40%) who elected ESS. Pursuing ESS was associated with worse SinoNasal Outcome Test (SNOT‐22) total, rhinologic, psychological, and sleep dysfunction domain scores; worse Patient Health Questionnaire‐9‐Revised depression scores; worse Pittsburgh Sleep Quality Index total scores; worse weight, role, emotion, and eating domain scores on the Cystic Fibrosis Questionnaire‐Revised; more severe disease on nasal endoscopy; and lack of modulator therapy (all p < 0.050). Multivariable regression identified that worse SNOT‐22 total score was associated with electing ESS (odds ratio [OR] 1.09, 95% confidence interval [CI] 1.02–1.16, p = 0.015) and elexacaftor/tezacaftor/ivacaftor (ETI) treatment (OR 0.04, 95% CI 0.004–0.34, p = 0.004) was associated with pursing medical therapy.

Conclusions

Worse sinonasal symptom burden, lack of ETI treatment, sleep quality, depression, and nasal endoscopy scores were associated with electing ESS, while lung disease severity and sinus CT scores were not. ETI use was associated with lower odds of pursuing ESS independent of sinonasal symptom burden.
Metal‐Free Electrocatalytic Diacetoxylation of Alkenes
Authors: Vanhoof Jef R. , De Smedt Pieter J. , Derhaeg Jan , Ameloot Rob , De Vos Dirk E.
Published: September 2023

1,2‐Dioxygenation of alkenes leads to a structural motif ubiquitous in organic synthons, natural products and active pharmaceutical ingredients. Straightforward and green synthesis protocols starting from abundant raw materials are required for facile and sustainable access to these crucial moieties. Especially industrially abundant aliphatic alkenes have proven to be arduous substrates in sustainable 1,2‐dioxygenation methods. Here, we report a highly efficient electrocatalytic diacetoxylation of alkenes under ambient conditions using a simple iodobenzene mediator and acetic acid as both the solvent and an atom‐efficient reactant. This transition metal‐free method is applicable to a wide range of alkenes, even challenging feedstock alkenes such as ethylene and propylene, with a broad functional group tolerance and excellent faradaic efficiencies up to 87 %. In addition, this protocol can be extrapolated to alkenoic acids, resulting in cyclization of the starting materials to valuable lactone derivatives. With aromatic alkenes, a competing mechanism of direct anodic oxidation exists which enables reaction under catalyst‐free conditions. The synthetic method is extensively investigated with cyclic voltammetry.
Intrinsic Stress‐strain in Barium Titanate Piezocatalysts Enabling Lithium−Oxygen Batteries with Low Overpotential and Long Life
Authors: Zheng Li‐Jun , Song Li‐Na , Wang Xiao‐Xue , Liang Shuang , Wang Huan‐Feng , Du Xing‐Yuan , Xu Ji‐Jing
Published: September 2023

Rechargeable lithium−oxygen (Li−O2) batteries with high theoretical energy density are considered as promising candidates for portable electronic devices and electric vehicles, whereas their commercial application is hindered due to poor cyclic stability caused by the sluggish kinetics and cathode passivation. Herein, the intrinsic stress originated from the growth and decomposition of the discharge product (lithium peroxide, Li2O2) is employed as a microscopic pressure resource to induce the built‐in electric field, further improving the reaction kinetics and interfacial Lithium ion (Li+) transport during cycling. Piezopotential caused by the intrinsic stress‐strain of solid Li2O2 is capable of providing the driving force for the separation and transport of carriers, enhancing the Li+ transfer, and thus improving the redox reaction kinetics of Li−O2 batteries. Combined with a variety of in situ characterizations, the catalytic mechanism of barium titanate (BTO), a typical piezoelectric material, was systematically investigated, and the effect of stress‐strain transformation on the electrochemical reaction kinetics and Li+ interface transport for the Li−O2 batteries is clearly established. The findings provide deep insight into the surface coupling strategy between intrinsic stress and electric fields to regulate the electrochemical reaction kinetics behavior and enhance the interfacial Li+ transport for battery system.
Frontier Molecular Orbital Engineering: Constructing Highly Efficient Narrowband Organic Electroluminescent Materials
Authors: Xu Yincai , Wang Qingyang , Cai Xinliang , Li Chenglong , Jiang Shimei , Wang Yue
Published: September 2023

It is of great strategic significance to develop highly efficient narrowband organic electroluminescent materials that can be utilized to manufacture ultra‐high‐definition (UHD) displays and meet or approach the requirements of Broadcast Television 2020 (B.T.2020) color gamut standards. This motif poses challenges for molecular design and synthesis, especially for developing generality, diversity, scalability, and robustness of molecular structures. The emergence of multiple resonance thermally activated delayed fluorescence (MR‐TADF) emitters has ingeniously solved the problems and demonstrated bright application prospects in the field of UHD displays, sparking a research boom. This Minireview summarizes the research endeavors of narrowband organic electroluminescent materials, with emphasis on the tremendous contribution of frontier molecular orbital engineering (FMOE) strategy. It combines the outstanding advantages of MR framework and donor‐acceptor (D−A) structure, and can achieve red‐shift and narrowband emission simultaneously, which is of great significance in the development of long‐wavelength narrowband emitters with emission maxima especially exceeding 500 nm. We hope that this Minireview would provide some inspiration for what could transpire in the future.
A High Pressure Operando Spectroscopy Examination of Bimetal Interactions in ‘Metal Efficient’ Palladium/In2O3/Al2O3 Catalysts for CO2 Hydrogenation
Authors: Potter Matthew E. , Mediavilla Madrigal Sofia , Campbell Emma , Allen Lisa J. , Vyas Urvashi , Parry Stephen , García‐Zaragova Adrián , Martínez‐Prieto Luis M. , Oña‐Burgos Pascual , Lützen Mads , Damsgaard Christian D. , Rodríguez‐Castellón Enrique , Schiaroli Nicola , Fornasari Giuseppe , Benito Patricia , Beale Andrew M.
Published: September 2023

CO2 hydrogenation to methanol has the potential to serve as a sustainable route to a wide variety of hydrocarbons, fuels and plastics in the quest for net zero. Synergistic Pd/In2O3 (Palldium on Indium Oxide) catalysts show high CO2 conversion and methanol selectivity, enhancing methanol yield. The identity of the optimal active site for this reaction is unclear, either as a Pd−In alloy, proximate metals, or distinct sites. In this work, we demonstrate that metal‐efficient Pd/In2O3 species dispersed on Al2O3 can match the performance of pure Pd/In2O3 systems. Further, we follow the evolution of both Pd and In sites, and surface species, under operando reaction conditions using X‐ray Absorption Spectroscpy (XAS) and infrared (IR) spectroscopy. In doing so, we can determine both the nature of the active sites and the influence on the catalytic mechanism.
Hydrothermal and microwave‐assisted synthesis of levulinic acid from watermelon residue
Authors: Bazoti Suzana F. , Camargo Aline Frumi , Bonatto Charline , Kubeneck Simone , Treichel Helen , de Oliveira Débora
Published: September 2023

Levulinic acid (LA) is considered a versatile chemical building block and has emerged as one of the leading platforms for products derived from biomass. It is regarded as important from an economic perspective. The main route of synthesis to obtain LA is from the degradation of cellulose by acid catalysis, with lignocellulosic biomass being a promising and sustainable way to obtain it. In this study, for the first time, the use of watermelon residues was proposed for the synthesis of levulinic acid, adding value to a residual biomass that has still been little explored for this purpose.

Watermelon residues were subjected to acid hydrolysis using H2SO4 or HCl. Two reactors were analyzed for this purpose – autoclave and microwave assisted. The experiments were optimized through a central composite design, where temperature, biomass load, and acid concentration in the microwave were evaluated as variables. In the autoclave, the variables investigated were catalyst concentration and biomass loading.

The highest yields, 14.8% and 17% by weight, were obtained with solid fraction (SF) in micro wave (MW). In the best condition obtained in the central composite design, the liquid fraction (LF) and SF were analyzed. It was observed that a clean product, containing only levulinic acid and formic acid, was in the liquid fraction. The MW was more efficient and is a promising alternative for reactions requiring energy. This study contributes to an energy‐saving strategy, using waste and low‐cost catalysts, sustainably contributing to a circular carbon economy based on agricultural waste.
A state‐of‐the‐science review of analytical methods for urinary dialkylphosphate metabolites in the assessment of exposure to organophosphate pesticides: From 2000 to 2022
Authors: Neves Ana Paula , Rosa Ana Cristina Simões , Larentis Ariane Leites , da Silva Rodrigues Vidal Priscila Jeronimo , Gonçalves Eline Simões , Geraldino Barbara Rodrigues , da Silveira Gabriel Rodrigues , de Carvalho Leandro Vargas Barreto , Alves Sergio Rabello
Published: September 2023

The general population and workers are exposed to organophosphate insecticides, one of the leading chemical classes of pesticides used in rural and urban areas. This paper aims to conduct an integrative review of the most used analytical methods for identifying and quantifying dialkylphosphate—which are metabolites of organophosphate insecticides—in the urine of exposed workers, discussing their advantages, limitations and applicability. Searches utilized the PubMed, the Scientific Electronic Library Online and the Brazilian Digital Library of Theses and Dissertations databases between 2000 and 2021. Twenty‐five studies were selected. The extraction methods most used were liquid–liquid extraction (LLE) (36%) and solid‐phase extraction (SPE) (36%), with the SPE being more economical in terms of time and amount of solvents needed, and presenting the best percentage of recovery of analytes, when compared with LLE. Nineteen studies (76%) used the gas chromatography method of separation, and among these, 12 records (63%) indicated mass spectrometry used as a detection technology (analyzer). Studies demonstrate that dialkylphosphates are sensitive and representative exposure biomarkers for environmental and occupational organophosphate exposure.
Discrimination of ground‐glass nodular lung adenocarcinoma pathological subtypes via transfer learning: A multicenter study
Authors: Fu Chun‐Long , Yang Ze‐Bin , Li Ping , Shan Kang‐Fei , Wu Mei‐Kang , Xu Jie‐Ping , Ma Chi‐Jun , Luo Fang‐Hong , Zhou Long , Sun Ji‐Hong , Zhao Fen‐Hua
Published: September 2023

Background

The surgical approach and prognosis for invasive adenocarcinoma (IAC) and minimally invasive adenocarcinoma (MIA) of the lung differ. However, they both manifest as identical ground‐glass nodules (GGNs) in computed tomography images, and no effective method exists to discriminate them.

Methods

We developed and validated a three‐dimensional (3D) deep transfer learning model to discriminate IAC from MIA based on CT images of GGNs. This model uses a 3D medical image pre‐training model (MedicalNet) and a fusion model to build a classification network. Transfer learning was utilized for end‐to‐end predictive modeling of the cohort data of the first center, and the cohort data of the other two centers were used as independent external validation data. This study included 999 lung GGN images of 921 patients pathologically diagnosed with IAC or MIA at three cohort centers.

Results

The predictive performance of the model was assessed using the area under the receiver operating characteristic curve (AUC). The model had high diagnostic efficacy for the training and validation groups (accuracy: 89%, sensitivity: 95%, specificity: 84%, and AUC: 95% in the training group; accuracy: 88%, sensitivity: 84%, specificity: 93%, and AUC: 92% in the internal validation group; accuracy: 83%, sensitivity: 83%, specificity: 83%, and AUC: 89% in one external validation group; accuracy: 78%, sensitivity: 80%, specificity: 77%, and AUC: 82% in the other external validation group).

Conclusions

Our 3D deep transfer learning model provides a noninvasive, low‐cost, rapid, and reproducible method for preoperative prediction of IAC and MIA in lung cancer patients with GGNs. It can help clinicians to choose the optimal surgical strategy and improve the prognosis of patients.
Real‐world experience of tyrosine kinase inhibitors in children, adolescents and adults with relapsed or refractory bone tumours: A Canadian Sarcoma Research and Clinical Collaboration (CanSaRCC) study
Authors: Peretz Soroka Hagit , Vora Tushar , Noujaim Jonathan , Marcoux Nicolas , Cohen‐Gogo Sarah , Alcindor Thierry , Holloway Caroline , Rodrigues Caroline , Karachiwala Hatim , Alvi Saima , Lee Ursula , Cheng Sylvia , Banerji Shantanu , Oberoi Sapna , Feng Xiaolan , Smrke Alannah , Simmons Christine , Razak Albiruni Abdul , Gupta Abha A.
Published: September 2023

Objectives

We conducted a retrospective multi‐centre study to assess the real‐world outcome of regorafenib (REGO) and cabozantinib (CABO) in recurrent/refractory bone tumours (BTs) including osteosarcoma (OST), Ewing sarcoma (EWS) and chondrosarcoma (CS)/extra‐skeletal mesenchymal CS (ESMC).

Methods

After regulatory approval, data from patients with recurrent BT (11 institutions) were extracted from CanSaRCC (Canadian Sarcoma Research and Clinical Collaboration) database. Patient characteristics, treatment and outcomes were collected. Progression‐free survival (PFS) and overall survival (OS) were estimated using the Kaplan–Meier method.

Results

From July 2018 to May 2022, 66 patients received REGO or CABO; 39 OST, 18 EWS, 4 CS and 5 ESMC. Median age was 27.8 years (range 12–76); median starting dose was 60 mg for CABO (n = 37, range 40–60) and 120 mg for REGO (n = 29, range 40–160). Twenty‐eight (42.4%) patients required dose reduction: hand‐foot syndrome 7 (10.6%), nausea/vomiting 1 (1.5%), diarrhoea 1 (1.5%), 2 elevated LFTs (3%), elevated bilirubin 1 (1.5%) and mucositis 1 (1.5%). The median OS for patients with OST, EWS, CS and ESMC was 8.5 months (n = 39, 95% CI 7–13.1); 13.4 months (n = 18, 95% CI 3.4–27.2), 8.1 (n = 4, 95% CI 4.1–9.3) and 18.2 (n = 5, 95% CI (10.4–na), respectively. Median PFS for OST, EWS, CS and ECMS was 3.5 (n = 39, 95% CI 2.8–5), 3.9 (n = 18, 95% CI 2.1–5.9), 5.53 (n = 4. 95% CI 2.13–NA) and 11.4 (n = 5, 95% CI 1.83–14.7), respectively. Age, line of therapy, REGO versus CABO, or time from diagnosis to initiation of TKI were not associated with PFS on univariable analysis.

Conclusion

Our real‐world data show that TKIs have meaningful activity in recurrent BT with acceptable toxicities when started at modified dosing. Inclusion of TKIs in earlier lines of treatment and/or maintenance therapy could be questions for future research.
The efficacy and safety of chemo‐free therapy in epidermal growth factor receptor tyrosine kinase inhibitor‐resistant advanced non‐small cell lung cancer: A single‐arm, phase II study
Authors: Zhang Shuyang , Yang Lu , Yang Yaning , Yang Guangjian , Xu Haiyan , Niu Xueliang , Wang Yan
Published: September 2023

Objectives

The purpose of this study was to explore the efficacy and safety of toripalimab combined with anlotinib in patients with advanced non‐small cell lung cancer (NSCLC) who acquired resistance to epidermal growth factor receptor tyrosine kinase inhibitors (EGFR‐TKIs).

Materials and Methods

Patients who developed resistance after using first‐ or second‐generation EGFR‐TKIs as their first‐line regimen without EGFR T790M mutation or had disease progression after being treated with third‐generation EGFR‐TKIs as first‐ or second‐line therapy were enrolled. All patients received toripalimab (240 mg/day on Day 1, intravenously) combined with anlotinib (12 mg/day, Days 1–14, orally) once every 3 weeks. Treatment continued until disease progression, or if toxicity was intolerable. The primary endpoint was the objective response rate (ORR) assessed by the investigator. The secondary endpoint was the progression‐free survival (PFS).

Results

In total, 19 patients were enrolled between May 2020 and October 2021.The ORR was 0%, and a median PFS was 2.1 months (95% CI 0.251–3.949). Grade ≥3 treatment‐related adverse events (AEs) occurred in 11% patients. Common adverse events included hypothyroidism (12/19), fatigue (9/19), and hypertension (8/19). Patients in stable disease (SD) group had lower abundance of EGFR mutation allele frequency (AF) before enrollment than those in progressive disease (PD) group (p = 0.031). Patients without detectable EGFR mutation (EGFR−) had longer PFS compared to the ones with EGFR mutations (p = 0.059). Patients with high levels of soluble programmed cell death ligand 1 (PD‐L1) at baseline also tended to have longer PFS (p = 0.160).

Conclusion

Toripalimab combined with anlotinib was tolerable in EGFR‐TKI‐resistant advanced NSCLC patients not previously treated with chemotherapy. Patients without detectable EGFR mutation and high soluble PD‐L1 levels may benefit from this chemotherapy‐free treatment.
Analysis on the risk of myasthenia gravis related to immune checkpoint inhibitors based on the US FDA Adverse Event Reporting System
Authors: Kong Qingli , Wang Hui , Ren Xiaolei , Zhuo Yue , Peng Jing
Published: September 2023

Objective

To evaluate the risk of myasthenia gravis (MG) associated with immune checkpoint inhibitors (ICI).

Methods

Adverse event (AE) reports related to MG, myasthenic syndrome, and MG crisis for durvalumab, atezolizumab, pembrolizumab, nivolumab, avelumab, and ipilimumab in the US FDA Adverse Event Reporting System (FAERS) from Q1 2004 to Q3 2022 were collected. The proportional reporting odds ratio (PRR) method was used to evaluate the correlation between the six drugs and the three AEs. Statistical significance was defined as having reports ≥3, PRR ≥ 2, and chi‐square (χ2) ≥ 4.

Results

A total of 36, 78, 276, 380, 5, and 53 AE reports were collected for durvalumab, atezolizumab, pembrolizumab, nivolumab, avelumab, and ipilimumab, respectively. For myasthenic syndrome, the PRR values reflecting the correlation with the drugs were 27.83 (χ2 = 102.66), 26.20 (χ2 = 235.67), 44.17 (χ2 = 1313.98), 32.09 (χ2 = 1229.54), 21.31 (χ2 = 151.15), and 0 for durvalumab, atezolizumab, pembrolizumab, nivolumab, avelumab, and ipilimumab, respectively. For MG, the PRR values reflecting the correlation with the drugs were 24.21 (χ2 = 682.04), 18.34 (χ2 = 900.27), 39.32 (χ2 = 7945.15), 26.93 (χ2 = 6636.45), 14.73 (χ2 = 566.47), and 15.69 (χ2 = 54.77) for durvalumab, atezolizumab, pembrolizumab, nivolumab, avelumab, and ipilimumab, respectively. For MG crisis, there were no data for durvalumab, atezolizumab, avelumab, and ipilimumab; the PRR values reflecting the correlation with the drugs were 16.54 (χ2 = 225.23) and 9.20 (χ2 = 119.14) for pembrolizumab and nivolumab, respectively. All six drugs were statistically correlated with their corresponding AEs.

Conclusions

ICI may lead to ICIs‐associated MG during therapy. Analysis of FAERS data identified signals for AEs of MG with ICI regimens. Practitioners should consider the factors that may increase the likelihood of MG. The findings support a continued surveillance and risk factor identification.
Operating microscope‐assisted reconstructive strategy for peri‐implantitis: A case series report
Authors: Chiang Yi‐Chen , Sirinirund Benyapha , Rodriguez Amanda , Velasquez Diego , Chan Hsun‐Liang
Published: September 2023

Background

Treating peri‐implantitis with reconstructive means has been largely unpredictable due to access limitations for surface decontamination, unfavorable bony topography, difficulty in achieving wound stability, and inferior soft tissue qualities. A microsurgical approach with the use of the operating microscope (OM) that provides adjustable higher magnification (∼5–30 times) and coaxial illumination, coupled with the use of microsurgical instruments, may overcome, or alleviate some of the abovementioned obstacles, resulting in more predictable outcomes.

Methods

Three patients received reconstructive therapy for correcting peri‐implant defects under OM in private practice settings. After precise incisions to preserve soft tissue volume, the flaps were dissected prudently from underlying granulomatous tissues, which were subsequently removed, followed by controlled flap releasing under ∼10–15x magnification. Surface decontamination was performed using a piezoelectric ultrasonic device, air polishing, and hand instruments at ∼30x magnification. The biomaterial selections were dehydrated human de‐epithelialized amnion‐chorion membrane with mineralized allograft particulates in two cases and xenografts in one case, based on the surgeons’ preference. Wound closure followed the non‐submerged approach.

Results

These cases demonstrated uneventful soft tissue healing, favorable radiographic bone fill, and disease resolution with follow‐ups ranging from 2 to 4 years.

Conclusions

Preliminary data suggest encouraging outcomes after the microsurgical approach following biological as well as biomechanical principles for peri‐implant defect reconstruction.
Can manipulating control‐display ratio dynamically really work in changing pseudo‐haptic weight?
Authors: Chen Yonghua , Yang Xubo
Published: September 2023

Due to the limited hardware available in virtual reality, such as VR controllers or simple motion capture devices, users will need more tactile feedback, like the weight of virtual objects. Pseudo‐tactile feedback, such as the control display (C/D) ratio manipulation method, is considered a standard method to simulate weight perception. In past studies, this method was basically used in a static environment, and the C/D ratio was usually determined initially. Can this method still work if the C/D ratio changes in dynamic usage scenarios? In a series of experiments, we tried to answer this question. We proved that the dynamic change of C/D ratio could simulate the weight change and improve the sense of embodiment through another hand redirection method.
Combining Ligand Deuteration with Ligand Bulkiness in Non‐Heme Iron Oxidation Catalysis: Enhancing Catalyst Lifetime and Site‐Selectivity
Authors: Li Fanshi , Meijer Isabelle , Kniestedt Bauke , Lutz Martin , Broere Daniël L. J. , Klein Gebbink Robertus J. M.
Published: September 2023

Bulky tri‐isopropyl silyl (TIPS) substituents and deuterium atoms in the ligand design have been shown to enhance the site‐selective oxidation of aliphatic C−H bonds and the epoxidation of C=C bonds in non‐heme iron oxidation catalysis. In this work, a series of non‐heme iron complexes were developed by combining TIPS groups and deuterium atoms in the ligand. These bulky deuterated complexes show a significant increase in catalytic performance compared to their counterparts containing only TIPS groups or deuterium atoms. A broad range of substrates was oxidized with excellent yields, particularly, using [Fe(OTf)2((S,S)‐TIPSBPBP‐D4)] (1‐TIPS‐D4) (0.1 mol % to 1 mol %) via a fast or slow oxidant addition protocol, resulting in an overall improvement in catalytic performance. Notably, in the oxidation of the complex substrate trans‐androsterone acetate, the use of a slow addition protocol and a lower catalyst loading of 1‐TIPS‐D4 resulted in significant increases in reaction efficiency. In addition, kinetic and catalytic studies showed that deuteration does not affect the catalytic activity and the secondary C−H site‐selectivity but increases the catalysts’ lifetime resulting in higher conversion/yield. Accordingly, the yield of selectively oxidized secondary C−H products also increases with the overall yield by using the bulky deuterated iron complexes as catalysts. These catalytic improvements of the bulky deuterated complexes exemplify the enhanced design of ligands for homogeneous oxidation catalysis.
Soil sampling depth effect on critical soil test values of phosphorus for conservation agriculture
Authors: Tiecher Tales , Gatiboni Luke , Osmond Deanna , Hardy David
Published: September 2023

The critical soil test value (CSTV) of phosphorus (P) is the threshold where it is possible to obtain 95–100% of the maximum crop yield. Although the P buildup in the topsoil of conservation tillage may affect this threshold, the effect of soil sampling depth on CSTV value has not been determined for conservation tillage in the southern United States. The objective of this study was to evaluate CSTV of P using different soil layers from two long‐term experiments managed under varying P rates, planted to corn (Zea mays L.)/soybean [Glycine max (L.) Merr.] rotation under minimum tillage (Tidewater) or no‐tillage (Piedmont) in North Carolina. Soil samples were taken from depths of 0–2, 2–4, 4–8, and 8–12 inches. The CSTV for different soil layers was calculated using a quadratic‐plateau model with Mehlich‐3 P and relative yield of soybean and corn (2021–2022). The CSTV decreased as the soil sampling depth increased. The CSTV of P at the Tidewater site was 128, 111, 86, and 74 lb ac−1, and at the Piedmont site was 28, 20, 16, and 15 lb ac−1 for the 0–2, 0–4, 0–8, and 0–12 inches soil layers, respectively. Using multiple sampling layers or deeper layers did not improve the quality of CSTV measurement. The current sampling depths used in North Carolina are appropriate for minimum tillage (0–8 inches) and no tillage (0–4 inches), as similar quality models were obtained using either soil layers in both sites. However, it is important to be cautious when changing the sampling depth, as this affects the CSTV value.
Dyads and Triads of Boron Difluoride Formazanate and Boron Difluoride Dipyrromethene Dyes
Authors: Buguis Francis L. , Hsu Nathan Sung Y. , Sirohey Sofia A. , Adam Matheus C. , Goncharova Lyudmila V. , Gilroy Joe B.
Published: September 2023

Dye‐dye conjugates have attracted significant interest for their utility in applications such as bioimaging, theranostics, and light‐harvesting. Many classes of organic dyes have been employed in this regard; however, building blocks don't typically extend beyond small chromophores. This can lead to minor changes to the optoelectronic properties of the original dye. The exploration of dye–dye structures is impeded by long synthetic routes, incompatible synthetic conditions, or a mismatch of the desired properties. Here, we present the first‐of‐their‐kind dye‐dye conjugates of boron difluoride complexes of formazanate and dipyrromethene ligands. These conjugates exhibit dual photoluminescence bands that reach the near‐infrared spectral region and implicate anti‐Kasha processes. Cyclic voltammetry experiments revealed the generation of polyanionic species that can reversibly tolerate the uptake of up to 6 electrons. Ultimately, we demonstrate that BF2 formazanates can serve as a synthetically accessible platform to build upon new classes of dye‐dye conjugates.
An Investigation of Allyl‐Substituted Bis(Diphosphine) Iron Complexes: Towards Precursors for Cooperative CO2 Activation
Authors: Durfy Connor S. , Zurakowski Joseph A. , Jobin Gabriel , Drover Marcus W.
Published: September 2023

In developing homogenous catalysts capable of CO2 activation, interaction with a metal center is often imperative. This work provides primary efforts towards the cooperative activation of CO2 using a Lewis acidic secondary coordination sphere (SCS) and iron via a paired theoretical/experimental approach. Specifically, this study reports efforts towards [Fe(diphosphine)2(N2)] as a CO2‐coordinated synthon where diphosphine=1,2‐bis(di(3‐cyclohexylboranyl)propylphosphino)ethane) (P2BCy4) or its precursor, 1,2‐bis(diallylphosphino)ethane (tape). Initial efforts toward the {Fe(0)‐N2} complex were focused on deprotonation reactions of [Fe(diphosphine)2(H)(NCCH3)]+ and reduction of [Fe(tape)2Cl2]. In the latter case, a mixture of intramolecularly π‐bonded alkene and associated metallacyclic Fe(II)—H species were produced – heating this mixture provided the hydride as the major product. Notably, the interconversion of this pair counters that of related intermolecular reactions between [Fe(depe)2] (depe=1,2‐bis(diethylphosphino)ethane) and ethylene, where hydride formation occurs subsequent to π‐coordination; this has been probed by theoretical calculations. Finally, reactivity of the metallacyclic {Fe(II)—H} complex with CO2 was probed, resulting in a pair of isomeric ferra(II)lactones.
Aptamer‐Based Antibiotic Electrochemical Detection Platform Using Portable Plastic Gold Electrode and Multichannel Chip
Authors: Bao Yin , Cai Kaiwei , Liu Yichen , Li Bingling
Published: September 2023

Comprehensive Summary

The development of accurate, rapid and practical electrochemical sensing technology for antibiotic detection has an important application prospect in many fields such as food safety, environmental monitoring, medical and health care. In this research, kanamycin specific DNA aptamer and its partially complementary short chain were self‐assembled onto the surface of an integrated portable plastic gold electrode (PGE) by Au—S bond, and a simple kanamycin electrochemical biosensor interface was constructed. At the same time, the epoxy resin channel layer was designed, and the auxiliary instrument was set up independently in the laboratory, which could help to measure and analyze eight groups of samples automatically in turn. The quantitative analysis results showed that in 20 min, the sensor had a good linear relationship between the peak current change of square wave voltammetry and the negative logarithm of kanamycin concentration when kanamycin concentration was in the range of 1—1000 μmol/L, and the detection limit could reach 0.40 μmol/L. In addition, the discrimination could be achieved within 5 min in the real‐time analysis mode. The sensor had a simple construction method, good selectivity and stability, and could be used for rapid or real‐time detection of kanamycin residues in actual water samples, which provided a new direction for the practical detection of kanamycin in environmental water samples.
Relationship between ideal cardiovascular health score and perioperative acute kidney injury: A case‐control study
Authors: Li Jin‐Qiu , An Yuan , Wang Tai , Guo Ping‐Xuan , Chen Shuo‐Hua , Liu Bing‐Bing , Liu Hai
Published: September 2023

Background

Maintaining ideal cardiovascular health scores (CHS) may indirectly contribute to reducing the risk of perioperative acute kidney injury (AKI), which has never been explored previously. In this study, we aimed to explore the relationship between CHS and AKI and provide new ideas for AKI prevention and treatment.

Methods

We examined the effects of CHS on the occurrence of AKI among 2783 participants from the Kailuan study, who received general anesthesia during noncardiac surgery from 2016 to 2020. The odds ratios (ORs) and 95% confidence intervals (95% CIs) for AKI were calculated by using the logistic regression.

Results

Among 2783 participants 187 were diagnosed with perioperative AKI. We found an inverse relationship between the CHS scores and the risk of AKI. Participants with CHS score ≥ 10 had 57% decreased risk of AKI (OR = 0.43, 95% CI = 0.23, 0.79), compared with participants with CHS score ≤ 7, especially in men (OR = 0.39, 95% CI: 0.20, 0.76). In addition, participants who never smoked, exercised frequently, and had normal blood pressure had decreased risk of AKI, with corresponding ORs (95% CIs) of 0.66 (0.47, 0.91), 0.73 (0.60, 0.92), and 0.46 (0.28, 0.75), respectively.

Conclusions

CHS was strongly associated with the risk of perioperative AKI, and higher CHS scores were associated with a lower risk of AKI. Further research is needed to explore the long‐term effects of achieving and maintaining an ideal CHS on AKI risk.
Molecular Conformations of Shape Anisometrically Variant Mesogens in Liquid Crystalline Phase Studied by 13C NMR Spectroscopy
Authors: Veeraprakash Bathini , Shanavas Abdul K. J. , Reddy Goddeti S. M. , Lobo Nitin P. , Ramanathan Krishna V. , Narasimhaswamy Tanneru
Published: September 2023

Mesogens that vary in shape anisometry have been investigated by 13C solid‐state NMR in the liquid crystalline phase to inspect the conformations. The molecules examined comprise of (i) rod‐like mesogen with three‐phenyl ring core and terminal hexyloxy chains, (ii) three‐ring core linked to the fourth phenyl ring via a spacer, and (iii) trimesic acid connected to three side arms core units through a spacer. The order parameter (Szz) values for the phenyl rings of the rod‐like mesogen are 0.65–0.68, while the mesogen with a three‐ring core linked to a phenyl ring via spacer showed dissimilarity. Consequently, for the core unit phenyl rings, Szz is ~0.70, and the terminal phenyl ring showed a low value of 0.12. For the trimesic acid based mesogen, the Szz value for the side arm phenyl rings is ~0.53, and for the central phenyl ring, a very low value of 0.11 is witnessed. By considering the ordering of the rod‐like mesogen as a yardstick and employing the ratios of Szz values of the phenyl rings, the average conformations of other mesogens are arrived. Accordingly, for the trimesic acid based mesogen, a tripod‐like conformation instead of λ shape is proposed in the liquid crystalline phase.
Computational Energy Spectra of the H2O@C70 Endofullerene
Authors: Carrillo‐Bohórquez Orlando , Valdés Álvaro , Prosmiti Rita
Published: September 2023

A water molecule confined inside the C70 fullerene was quantum‐mechanically described using a computational approach within the MCTDH framework. Such procedure involves the development of a full‐dimensional coupled hamiltonian, with an exact kinetic energy operator, including all rotational, translational and vibrational degrees of freedom of the endofullerene system. In turn, through an effective pairwise potential model, the ground and rotationally excited states of the encapsulated H2O inside the C70 cage were calculated, and traced back to the isotropic case of the H2O@C60 endofullerene in order to understand the nature and physical origin of the symmetry breaking observed experimentally in the latter system. Moreover, the computational scheme used here allows to study the quantization of the translational movement of the encapsulated water molecule inside the C70 fullerene, and to investigate the confinement effects in the vibrational energy levels of the H2O@C70 system.
Evaluating Prognostic Value of Dynamics of Circulating Lactate Dehydrogenase in Colorectal Cancer Using Modeling and Machine Learning
Authors: Ding Haolun , Yuan Min , Yang Yaning , Gupta Manish , Xu Xu Steven
Published: September 2023

Pretreatment serum lactate dehydrogenase (LDH) levels have been associated with poor prognosis in several types of cancer, including metastatic colorectal cancer (mCRC). However, very few models link survival to longitudinal LDH measured repeatedly over time during treatment. We investigated the prognostic value of on‐treatment LDH dynamics in mCRC. Using data from two large phase III studies (2L and 3L+ mCRC settings, n = 824 and 210, respectively), we found that integrating longitudinal LDH data with baseline risk factors significantly improved survival prediction. Current LDH values performed best, enhancing discrimination ability (area under the receiver operating characteristic curve) by 4.5~15.4% and prediction accuracy (Brier score) by 3.9~15.0% compared with baseline variables. Combining all longitudinal LDH markers further improved predictive performance. After controlling for baseline covariates and other longitudinal LDH indicators, current LDH levels remained a significant risk factor in mCRC, increasing mortality risk by over 90% (P < 0.001) in 2L patients and 60–70% (P < 0.01) in 3L+ patients per unit increment in current log (LDH). Machine‐learning techniques, like functional principal component analysis (FPCA), extracted informative features from longitudinal LDH data, capturing over 99% of variability and allowing prediction of survival. Unsupervised clustering based on the extracted FPCA features stratified patients into three groups with distinct LDH dynamics and survival outcomes. Hence, our approaches offer a valuable and cost‐effective way for risk stratification and improves survival prediction in mCRC using LDH trajectories.
19‐color, 21‐Antigen Single Tube for Efficient Evaluation of B‐ and T‐cell Neoplasms
Authors: Chan Alexander , Gao Qi , Roshal Mikhail
Published: September 2023

Non‐Hodgkin lymphoma (NHL) is a heterogeneous disease, encompassing a wide variety of individually distinct neoplastic entities of mature B‐, T‐, and NK‐cells. While they constitute a broad category, they are the most common hematologic malignancies in the world. The distinction between different neoplastic entities requires a multi‐modal approach, such as flow cytometric immunophenotyping, which can exclude a neoplastic proliferation and help narrow the differential diagnosis. This article describes a flow cytometric test developed at Memorial Sloan Kettering Cancer Center to assess B‐, T‐, and NK‐cells in a single tube, 21‐antibody, 19‐color assay. The assay can identify most B‐ and T‐cell NHLs with high specificity and sensitivity and significantly narrow the differential when a specific diagnosis cannot be made. The basic protocol provides a detailed operational procedure for sample processing, staining, and cytometric acquisition. The support protocol provides typical steps and caveats for data analysis in lymphoproliferative disorders and in discriminating a variety of specific disease entities from each other and normal lymphoid populations. © 2023 Wiley Periodicals LLC.

Basic Protocol: Processing, staining, and cytometric analysis of samples for B‐ and T‐cell assessment

Support Protocol: Analysis and interpretation of the B‐ and T‐cell lymphocyte assay
Exploring the trait‐yield association patterns in different oat mega‐environments of Canada
Authors: Yan Weikai , Hadinezhad Mehri , Dehaan Brad , Hayes Matt , Orozovic Savka , Nilsen Kirby T. , MacEachern Dan , Telmosse Genevieve , Beattie Aaron , Booker Helen , Byker Holly , Cummiskey Allan , Morasse Isabelle , Mountain Nathan , Drummond Melinda , Zhang Zhanghan , Holzworth Michael , Durand Julie , Chen Yuanhong
Published: September 2023

This article presents a graphical method to visually analyze the trait–yield association (TYA) patterns based on data from multi‐location, multi‐year crop variety trials, exemplified using oat data from trials conducted across Canada from 2017 to 2022. Each year a new set of 60–66 oat (Avena sativa L.) breeding lines were tested in replicated yield trials at 9–11 locations, and data for yield, key agronomic and quality traits, and crown rust scores were collected at all or some of the locations. Pearson correlation coefficient was calculated between yield and each trait for each trial. The correlation coefficients from different locations and years were arranged in a TYA × trial (TYT) two‐way table. This table was subjected to singular value decomposition, and the resulting first two principal components were used to generate a TYT biplot. The TYT biplot revealed three oat mega‐environments (MEs) in Canada, consistent with the conclusion from previous ME analyses, indicating that each ME had its characteristic TYA patterns. It was found that yield was consistently and positively correlated with crown rust (Puccinia coronata var. avenae) resistance, test weight, kernel weight, and groat content in ME1 (the crown rust‐prone regions of Ontario); yield was correlated positively with plant height but negatively with oil content in ME2 (the northern regions of eastern Canada). Interestingly, crown rust resistance was found to contribute negatively to yield in ME2. No strong and consistent TYAs were found in ME3 (the Canadian prairies). Different types of TYAs have different uses in genotypic selection.
The Underlying Catalytic Role of Oxygen Vacancies in Fatty Acid Methyl Esters Ketonization over TiOx Catalysts
Authors: Yazdanpanah Mohammad , Fereidooni Mohammad , Márquez Victor , Paz C. V. , Saelee Tinnakorn , Salazar Villanueva Martin , Rittiruam Meena , Khajondetchairit Patcharaporn , Praserthdam Supareak , Praserthdam Piyasan
Published: September 2023

Recently, interest in converting bio‐derived fatty acid methyl esters (FAMEs) into added‐value products has significantly increased. The selectivity of ketonization reaction in the conversion of the FAMEs has significantly hampered the efficiency of this process. Herein, this work reports the preparation of catalysts with different levels of oxygen vacancies while the crystal phase remained unchanged. The catalyst with the highest level of oxygen vacancy exhibited the maximum selectivity. The density functional theory (DFT) simulation showed an increase in interatomic distances leading to the formation of frustrated Lewis pairs (FLPs) upon the creation of oxygen vacancies. The surface measurements, type and density of acid sites of the catalysts, showed that the Lewis acid sites enhanced the selectivity for ketone production; while Bronsted acid sites increased the formation of by‐products. Moreover, the ketone formation rate was directly proportional to acid density. The findings of this research provide a different approach for catalyst design, based on defects engineering and their effect on the surface activity, which could be used for enhancing the catalytic performance of novel metal oxides.
Interface Charge Distribution Engineering of Pd‐CeO2/C for Efficient Carbohydrazide Oxidation Reaction
Authors: Hu Tianjun , Liu Jiali , Yuan Hongjie , Zhang Limin , Wang Ying
Published: September 2023

Carbohydrazide electrooxidation reaction (COR) is a potential alternative to oxygen evolution reaction in water splitting process. However, the sluggish kinetics process impels to develop efficient catalysts with the aim of the widespread use of such catalytic system. Since COR concerns the adsorption/desorption of reactive species on catalysts, the electronic structure of electrocatalyst can affect the catalytic activity. Interface charge distribution engineering can be considered to be an efficient strategy for improving catalytic performance, which facilitates the cleavage of chemical bond. Herein, highly dispersed Pd nanoparticles on CeO2/C catalyst are prepared and the COR catalytic performance is investigated. The self‐driven charge transfer between Pd and CeO2 can form the local nucleophilic and electrophilic region, promoting to the adsorption of electron‐withdrawing and electron‐donating group in carbohydrazide molecule, which facilitates the cleavage of C−N bond and the carbohydrazide oxidation. Due to the local charge distribution, the Pd‐CeO2/C exhibits superior COR catalytic activity with a potential of 0.27 V to attain 10 mA cm−2. When this catalyst is used for energy‐efficient electrolytic hydrogen production, the carbohydrazide electrolysis configuration exhibits a low cell voltage (0.6 V at 10 mA cm−2). This interface charge distribution engineering can provide a novel strategy for improving COR catalytic activity.
Position‐only planar hexagonal array antenna pattern nulling with simultaneous side lobe reduction at multiple azimuth planes
Authors: Misra Bitan , Mahanti Gautam Kumar
Published: September 2023

This article presents a study on the placement of multiple nulls as well as minimization of side lobe level in the radiation pattern using a planar hexagonal antenna array structure in two different vertical planes. The desired null depth is achieved to suppress the interference signal by the position‐only control of the uniformly excited isotropic antennas in the array structure. The immediate solution to the mentioned computational problem is reached by various meta‐heuristic optimization algorithms such as teaching learning‐based optimization (TLBO), symbiotic organism search (SOS), and moth fly optimization (MFO) within a considerably reduced processing time with a control over the design constrains. Various examples for diversified scenarios are demonstrated to place multiple deep nulls in the radiation pattern without compromising the pattern constraints and all other radiation pattern characteristics. This experiment sought to illustrate and quantify the unique benefits and limitations of proposed technique using three considered meta‐heuristic optimization algorithm.