bluuebunny/crossref_metadata_2025 huggingface dataset:
Dual‐Band Operating Metaholograms with Heterogeneous Meta‐Atoms in the Visible and Near‐Infrared
Authors: Kim Inki , Jeong Heonyeong , Kim Joohoon , Yang Younghwan , Lee Dasol , Badloe Trevon , Kim Gyeongtae , Rho Junsuk
Published: June 2021

Metasurfaces consisting of sub‐wavelength structures have been researched as an alternative ultra‐thin platform for flat optical devices. One promising application is in multifunctional metaholograms for anticounterfeit purposes. By extending the operating wavelength band of conventional meta‐holographic optics, which typically operate only in the visible, it is possible to realize a security‐enhanced anticounterfeit technology. Here, a dual‐band reflective metahologram that operates simultaneously in the visible and near‐infrared domains using heterogeneous meta‐atoms, is proposed. The device consists of both hydrogenated amorphous silicon and gold metasurfaces in the same plane, where the two materials exhibit maximized conversion efficiency at wavelengths of 532 and 980 nm, respectively. The demonstrated wavelength‐multiplexed metahologram can provide a pragmatic path toward a security‐enhanced anticounterfeit technology.
Stereodefined tetraarylethylenes: Synthesis and applications
Authors: Zhang Minghao , Zhao Wanxiang
Published: June 2021

Luminescent materials with efficient aggregate‐state emissions are of growing interest due to their widespread applications in chemo‐/biosensing and optoelectronic devices. Aggregation‐induced emission (AIE) opens a new avenue for the applications of aggregate‐state luminescent materials. Among the AIE luminogens (AIEgens), tetraarylethylenes (TAEs) are typical AIEgens with a simple molecule scaffold and could be utilized as a framework for further elaboration, enabling structure‐property‐function relationship studies and multi‐functional applications. Since the existing approaches for the preparation of tetraarylethenes (TAEs) typically produce stereoisomeric mixtures, stereoselective synthesis of tetraarylethenes with desired geometry is a great challenge. In this review, we systematically compile the synthetic methodologies for the construction of TAEs in excellent regio‐ and stereoselectivities. The virtues and limitations of each methodology are discussed in detail as well. Meanwhile, the applications and the differences of properties between TAEs stereoisomers are introduced.
Effect of plant origin and phenological stage on the allelopathic activity of the invasive species Oxalis pes‐caprae
Authors: Lorenzo Paula , González Luís , Ferrero Victoria
Published: June 2021

PREMISE

Invasion processes involve several mechanisms, some of which have received little attention. Allelopathy has been invoked as an invasion driver according to the novel weapon hypothesis (NWH), and polyploidization can also be an important factor for invasion success. However, very few studies have addressed both topics together. We analyzed the allelopathic effect of the polyploid Oxalis pes‐caprae, an invader in mediterranean‐climate areas worldwide, from different origins and ploidy levels (native: South Africa; invaded: Chile, Australia, California, and the Mediterranean Basin) on Lactuca sativa as a model species.

METHODS

We measured seed germination, initial plant height, and aboveground and belowground biomass of Lactuca grown in field soil mixed with Oxalis material and with or without activated carbon in a common garden experiment. We performed the experiment twice, when Oxalis was vigorous and when senescent.

RESULTS

Vigorous plants of Oxalis tended to reduce Lactuca germination, but both vigorous and senescent Oxalis plants increased Lactuca biomass, probably due to an increase in nutrients provided by plant material. The highest increase in Lactuca traits occurred with Oxalis plants from the Iberian Peninsula. Allelopathy only happened when Oxalis was senescent and was especially strong with plants from Chile.

CONCLUSIONS

Although we did not find broad evidence for the NWH considering all areas together, we reported differences in the allelopathic potential of Oxalis plants depending on their origin. These results highlight the independent evolution of invasiveness traits in distant introduced ranges and the importance of the invaders’ origin when testing hypotheses about invasion drivers.
Fragmentation in the future of work: A horizon scan examining the impact of the changing nature of work on workers experiencing vulnerability
Authors: Jetha Arif , Shamaee Ali , Bonaccio Silvia , Gignac Monique A. M. , Tucker Lori B. , Tompa Emile , Bültmann Ute , Norman Cameron D. , Banks Cristina G. , Smith Peter M.
Published: June 2021

Introduction

The future of work is characterized by changes that could disrupt all aspects of the nature and availability of work. Our study aims to understand how the future of work could result in conditions, which contribute to vulnerability for different groups of workers.

Methods

A horizon scan was conducted to systematically identify and synthesize diverse sources of evidence, including academic and gray literature and resources shared over social media. Evidence was synthesized, and trend categories were developed through iterative discussions among the research team.

Results

Nine trend categories were uncovered, which included the digital transformation of the economy, artificial intelligence (AI)/machine learning‐enhanced automation, AI‐enabled human resource management systems, skill requirements for the future of work; globalization 4.0, climate change and the green economy, Gen Zs and the work environment; populism and the future of work, and external shocks to accelerate the changing nature of work. The scan highlighted that some groups of workers may be more likely to experience conditions that contribute to vulnerability, including greater exposure to job displacement or wage depression. The future of work could also create opportunities for labor market engagement.

Conclusion

The future of work represents an emerging public health concern. Exclusion from the future of work has the potential to widen existing social and health inequities. Thus, tailored supports that are resilient to changes in the nature and availability of work are required for workers facing vulnerability.
Macrodiolide Diversification Reveals Broad Immunosuppressive Activity That Impairs the cGAS‐STING Pathway
Authors: Liu Han , Ottosen Rasmus N. , Jennet Kira M. , Svenningsen Esben B. , Kristensen Tobias F. , Biltoft Mette , Jakobsen Martin R. , Poulsen Thomas B.
Published: June 2021

The development of new immunomodulatory agents can impact various areas of medicine. In particular, compounds with the ability to modulate innate immunological pathways hold significant unexplored potential. Herein, we report a modular synthetic approach to the macrodiolide natural product (−)‐vermiculine, an agent previously shown to possess diverse biological effects, including cytotoxic and immunosuppressive activity. The synthesis allows for a high degree of flexibility in modifying the macrocyclic framework, including the formation of all possible stereoisomers. In total, 18 analogues were prepared. Two analogues with minor structural modifications showed clearly enhanced cancer cell line selectivity and reduced toxicity. Moreover, these compounds possessed broad inhibitory activity against innate immunological pathways in human PBMCs, including the DNA‐sensing cGAS‐STING pathway. Initial mechanistic characterization suggests a surprising impairment of the STING‐TBK1 interaction.
Triple‐Vertex Linkage of (BO4)‐Tetrahedra in a Borosulfate: Synthesis, Crystal Structure, and Quantum‐Chemical Investigation of Sr[B3O(SO4)4(SO4H)]
Authors: Pasqualini Leonard C. , Huppertz Hubert , Je Minyeong , Choi Heechae , Bruns Jörn
Published: June 2021

Borosulfates are classified as silicate analogue materials. The number of crystallographically characterized compounds is still limited, whereas the structural diversity is already impressive. The anionic substructures of borosulfates exhibit vertex‐connected (BO4)‐ and (SO4)‐tetrahedra, whereas bridging between two (SO4)‐ or even between two (BO4)‐tetrahedra is scarce. The herein presented compound Sr[B3O(SO4)4(SO4H)] is the first borosulfate with a triple‐vertex linkage of three (BO4) tetrahedra via one common oxygen atom. DFT calculations complement the experimental studies. Bader charges (calculated for all atoms) as well as charge‐density calculations give hint to the electron distribution within the anionic substructure and density‐of‐states calculations support the interpretation of the bonding situation.
Interactions between affect, cognition, and information behavior in the context of fibromyalgia
Authors: Chen Annie T.
Published: June 2021

It is widely recognized that affect and cognition can have a profound influence on information behavior. However, how these factors affect information behavior in the context of chronic, stigmatized conditions is less clear. This study employed a qualitative approach to explore the interrelatedness of affect, cognition, and information behavior among persons with fibromyalgia. Persons with fibromyalgia were recruited using multiple recruitment strategies (e.g., listservs and social media) for an interview study. The interview guided participants to tell their story as they drew a timeline. Data were analyzed using qualitative data analysis methods based on the Grounded Theory Methodology. Participants' narratives illustrated that affect and cognition had diverse effects on participants' information and health behaviors: uncertainty and negative affect promoted information seeking; affect and information facilitated reconceptualization and self‐growth; and online venues facilitated venting, gave rise to validating experiences, and provided opportunities to help others. This study's findings contribute to extant knowledge by connecting affect, cognition, and action in long‐term health management. The study also provides recommendations for practice: a need to focus on practical management strategies in information provision, develop information resources to address the needs of diverse populations, and promote empathy and awareness concerning invisible conditions.
Asymmetric Sulfoxidation of Thioether Catalyzed by Soybean Pod Shell Peroxidase to Form Enantiopure Sulfoxide in Water‐in‐Oil Microemulsions: A Kinetic Model
Authors: Li Huiling , Deng Yashan , Du ShanShan , Liu Cui , Li Kaiyuan , Xue Xiao , Xu Hui , Zhang Yuanyuan , Yi Tingting , Gao Xin
Published: June 2021

Esomeprazole with chiral sulfoxides structure is used to treat gastric ulcer disease. Soybean pod shell peroxidase (SPSP) is a peroxidase extracted from soybean pods shells which are one of the most abundant natural resources in the world. In the production of chiral sulfoxides catalyzed by SPSP, it is very important to establish the reaction kinetic model and explore the reaction mechanism for the development of the process, however, there is no report on the establishment of the model. Asymmetric sulfoxidation reactions catalyzed by SPSP in water‐in‐oil microemulsions were carried out, and the King‐Altman approach was used to establish a kinetic model. A yield of 91% and e.e. value of 96% for esomeprazole were obtained at the activity of SPSP of 3200 U ml−1 and 50 °C for 5 h. The mechanism with a two‐electron reduction of SPSP‐I is accompanied with a single‐electron transfer to SPSP‐I and nonenzymatic reactions, indicating that three concomitant sub‐mechanisms contribute to the asymmetric oxidation involving five enzymatic and two nonenzymatic reactions, which can represent the asymmetric sulfoxidation of organic sulfides to form enantiopure sulfoxides. With 5.44% of the average relative deviation, a kinetic model fitting experimental data was developed. The enzymatic reactions may follow ping‐pong mechanism with substrate inhibition of H2O2 and product inhibition of esomeprazole, while nonenzymatic reactions follow a power law. Those results indicate that SPSP with a lower cost and higher thermal stability may be used as an effective substitute for horseradish peroxidase.
Co‐Catalysis for Hydroamidocarbonylation of Alkynes with Amides over a Bifunctional Ligand‐Based Pd Catalyst
Authors: Yang Da , Zhou Guang‐Zhao , Zhang Long‐Li , Liu Huan
Published: June 2021

The hydroamidocarbonylation of alkynes with amides allows for the synthesis of α,β‐unsaturated imides with the advantage of 100% atomic economy. Herein, the bifunctional ligand (L1) containing a sulfonic acid group (‐SO3H) and phosphino‐fragment enable the Pd catalyst to accomplish the hydroamidocarbonylation of alkynes with amides. It was found that, due to an intramolecular synergetic effect, the L1‐based Pd‐catalyst exhibited much higher activity than the individual mechanical mixtures of Xantphos‐based Pd‐complex and MeSO3H. The formation and stability of Pd‐H species were promoted by the presence of L1, which was verified by in situ high‐pressure FT‐IR analysis. Under the optimized conditions, the target products of the branched imides were obtained with yields in the range of 46–87% over the L1‐based Pd‐catalyst. Advantageously, as an ionic ligand, the L1‐based Pd‐catalyst could be recycled for 4 runs in the ionic liquid of [Bmim]NTf2 without any obvious activity loss and detectable metal leaching.
Synthesis of 8,12‐Dibromocorrole and Its Transformation to Antiaromatic 8,10‐Fused Iminoisocorrole with a Polarized Resonance Contribution
Authors: Ueta Kento , Nakai Akito , Tanaka Takayuki , Osuka Atsuhiro
Published: June 2021

8,12‐Dibromo‐5,15‐bis(pentafluorophenyl)corrole and its Ag(III) complex were prepared via intramolecular oxidative coupling of a 8,12‐dibromobilane precursor. The Ag(III) complex was allowed for further transformation via Suzuki coupling reaction. Thus, 2‐aminophenyl group was coupled at one of the β‐positions, and subsequent demetalation followed by oxidation with MnO2 afforded 8,10‐fused iminoisocorrole in good yields. The iminoisocorrole exhibited weak antiaromaticity due to the C(+)−N(−) polarized resonance contribution as evidenced by 1H NMR spectrum, UV/vis absorption spectra, cyclic voltammetry, and theoretical calculations.
Orthonormal shifted discrete Hahn polynomials for a new category of nonlinear variable‐order fractional 2D optimal control problems
Authors: Heydari Mohammad Hossein , Avazzadeh Zakieh , Cattani Carlo
Published: June 2021

The present work provides a formulation for the orthonormal shifted discrete Hahn polynomials on an arbitrary domain. We also extract some useful matrix relationshipsrelating to these discrete polynomials. These polynomials and the obtained relations are employed with the Lagrange multipliers technique to design a numerical method for solving a class of variable‐order (VO) fractional 2D optimization problems subject to Robin boundary value conditions. The proposed method converts the VO fractional system into a system of algebraic equations which readily can be solved. Some numerical examples are studied to validate and illustrate the accuracy of the introduced technique.
Spatial transcriptomics and proteomics technologies for deconvoluting the tumor microenvironment
Authors: Wang Nan , Li Xia , Wang Rongshui , Ding Zhiyong
Published: June 2021

The tumor microenvironment (TME) harbors heterogeneous contents and plays critical roles in tumorigenesis, metastasis, and drug resistance. Therefore, the deconvolution of the TME becomes increasingly essential to every aspect of cancer research and treatment. Novel spatially‐resolved high‐plex molecular profiling technologies have been emerging rapidly as powerful tools to obtain in‐depth understanding from TME perspectives due to their capacity to allow high‐plex protein and RNA profiling while keeping valuable spatial information. Based on our practical experience, we review a variety of available spatial proteogenomic technologies, including 10X Visium, GeoMx Digital Spatial Profiler (DSP), cyclic immunofluorescence‐based CODEX and Multi‐Omyx, mass spectrometry (MS)‐based imaging mass spectrometry (IMS) and multiplex ion‐beam imaging (MIBI). We also discuss FISSEQ, MERFISH, Slide‐seq, and HDST, some of which may become commercially available in the near future. In particular, with our experience, we elaborate on DSP for spatial proteogenomic profiling and discuss its unique features designed for immuno‐oncology and propose anticipation towards its future direction. The emerging spatially technologies are rapidly reshaping the magnitude of our understanding of the TME.
Lamotrigine for acute bipolar depression: An exploratory item‐level analysis
Authors: Peters Evyn M. , Lodhi Rohit J. , Zhang Yanbo , Li Hua , Balbuena Lloyd
Published: June 2021

Objectives

Lamotrigine is used to treat bipolar depression despite inconsistent evidence. Here we present the results of an exploratory item‐level analysis of pooled data from five randomized placebo‐controlled trials of lamotrigine for acute bipolar depression. The goal was to determine if certain depression scale items were more responsive to lamotrigine treatment.

Methods

The pooled sample contained 1072 adult outpatients treated for up to 7–10 weeks. Depressive symptoms were measured with the Hamilton Depression Rating Scale and the Montgomery–Åsberg Depression Rating Scale. Change scores on individual scale items were compared between treatment groups.

Results

There were statistically significant effects on items assessing depressed mood/sadness, lack of interest/anhedonia, pessimism/guilt, and anergia/fatigue, on both scales. However, there was marked variation in the baseline symptom prevalence, and items with higher scores at baseline tended to have larger and statistically significant treatment effects.

Conclusions

The results suggested a significant treatment effect on core symptoms of depression. A floor effect appeared to limit the sensitivity of other scale items. Given the exploratory nature of the analysis, firm conclusions cannot be drawn, although the results were consistent with past research. Relying on total depression scale sum scores over targeted assessments of core depressive symptoms may have impeded signal detection in the original trials.
A comparative analysis of 375 patients with lateral and medial medullary infarction
Authors: Tao Lin‐Shuang , Lin Jing‐Jing , Zou Ming , Chen Song‐Fang , Weng Yi‐Yun , Chen Ke‐Yang , Hu Bei‐Lei
Published: June 2021

Background

Few studies have compared the etiology and clinical features between pure lateral medullary infarction (LMI) and pure medial medullary infarction (MMI).

Methods

All patients included were hospitalized at The First Affiliated Hospital and The Second Affiliated Hospital of Wenzhou Medical University from January 2015 to July 2020. Their risk factors, clinical manifestation, stroke mechanisms and short‐term prognosis were analyzed retrospectively.

Results

Among the 387 patients enrolled, 266 (68.7%) had LMI, 109 (28.2%) had MMI, and 12 (3.1%) (nine men and three women) had LMI plus MMI. We analyzed the 375 patients of LMI and MMI. The average ages of LMI and MMI were 59.4 years and 62.69 years, respectively. Univariate analysis and multivariable logistic regression was used to investigate the existing risk factors of MMI relative to LMI. Prior infarction, poor glycemic control, and atherosclerosis were more frequently associated with MMI than with LMI. The clinical manifestation was significantly different between LMI and MMI. We used modified Rankin Scale (mRS) score as the short‐term prognostic evaluation criteria, and MMI appeared worse than LMI.

Conclusions

This study reveals that: (1) patients with MMI are older than those with LMI; (2) prior infarction, poor glycemic control, and atherosclerosis are independent risk factors of MMI than that of LMI; (3) the clinical manifestations of LMI and MMI are heterogeneous; (4) short‐term prognosis of MMI is worse than LMI.
Trend of recognizing depression symptoms and antidepressants use in newly diagnosed Parkinson's disease: Population‐based study
Authors: Orayj Khalid , Almeleebia Tahani , Vigneshwaran Easwaran , Alshahrani Sultan , Alavudeen Sirajudeen. S. , Alghamdi Wael
Published: June 2021

Objectives

Although depression symptoms are common among patients with Parkinson's disease (PD), the medical literature still reports underrecognition of depression in patients with PD. Our main objective is to examine the trend of depression recognition during the first year of PD diagnosis using large population data.

Methods

We conducted a population‐based study of residents in Wales, using the Secure Anonymized Information Linkage (SAIL) Databank. We included newly diagnosed patients with PD aged 40 years or older with a first PD diagnosis between 2000 and 2015. Depression and antidepressants related data were extracted from SAIL. A series of multilevel logistic regressions were run to determine the factors affecting depression recognition. The results were presented using odds ratios (ORs) with 95% confidence intervals (CI).

Results

The study included 6596 patients with PD. About 38% of patients had a recorded code of antidepressants, depression diagnosis, or both within the first year of PD diagnosis. There was a significant association of depression diagnosis, antidepressant use, or both with the year of PD diagnosis (OR 0.972, 95% CI 0.962–0.983). We also found that patients who used monoamine oxidase inhibitors (MAO‐B inhibitors) were associated with a lower depression diagnosis, use antidepressants, or both, compared to those who did not use MAO‐B inhibitors (OR 0.769, 95% CI 0.627–0.943).

Conclusion

There is a slight decrease in depression recognition in PD patients between 2000 and 2015, which could be due to an increase in depression recognition during the prodromal phase of PD.
Factor analysis of the relationship between PANSS score and family burden of patients with schizophrenia
Authors: Huang Jiang , Wei Wei‐Xiang , Zheng Pan‐Pan , Tang Tao , Zhang Pei‐Hao , Long Mao‐Yuan , Li Mei‐Ling , Ning Xiao‐Yu , Tian Ying‐Yun , Cheng Yu , Wu Jun
Published: June 2021

Objective

This study aims to investigate the burden of family caregivers of patients with schizophrenia, and its influencing factors

Methods

A total of 105 patients with schizophrenia and their caregivers were investigated using the positive and negative symptom scale (PANSS) and family burden scale of disease (FBS)

Results

There was a strong correlation between the patient's recovery and family burden, especially between positive and negative symptoms and family financial burden, family daily activities, family recreational activities, and family relationship

Conclusion

There is a strong correlation between the patient's recovery and family burden, and this is especially correlated to family economic burden, family daily activities, family recreational activities, and family relationship. Medical staff should pay attention to the psychological characteristics of patients and fully understand and avoid the adverse effects of family burden on the rehabilitation of patients.
The problem with assumptions: Revisiting “The dark figure of sexual recidivism”
Authors: Lave Tamara Rice , Prescott J.J. , Bridges Grady
Published: June 2021

What is the actual rate of sexual recidivism given the well‐known fact that many crimes go unreported? This is a difficult and important problem, and in “The dark figure of sexual recidivism,” Nicholas Scurich and Richard S. John (2019) attempt to make progress on it by “estimat[ing] actual recidivism rates . . . given observed rates of reoffending” (p. 171). In this article, we show that the math in their probabilistic model is flawed, but more importantly, we demonstrate that their conclusions follow ineluctably from their empirical assumptions and the unrepresentative empirical research they cite to benchmark their calculations. Scurich and John contend that their analysis undermines what they call the “orthodoxy in academic circles” (p. 173) of low sexual recidivism rates among individuals convicted of sexual offenses, but we underscore that their article does not analyze data in the traditional sense; instead, it just interprets past scholarly work through the use of strong assumptions in a way that, for practitioners, is likely to be opaque and misleading (and, for us, strays into speculation, argument, or advocacy and away from objective research). Our simple calculations show that their findings are highly sensitive to their assumptions, and we conclude that courts and others should recognize Scurich and John's work for what it is—a set of complex hypotheticals that are no more reliable than what judges and lawyers accomplish on their own by simply recognizing the basic problem that not all sexual offenses are reported.
A five‐gene signature is a prognostic biomarker in pan‐cancer and related with immunologically associated extracellular matrix
Authors: Yu Chunlai , You Mingliang , Zhang Peizhen , Zhang Sheng , Yin Yuzhu , Zhang Xiao
Published: June 2021

The tumor microenvironment (TME) is related to extracellular matrix (ECM) dynamics and has a broad fundamental and mechanistic role in tumorigenesis and cancer progression. We hypothesized that ECM regulators might play an essential role in pan‐cancer attribution by causing a generic effect through its regulation of the dynamics of ECM alteration. By analyzing data from TCGA using GSEA and univariate Cox regression analysis, we found that ECM regulator genes were significantly enriched and contributed to mortality in various cancer types. Notably, UMAP analysis revealed that ECM regulator genes dominated the differences between tumor and adjacent normal tissues based on 59 or 31 pan‐survival‐related ECM gene sets. Subsequently, a five‐gene signature consisting of the predominant ECM regulators ADAM12, MMP1, SERPINE1, PLOD3, and P4HA3 was identified. We found that this five‐gene signature was pro‐mortality in 18 types of cancer in TCGA, and validated eleven other cancer types in TCGA and seven types in the TARGET and CoMMpass databases using overall survival analysis. KEGG pathway enrichment and Pearson correlation analysis indicated that these five component genes that were correlated with specific ECM proteins involved in tumorigenesis from the ECM receptor interaction gene set. Additionally, the fitted results of a linear model were applied to strengthen the discovery, demonstrating that the five genes were correlated with immune infiltration score and especially associated with typically immunologically “cold” tumors. We thus conclude that the ADAM12, MMP1, SERPINE1, PLOD3, and P4HA3 signature showed a close association with a pan‐cancer effect on prognosis and is related to ECM proteins in the TME which corresponding with immunologically “cold” cancer types.
Association of immune‐related pneumonitis with clinical benefit of anti‐programmed cell death‐1 monotherapy in advanced non‐small cell lung cancer
Authors: Ono Kana , Ono Hirotaka , Toi Yukihiro , Sugisaka Jun , Aso Mari , Saito Ryohei , Kawana Sachiko , Aiba Tomoiki , Odaka Tetsuo , Matsuda Suguru , Saito Shin , Narumi Akane , Ogasawara Takahiro , Shimizu Hisashi , Domeki Yutaka , Terayama Keisuke , Kawashima Yosuke , Nakamura Atsushi , Yamanda Shinsuke , Kimura Yuichiro , Honda Yoshihiro , Sugawara Shunichi
Published: June 2021

Background

The association between the development of checkpoint inhibitor pneumonitis (CIP) with tumor response and survival has remained unclear so far. The aim of the present study was to evaluate the association between CIP and the clinical efficacy of anti‐programmed cell death‐1 antibody in patients with advanced non‐small cell lung cancer (NSCLC).

Methods

Between January 2016 and August 2019, 203 advanced NSCLC patients were administered with nivolumab or pembrolizumab. Comparisons were made between patients with and without CIP. We evaluated the time‐to‐treatment failure (TTF), progression‐free survival (PFS), and overall survival (OS).

Results

CIP was observed in 28 (14%) patients. CIP was associated with a longer PFS (18.9 months [95% confidence interval, CI: 8.7 months–not reached] vs. 3.9 months [95% CI: 3.4–5.1 months, p < 0.01]) and longer OS (27.4 [95% CI: 20.7 months–not reached] vs. 14.8 months [95% CI: 11.2–17.9 months, p = 0.003]). Most patients discontinued the immune checkpoint inhibitor (ICI) treatment when they developed CIP. Seven patients (25%) lived for more than 300 days from treatment discontinuation and did not show any long‐term tumor growth after treatment discontinuation.

Conclusion

CIP was associated with prolonged PFS and OS. Additionally, 25% of CIP patients did not show any tumor growth for long periods after treatment discontinuation. Careful management of CIP can help in obtaining the best clinical efficacy from anti‐PD‐1 antibody.
Preparation of One‐Pot Immobilized Lipase with Fe3O4 Nanoparticles Into Metal‐Organic Framework For Enantioselective Hydrolysis of (R,S)‐Naproxen Methyl Ester
Authors: Ozyilmaz Elif , Ascioglu Sebahat , Yilmaz Mustafa
Published: June 2021

Immobilization of enzyme to magnetic metal‐organic frameworks (MOF) can preserve biological functionality in harsh environments to increase enzymes activity, stability, and improve reusability. The magnetic Fe3O4 nanoparticles were treated with calix[4]arene tetracarboxylic acid (Calix) and Candida rugosa lipase (CRL), and then encapsulated into the zeolitic imidazole framework‐8 (Fe3O4@Calix‐ZIF‐8@CRL). The lipase activity data of Fe3O4@Calix‐ZIF‐8@CRL was 2.88 times higher than that of the Fe3O4@ZIF‐8@CRL (without Calix). The catalytic properties of immobilized lipases were studied on the enantioselective hydrolysis of R/S‐naproxen methyl ester. It was also observed that Fe3O4@Calix‐ZIF‐8@CRL has excellent enantioselectivity (E=371) compared to Fe3O4@ZIF‐8@CRL (E=131). Furthermore, Fe3O4@Calix‐ZIF‐8@CRL was seen to still retain 30 % of the conversion rate after the fifth reuse. This work may also be useful for the pharmaceutical industry due to the increased reusability and stability of enzymes, the enantiomeric selectivity exhibited by MOF‐enzyme biocomposites, and the significant differences in the biological activities of the enantiomers.
Catalytic Kinetics Considerations and Molecular Tools for the Design of Multienzymatic Cascade Nanoreactors
Authors: Chauhan Kanchan , Zárate‐Romero Andrés , Sengar Prakhar , Medrano Carlos , Vazquez‐Duhalt Rafael
Published: June 2021

Within the cellular microenvironment of organisms, the surface‐ and volume‐ enclosed multiple enzymes perform highly complex series of chemical reactions for very selective and efficient synthesis of biomolecules. Several efforts have been carried out to mimic these timely and spatially defined natural enzyme cascade reactions onto the artificial multienzyme nano‐assemblies via immobilization of two or more enzymes on nanosupport, while maintaining the catalytic activity. These biocatalytic systems undergo cascade reactions for the efficient production of chemicals and materials of interest. Their increasing interest is based on their numerous potential applications in the area of environmental, biomedical and applied chemistry. A variety of nanosupports and multienzyme immobilization techniques have been optimized and reported. Nanoreactors usually show molecular crowding and anomalous diffusion of substances that modify the mass action kinetic laws. Thus, the kinetics is different than those shown by free diluted enzymes. Consequently, the catalytic activity considerations in cascade reactions on nanoassemblies are of great importance. Thus, in this work, important parameters of enzyme kinetics in cascade reaction and the molecular tools for the design and optimization of bi‐ and multi‐enzymatic nanobioreactors reactions are discussed.
Bonding in Barium Boryloxides, Siloxides, Phenoxides and Silazides: A Comparison with the Lighter Alkaline Earths
Authors: Le Coz Erwann , Hammoud Joanna , Roisnel Thierry , Cordier Marie , Dorcet Vincent , Kahlal Samia , Carpentier Jean‐François , Saillard Jean‐Yves , Sarazin Yann
Published: June 2021

Barium complexes ligated by bulky boryloxides [OBR2]− (where R=CH(SiMe3)2, 2,4,6‐iPr3‐C6H2 or 2,4,6‐(CF3)3‐C6H2), siloxide [OSi(SiMe3)3]−, and/or phenoxide [O‐2,6‐Ph2‐C6H3]−, have been prepared. A diversity of coordination patterns is observed in the solid state for both homoleptic and heteroleptic complexes, with coordination numbers ranging between 2 and 4. The identity of the bridging ligand in heteroleptic dimers [Ba(μ2‐X1)(X2)]2 depends largely on the given pair of ligands X1 and X2. Experimentally, the propensity to fill the bridging position increases according to [OB{CH(SiMe3)2}2)]−<[N(SiMe3)2]−<[OSi(SiMe3)3]−<[O(2,6‐Ph2‐C6H3)]−<[OB(2,4,6‐iPr3‐C6H2)2]−. This trend is the overall expression of 3 properties: steric constraints, electronic density and σ‐ and π‐donating capability of the negatively charged atom, and ability to generate Ba ⋅ ⋅ ⋅ F, Ba ⋅ ⋅ ⋅ C(π) or Ba ⋅ ⋅ ⋅ H−C secondary interactions. The comparison of the structural motifs in the complexes [Ae{μ2‐N(SiMe3)2}(OB{CH(SiMe3)2}2)]2 (Ae = Mg, Ca, Sr and Ba) suggest that these observations may be extended to all alkaline earths. DFT calculations highlight the largely prevailing ionic character of ligand‐Ae bonding in all compounds. The ionic character of the Ae‐ligand bond encourages bridging coordination, whereas the number of bridging ligands is controlled by steric factors. DFT computations also indicate that in [Ba(μ2‐X1)(X2)]2 heteroleptic dimers, ligand predilection for bridging vs. terminal positions is dictated by the ability to establish secondary interactions between the metals and the ligands.
Quadruple Role of Pd Catalyst in Domino Reaction Involving Aryl to Alkyl 1,5‐Pd Migration to Access 1,9‐Bridged Triptycenes
Authors: Iwata Takayuki , Kumagai Satoru , Yoshinaga Tatsuro , Hanada Masato , Shiota Yoshihito , Yoshizawa Kazunari , Shindo Mitsuru
Published: June 2021

A Pd‐catalyzed domino reaction of 1,8,13‐tribromo‐9‐methoxytriptycenes is reported. Under conventional Suzuki coupling conditions, the triptycenes underwent multiple transformations to give 1,9‐bridged triptycenes. Based on mechanistic investigations, a single Pd catalyst functions as Pd0, PdII and PdIV species to catalyze four distinct processes: (1) aryl to alkyl 1,5‐Pd migration, (2) intramolecular arylation, (3) homocoupling of phenylboronic acid and (4) Suzuki coupling. DFT calculations revealed that 1,5‐Pd migration likely proceeds via both concerted PdII and stepwise PdIV routes. Asymmetric synthesis of the chiral triptycenes, as well as optical resolution, and further transformation are also reported.
A‐site Cation Defects (Ba0.5Sr0.5)1–xCo0.8Fe0.2O3–δ Perovskites as Active Oxygen Evolution Reaction Catalyst in Alkaline Electrolyte†
Authors: Tang Lulu , Rao Yifei , Wei Lianwei , Zheng Hui , Liu Huimin , Zhang Wenhua , Tang Kaibin
Published: June 2021

Main observation and conclusion

Perovskites (Ba0.5Sr0.5)1–xCo0.8Fe0.2O3–δ (x = 0.02, 0.05, 0.1 denoted as BSCF‐0.98, BSCF‐0.95, BSCF‐0.9, respectively) with A‐site cation defects are synthesized by simple and efficient sol‐gel method and are proved to have better OER catalytic effect than the well‐known Ba0.5Sr0.5Co0.8Fe0.2O3–δ (BSCF) oxides. BSCF‐0.95 exhibits the best OER catalytic activity in the series perovskite. The current density of BSCF‐0.95 is about 56% higher than that of BSCF oxide at a potential of 1.7 V. The experimental studies have shown that compared with BSCF, BSCF‐0.95 oxide has a larger electrochemical surface area (ECSA), a higher content of O22– species related to surface oxygen vacancies, and faster charge transfer rate, which may be the factors for the enhancement of OER activity. The theoretical calculation results prove that the center positions of the O 2p‐band of perovskite with A‐site cation defects are closer to the Fermi level than BSCF oxide, which agrees with the OER performance trend of the material.
Allergen immunotherapy for respiratory allergy: Quality appraisal of observational comparative effectiveness studies using the REal Life Evidence AssessmeNt Tool. An EAACI methodology committee analysis
Authors: Di Bona Danilo , Paoletti Giovanni , Chu Derek K. , Pepys Jack , Macchia Luigi , Heffler Enrico , Canonica Giorgio Walter
Published: June 2021

Background

Observational comparative effectiveness studies in allergen immunotherapy (AIT) represent an important evidence source answering research questions that can be challenging to obtain from randomized controlled trials (RCTs), such as long‐term benefits of AIT, the effects on asthma prevention and the onset of new allergen sensitizations. However, observational studies are prone to several sources of bias, which limit their reliability.

The REal Life Evidence AssessmeNt Tool (RELEVANT) was recently developed to assist in quality appraisal of observational comparative research to enable identification of useful nonrandomized studies to be considered within guideline development.

Objective

To systematically appraise the quality of published observational comparative AIT studies using RELEVANT.

Methods

Observational studies comparing AIT to pharmacotherapy for respiratory allergies, assessing as outcome measures reduction of symptoms and/or medication use reduction, were retrieved by computerized bibliographic searches. According to RELEVANT, a failure to meet any one of primary items (background, design, measures, analysis, results, discussion/interpretation, and conflict of interest) represents a critical flaw, significantly undermining the validity of the study results.

Results

The 14 studies identified supported the benefit of AIT in real‐life, which persists after treatment discontinuation. However, none of them met all the 7 primary RELEVANT criteria. The main defects were reported in the design (28.6% of studies), measures and analysis (64.3% of studies), and results (78.6% of studies) items, due to selection bias and lack of methods for adjusting controls. Half of the studies did not report on conflict of interest.

Conclusion

There is a need for more robust observational research in AIT. RELEVANT appears as an easy‐to‐use and sensitive tool for quality appraisal in AIT studies.
Upper Tail Large Deviations in First Passage Percolation
Authors: Basu Riddhipratim , Ganguly Shirshendu , Sly Allan
Published: June 2021

For first passage percolation on with i.i.d. bounded edge weights, we consider the upper tail large deviation event, i.e., the rare situation where the first passage time between two points at distance n is macroscopically larger than typical. It was shown by Kesten [24] that the probability of this event decays as . However, the question of existence of the rate function, i.e., whether the log‐probability normalized by n2 tends to a limit, remains open. We show that under some additional mild regularity assumption on the passage time distribution, the rate function for upper tail large deviation indeed exists. The key intuition behind the proof is that a limiting metric structure that is atypical causes the upper tail large deviation event. The formal argument then relies on an approximate version of the above which allows us to use independent copies of the large deviation environment at a given scale to form an environment at a larger scale satisfying the large deviation event. Using this, we compare the upper tail probabilities for various values of n. © 2021 Wiley Periodicals LLC.
Therapeutic relationship and professional burnout in psychotherapists: A structural equation model approach
Authors: Zarzycka Beata , Jankowski Tomasz , Krasiczyńska Barbara
Published: June 2021

Previous studies on the therapists' burnout have focused on individual and environmental risk factors. This study aimed to analyse whether variables reflecting therapeutic relationship—the therapist experience of relational depth and quality of the therapeutic relationship—can be related to psychotherapist burnout. Four alternative path models were examined. A total of 101 humanistic–experiential psychotherapists, aged between 29 and 86 years, participated in the research. The Relational Depth Frequency Scale, the Scale to Assess the Therapeutic Relationship, the Psychological Well‐Being Scale and the Link Burnout Questionnaire were applied to the research. The results showed that relational depth and therapeutic quality correlated negatively with psychotherapist burnout. Relational depth is the main predictor of psychological well‐being and psychotherapist burnout through its effect on therapeutic quality. The experiences of relational depth, primarily of person‐centred therapists, have positive psychological potential in predicting lower professional burnout.
Trials for new antidepressants leave out suicidal patients, show little benefit
Authors: Knopf Alison
Published: June 2021

It will come as no surprise to practicing clinicians that shortcomings of randomized trials of newer antidepressant medications make interpretations of findings difficult. A recent meta‐analysis has found that most newer antidepressants may reduce symptoms compared to placebo, but these changes are “small and unimportant” for the majority of antidepressants, the researchers write. However, depression is a heterogeneous condition, and some patients may have a greater response. The researchers concluded that sertraline, escitalopram, duloxetine, as well as fluoxetine (which is currently the only treatment recommended for first‐line prescribing) could be considered as a first option.
The cross‐cultural effects of brand status and social facilitation on enhancing consumer perception toward circular fashion services
Authors: Ramkumar Bharath , Woo Hongjoo , Kim Naeun (Lauren)
Published: June 2021

While existing clothing consumption practices are contributing to increasing environmental degradation, circular fashion promises to be a more sustainable approach to keep used clothes in circulation instead of being sent to landfills. However, it is necessary to use more than just environmental benefits to motivate consumers to shop for secondhand clothing online through a circular fashion service. Therefore, through two experiments, this study tests the role of brand and social facilitation due to perceived economic and social benefits and the attitude and intention to use a circular fashion service among U.S. and Korean consumers. By applying commodity theory and social facilitation theory, this study found that brand status and a socially facilitating message can enhance perceived benefits, attitude, and intention toward using a circular fashion service, while specific effects are found differently between U.S. and Korean consumers. Implications of these findings and limitations of the study are discussed.
Wide slot tri‐band antenna for Wireless Local Area Network/World‐Wide Interoperability for Microwave Access applications
Authors: Patel Upesh , Parekh Megh , Desai Arpan , Upadhyaya Trushit
Published: June 2021

A low‐profile, tri‐band, wide slot antenna for the Wireless Local Area Network (WLAN) and World‐Wide Interoperability for Microwave Access (WiMAX) applications is proposed in this article. The surface dimension of the proposed planar antenna is 0.32λ × 0.32λ mm2 (lowest operating frequency). The antenna structure consists of a wide slot which is formed by carefully etching out the square and circular shapes from the basic patch antenna. The standard cost‐effective FR‐4 substrate with a thickness of 1.6 mm is used for the fabrication of the prototype. Tri‐band resonance at 2.4, 3.5, and 5.5 GHz is achieved with the peak gain of 3.33, 1.12, and 1.37 dBi, respectively. The impedance bandwidth at three resonant peaks is 15.36%, 11.7%, and 8.29% with Voltage Standing Wave Ratio (VSWR) well below the requirement of 1.5. Dipole‐shaped radiation patterns, average gain > 1.96 dBi, and efficiency of 83% make the antenna commercially viable for use in WLAN and WiMAX devices.
Dolphin swarm optimization algorithm for software‐defined antenna selection algorithm in underwater acoustic sensor network
Authors: S Sankar Ganesh , Rajaprakash S.
Published: June 2021

Underwater acoustic sensor network (UASN) employs to monitor the aquatic environment. The underwater nodes deploy for continuous and real‐time monitoring. The underwater nodes deploy at different depths to facilitate data forwarding from ocean floor sensor to buoys node. However, the underwater network has limited network resources such as the battery, bandwidth, and susceptibility to mobility, thermographic conditions, and propagation delay. The propagation delay and thermographic condition prolong node packet processing and delay network operation. The delayed network operation increases node battery consumption and overhead. Hence, a bio‐inspired dolphin swarm optimization algorithm (DSA) implements to select the optimal antenna for data transmission. The DSA selects the optimal antenna for data communication by evaluating the acknowledgment packet obtained for data transmitted through multiband antennas. The DSA was simulated in an NS2‐Aquasim environment and testbed to evaluate its performance. The DSA improved data reliability, packet delivery ratio by 97%, and reduced bit error rate (BER), end‐to‐end delay compared to traditional algorithms.
High foliar K and P resorption efficiencies in old‐growth tropical forests growing on nutrient‐poor soils
Authors: Urbina Ifigenia , Grau Oriol , Sardans Jordi , Margalef Olga , Peguero Guillermo , Asensio Dolores , LLusià Joan , Ogaya Romà , Gargallo‐Garriga Albert , Van Langenhove Leandro , Verryckt Lore T. , Courtois Elodie A. , Stahl Clément , Soong Jennifer L. , Chave Jerome , Hérault Bruno , Janssens Ivan A. , Sayer Emma , Peñuelas Josep
Published: June 2021

Resorption is the active withdrawal of nutrients before leaf abscission. This mechanism represents an important strategy to maintain efficient nutrient cycling; however, resorption is poorly characterized in old‐growth tropical forests growing in nutrient‐poor soils. We investigated nutrient resorption from leaves in 39 tree species in two tropical forests on the Guiana Shield, French Guiana, to investigate whether resorption efficiencies varied with soil nutrient, seasonality, and species traits. The stocks of P in leaves, litter, and soil were low at both sites, indicating potential P limitation of the forests. Accordingly, mean resorption efficiencies were higher for P (35.9%) and potassium (K; 44.6%) than for nitrogen (N; 10.3%). K resorption was higher in the wet (70.2%) than in the dry (41.7%) season. P resorption increased slightly with decreasing total soil P; and N and P resorptions were positively related to their foliar concentrations. We conclude that nutrient resorption is a key plant nutrition strategy in these old‐growth tropical forests, that trees with high foliar nutrient concentration reabsorb more nutrient, and that nutrients resorption in leaves, except P, are quite decoupled from nutrients in the soil. Seasonality and biochemical limitation played a role in the resorption of nutrients in leaves, but species‐specific requirements obscured general tendencies at stand and ecosystem level.
Magnesium Complexes of Ladanein: A Beneficial Strategy for Stabilizing Polyphenolic Antivirals
Authors: Martin‐Benlloch Xavier , Lanfranchi Don Antoine , Haid Sibylle , Pietschmann Thomas , Davioud‐Charvet Elisabeth , Elhabiri Mourad
Published: June 2021

Ladanein (noted FOMe) is a potent antiviral flavone that was shown to be active on a broad spectrum of enveloped viruses. This 5,6,7‐trihydroxylated flavone has, however, pharmacokinetic properties and a half‐life time that need to be improved for possible therapeutic applications. We herein took advantage of the complexation properties of ladanein (Fe(III)) to evaluate its ability to bind Mg(II) (biologically relevant and redox inert ion) precursors prepared beforehand from various carboxylic acids. The 5,6,7‐trihydroxylated pattern of ladanein and the ligands borne by the Mg(II) atom of the precursors were found to be essential for firm Mg(II) binding. In particular, a ternary Mg(II) complex of ladanein and pidolate (noted FOMe.MgPid) was isolated and considered for its pharmacokinetic and virucidal (Hepatitis C Virus ‐ HCV) properties. Mg(II) complexation significantly improved the physico‐chemical (solubility) and the pharmacokinetic properties (clearance, plasmatic concentration) of the flavone FOMe, while not altering its anti‐HCV capacity.