bluuebunny/crossref_metadata_2025 huggingface dataset:
A Multi-diagnostic Screening Study of the Prevalence and Risk Factors of Echinococcosis in First-degree Family Members of Infected Patients Undergoing Surgical Treatment
Authors: Kia Mahsa , Tohidinezhad Fariba , Pezeshki Rad Masoud , Afzal Aghaee Monavvar , Aliakbarian Mohsen
Published: May 2022

Background: Echinococcosis is a zoonotic infection caused by Echinococcus tapeworms. About 60% of patients remain asymptotic until severe stages. Early diagnosis of the infection in high-risk populations is of medical importance. Objectives: This study was designed to investigate the prevalence of echinococcosis among first-degree family members of the infected patients who underwent surgical treatment. Methods: A cross-sectional study was conducted to screen the first-degree family members of 96 patients who underwent surgical intervention at Imam Reza hospital, Mashhad, Iran, from September 2016 to March 2017. All family members were invited by phone calls to perform the serologic test, ultrasound examination, and chest X-ray test. Results: Forty-six (47.9%) patients participated in the study. A total of 114 family members performed the screening tests. Seven participants from five families (6.14%) were found to be infected in ultrasound examination (five females with a mean age of 36 years). There were no significant differences between the infected and non-infected groups concerning age (P = 0.921) and gender (P = 0.457). Conclusions: Screening the first-degree family members of patients with a confirmed echinococcosis infection results in the early diagnosis of infected patients, which is economically significant, especially in endemic areas.
Review of Molecular Approaches in Leishmaniasis Vaccines: Implications and Restrictions
Authors: Fattahi Bafghi Ail , Rezaee Elham , Ahmadi Somayeh , Gholamrezaei Mostafa , Firouzeh Nima
Published: May 2022

: Leishmaniasis, a cosmopolitan parasitic infection, is a sandfly-borne parasitic disease caused by different species of Leishmania. Many attempts have been made to discover effective and safe vaccines against leishmaniasis, but most of them are not accompanied by promising results. During the last decade, the characterization of new antigens for potential vaccine candidates based on classical and molecular protocols has been a hot research topic in immunological science. The present review focuses on the development and the status of various vaccines and potential vaccine candidates against leishmaniasis. Here, molecular approaches to leishmaniasis vaccine development are described. Also, implications and restrictions are discussed.
Comparative Evaluation of the Effects of Different Dietary Fibers as Natural Additives on the Shelf Life of Cooked Sausages
Authors: Aminzare Majid , Hashemi Mohammad , Afshari Asma , Noori Seyyed Mohammad Ali , Rezaeigolestani Mohammadreza
Published: May 2022

Background: The incorporation of dietary fibers in meat and processed meats has been introduced as an approach to amend the nutritional quality and technological properties of the products. Objectives: This study explores the effects of four dietary fibers, including orange fiber (OF), wheat fiber (WF), bamboo fiber (BF), and carrot fiber (CF), on shelf life of emulsion-type cooked sausages. Methods: Microbiological and sensory analyses were performed to evaluate the shelf life of the treated products during 60 days of storage under refrigeration condition (4°C). Results: The results showed that all tested fibers improved the shelf life of the samples. The microbiological examinations revealed that while all the fibers could hinder the growth of spoilage bacteria, OF sample with the mesophilic, psychrotrophic, and lactic acid bacteria counts of 5.95, 4.78, and 5.27 log10 colony-forming unit per gram (CFU/g), respectively showed the highest microbiological quality at the end of the storage. Taste, odor, and overall acceptability of the samples were not significantly affected by the fibers, and texture was the sole sensory attribute that improved in the dietary fiber incorporated products, especially in the OF sample. Conclusions: According to our results, among the various fibers, OF is recommended to the meat industry to extend the shelf life of cooked sausages.
The role of the World Health Organization in the global health governance
Authors: Malichenko Vladislav Sergeevich
Published: May 2022

The object of the study is public relations arising from the interaction of international intergovernmental organizations, states, and non-governmental organizations in the framework of ensuring the human right to the highest attainable level of health and forming the concept of "global health governance". The subject of the study are international legal norms, as well as acts of “soft law” that determine interaction between the WHO and other international actors in the field of healthcare regulation. The aim of the research is to analyze the main peculiarities of "global health governance" concept in frame of international law in order to determine the main directions for improving the activities of the WHO at the present stage. The article was prepared using general scientific methods of cognition, including formal logical and situational, and private law methods, such as comparative legal, historical legal and formal legal. The novelty of the article lies in the conceptual understanding of the content of the concept of "global health governance" in the system of international health law. The article discusses the historical stages in the development of international cooperation in the field of health care in order to determine the main trends in inter-institutional cooperation for the further development of international health regulation. The author summarizes the main problems in the implementation of the statutory powers of the WHO, including the features of the development and application of regulatory legal acts of a binding nature, as well as acts of "soft law" in the activities of the Organization. The author substantiates recommendations for improving the activities of the WHO to ensure the effective implementation of the concept of "global health governance".
Pachygenium laurense (Orchidaceae, Spiranthinae), a new orchid species from Argentina—morphological evidence and phylogenetic reconstruction
Authors: M. Martin Claudia , Morales Adriana Marisel , Dudek Magdalena , L. Szlachetko Dariusz
Published: May 2022

Background

Pachygenium embraces a group of terrestrial species formerly placed in Pelexia sensu lato. The genus currently comprises some 60 species, most of which are known from the southern parts of Brazil and Paraguay, with few species distributed in the Andean countries—only four species have been recorded from Argentina so far. In Jujuy Province, Argentina a new species of Pachygenium was found during our fieldwork. The aim of this article was to provide morphological and molecular evidence for its membership in this genus.

Methods

Materials from specimens were collected in the field and examined by classical taxonomic and molecular biological techniques, e.g., PCR and sequencing DNA. Phylogenetic reconstruction was performed by maximum-likelihood and Bayesian inference.

Results

Pachygenium laurense from Argentina is described and illustrated based on morphological evidence and its taxonomic position was confirmed by phylogenetic analyses. A new combination for Pachygenium gutturosa is also proposed. A key for identification is provided for the Pachygenium species occurring in Argentina.

Conclusion

Pachygenium laurense is the fifth species of the genus recorded from Argentina.
The English Text of the Treaty of Waitangi
Authors: Fletcher Ned
Published: May 2022

How was the English text of the Treaty of Waitangi understood by the British in 1840? That is the question addressed by historian and lawyer Ned Fletcher, in this extensive work. With one exception, the Treaty sheets signed by rangatira and British officials were in te reo Māori. The Māori text, Te Tiriti o Waitangi, was a translation by the missionary Henry Williams of a draft in English provided by William Hobson, the Consul sent by the British government to negotiate with Māori. Despite considerable scholarly attention to the Treaty, the English text has been little studied. In part, this is because the original English draft exists only in fragments in the archive; it has long been regarded as lost or ‘unknowable’, and in any event superseded by the authoritative Māori text. Now, through careful archival research, Fletcher has been able to set out the continuing relevance of the English text. The English Text of the Treaty of Waitangi emphasises that the original drafting of the Treaty by British officials in 1840 cannot be separated from the wider circumstances of that time. This context encompasses the history of British dealings with indigenous peoples throughout the Empire and the currents of thought in the mid-nineteenth century, a period of rapid change in society and knowledge. It also includes the backgrounds and motivations of those primarily responsible for framing the Treaty: British Resident James Busby, Consul and future Lieutenant-Governor William Hobson, and Colonial Office official James Stephen. Through groundbreaking scholarship, Fletcher concludes that the Māori and English texts of the Treaty reconcile, and that those who framed the English text intended Māori to have continuing rights to self-government (rangatiratanga) and ownership of their lands. This original understanding of the Treaty, however, was then lost in the face of powerful forces in the British Empire post-1840, as hostility towards indigenous peoples grew alongside increased intolerance of plural systems of government. The English Text of the Treaty of Waitangi enriches our understanding of the original purpose and vision of Te Titiri o Waitangi / The Treaty of Waitangi and its foundational role in Aotearoa New Zealand.
Hypoxia Inducible Factor 1 Alpha and Matrix Metalloproteinase-9 in Dysfunctional Uterine Bleeding
Authors: Khandhadiya Ketki , Gupta Mrinal , Kumar Shailesh
Published: May 2022

Introduction: Dysfunctional Uterine Bleeding (DUB) is prevalent in 10-15% of gynaecological patients. Matrix metallopeptidase-9 (MMP-9) expression is stimulated by reduced oxygen levels in a highly aggressive, metastatic breast cancer cell line, although MMP-2 expression is unaffected. Under hypoxic conditions, Hypoxia Inducible Factor 1 Alpha (HIF-1α) rapidly accumulates and transactivates hundreds of genes, including angiogenic growth factors as well as receptors. Aim: To compare and estimate the serum HIF-1alpha, serum MMP-9 in ultrasonographically proven DUB patients and in controls with normal menstruation. Materials and Methods: This case-control study was conducted in Department of Biochemistry at Heritage Institute of Medical Sciences, Varanasi, Uttar Pradesh, India, from July 2020 to November 2021. A random venous blood sample (4 mL) was drawn from the DUB cases and controls into a sterile red topped vacutainer which was allowed to clot for 30 minutes. The sample was centrifuged and the serum was separated and analysed for desired parameters. Serum HIF-1α and MMP-9 was estimated by using sandwich Enzyme Linked Immunosorbent Assay (ELISA) method. Student’s t test was used for comparison between the variables and pearson’s correlation test was used to assess the correlation between the parameters. Results: The mean age of controls was 33.9±7.10 years (N=40) compared to cases where it was 38.8±5.32 years (N=40). Serum HIF-1α showed significantly elevated levels of median in DUB cases (1.16 ng/mL) compared to normal control group (0.28 ng/ mL, p-value=0.04). Mean serum levels of MMP-9 significantly decreased in DUB cases as compared to normal control group (34,142±19,043, 61,500±16,169 respectively, p-value=0.003). Presence of hypoxia leading to HIF-1α and MMP-9 formation plays a role in endometrial thickness and angiogenesis leading to various signs and symptoms of DUB. The present study did not find any correlation between MMP-9 and endometrial thickness as well as HIF-1α and endometrial thickness in DUB cases and controls. There was significant low positive correlation between serum MMP-9 and HIF-1α in DUB cases (r-value=0.423, p-value <0.05). Conclusion: Elevated levels of HIF-1α and decreased levels of MMP-9 was observed in DUB cases. No correlation was found between MMP-9 and endometrial thickness as well as HIF-1α and endometrial thickness in DUB cases and controls. Hence, whether this can be used for diagnostic and therapeutic prospects needs to be further studied.
Low Bandgap Polymers
Authors: Neshchadin Andriy , Yu Luping
Published: May 2022

The field of low bandgap organic conjugated polymers has found broad applications with efforts over the past decade. This article gives a brief overview of the recent progress of their synthesis and several applications for polymer solar cells, photodetectors, and bioimaging materials. Synthetic methods cover ground from Stille and Suzuki polycondensations to direct arylation polymerization. Donor–acceptor or ‘push–pull’ structures are generally necessary to lower bandgap of conjugated polymers, and this design strategy provides a rational approach to tune polymer energy levels as HOMO is mostly determined by donor units and conjugation, while LUMOs are determined by acceptor moieties. Special attention is given to the extraction of principles for efficient design of materials with desired properties. For efficient device performance, it is important to match the energy levels of functional materials with other device components and chosen applications, while maintaining solubility and good processability.
Solid‐State
NMR
Spectroscopy
Authors: Wang Hao , Yan Zhiwei , Li Dongjia , Wang Xiaoliang , Zhang Rongchun
Published: May 2022

Solid‐state NMR spectroscopy is an indispensable tool for probing detailed structures and dynamics of polymers at an atomic level due to its capability to selectively manipulate various types of anisotropic spin interactions in solids and its nondestructive property. Herein, this article mainly describes the properties of those anisotropic spin interactions in solids, and how they are used to extract structural and dynamic information via sophisticated one‐ and multidimensional solid‐state NMR spectroscopy. We hope this article can be a good tutorial for the researchers interested in using solid‐state NMR to study polymers.
Are mindful people less aggressive? The role of emotion regulation in the relations between mindfulness and aggression
Authors: Kim El‐Lim , Gentile Douglas A. , Anderson Craig A. , Barlett Christopher P.
Published: May 2022

Inducing mindfulness has shown a promising effect on reducing aggression in both clinical and nonclinical populations, possibly because mindfulness can improve emotion regulation. The present study examined the association between mindfulness and aggression through potential mediating effects of several emotion regulation strategies. University and community samples of U.S. adults completed questionnaires on mindfulness, emotion regulation strategies, and trait aggression. Results indicate that mindfulness was associated with rumination and expressive suppression, which mediated the mindfulness‐aggression relationship. Most facets of mindfulness were unrelated to the use of reflection and cognitive reappraisal. The nonjudging of experience facet of mindfulness was negatively related to hostility through rumination and expressive suppression. In contrast, the observing mindfulness facet was positively related to verbal aggression and hostility; these relations were mediated by rumination and expressive suppression.
Factors predicting neuronal surface antibodies in the elderly with new‐onset and unknown seizures
Authors: Liu Xiao , Yu Tingting , Qi Jing , Lv Ruijuan , Wang Qun
Published: May 2022

Objective

To investigate risk factors of neuronal surface antibodies (NSAbs) and develop a nomogram that could identify patients at the odds of NSAbs among the elderly (aged 60 years or older) with new‐onset seizures of unknown etiology.

Methods

Clinical data for aged ≥60 years diagnosed with new‐onset seizures of unknown etiology were retrospectively reviewed. A nomogram based on multivariable logistic regression was constructed. Model performance of nomogram was evaluated using area under the curve (AUC), calibration curve, decision curve analysis (DCA), and clinical impact curve (CIC). Meanwhile, it was internally validated by bootstrap validation in current cohort.

Results

Of 147 patients included in final analysis, 68 (46.3%) had NSAbs‐mediated encephalitis. Six factors were identified: duration of seizures less than 3 months (OR:14.259; 95% CI: 4.480–45.386), focal‐onset seizures (OR:12.457; 95% CI: 2.710–57.261), psychiatric deficits (OR:10.063; 95% CI: 3.231–31.343), sleep disorders (OR:3.091; 95% CI: 1.011–9.454), hyponatremia (OR:6.252; 95% CI: 1.445–27.043), and medial temporal lobe (MTL) lesions on MRI (OR:4.102; 95% CI: 1.382–12.169). The nomogram had a good discrimination with an AUC of 0.916 and with a corrected AUC of 0.881 after the bootstrapping validation, our model also exhibited a better predictive performance than scoring systems commonly used clinically. Additionally, the calibration curve showed that predicted NSAbs‐positive rates of nomogram were closely aligned with actual observed results. Moreover, the nomogram achieved well on clinical utility by using the DCA and CIC.

Interpretation

Our nomogram may provide a convenient and useful tool for identifying the elderly with new‐onset seizures of unknown etiology who are at risk of NSAbs‐mediated encephalitis, which would allow these patients receive earlier immunotherapy.
Ag Nanoparticles Anchored on Nanotubular Porous Porphyrin Networks for Carboxylative Cyclization of Propargyl Alcohols with CO2
Authors: Chen Yaju , Lei Lin , Ren Qinggang , Li Jiashan , Gao Jingkang , Lin Jie , Qiu Yongjian , Ji Hongbing
Published: May 2022

A nanotubular porous porphyrin‐based network (NT‐PPN) was prepared through Friedel–Crafts alkylation polyreaction of meso‐tetraphenylporphyrin iron chloride and subsequent demetalization reaction with concentrated hydrochloric acid. As a superior support, NT‐PPN was decorated with Ag nanoparticles to generate the desired catalyst (Ag@NT‐PPN). Ag@NT‐PPN had a high BET surface area with plentiful hierarchical porosity, considerable CO2 adsorption uptake, as well as high CO2/N2 adsorption selectivity. In the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU), Ag@NT‐PPN exhibited excellent catalytic performance for the solvent‐free synthesis of α‐alkylidene cyclic carbonates from propargyl alcohols and CO2 at 30 °C. Ag@NT‐PPN also displayed robust constancy, excellent recyclability, and acceptable substrate expansibility for this reaction. Moreover, low concentration of CO2 derived from mixed gas (15% CO2+85% N2 in volume) was positively amenable to this catalytic protocol. This work might offer an opportunity to design metal NPs‐based heterogeneous catalysts and provide a promising candidate for application in the transformation of CO2 into valuable cyclic carbonates.
Eyeblink rate as an indicator of concentration on grooming in Japanese macaques (Macaca fuscata)
Authors: Hikida Kenichiro
Published: May 2022

In primates, social relationships with a high frequency of social grooming are referred to as “affiliate relationships,” “friendship,” “bonding,” and are described as involving positive emotion. However, the psychological state during social grooming has not been fully understood. In this study, I focused on blinking as a behavior that reflects psychological state during grooming in Macaca fuscata, a nonhuman wild primate, and examined for the first time whether the blink rate reflects concentration on social grooming. To test this hypothesis, I focused on ectoparasite removals during social grooming with the following three predictions: (1) blinks are synchronized with breakpoints (when monkeys can release visual attention) of mouthing ectoparasites during grooming, (2) the blink rate is lower during grooming (when requiring visual concentration) than during resting (when no visual concentration is required), and (3) the lower the blink rate during grooming (supposedly in high concentration), the higher the frequency of ectoparasites removals (outputs of the task). I recorded the faces of 10 wild female Japanese macaques on Kinkazan Island, Miyagi Prefecture, with video, while they were resting and grooming, and recorded the timing and frequency of eyeblink and ectoparasite removals. All three predictions were supported, suggesting that the blink rate during grooming can be an indicator of concentration on grooming in nonhuman primates. Whether grooming concentration is associated with an affiliative relationship with the grooming partner is an issue that should be carefully examined in future studies, but eyeblink studies may provide new perspectives for understanding the psychological state of individuals during grooming in a noninvasive manner.
Factors associated with emergency department length of stay of foreign patients visiting a regional core hospital in Japan
Authors: Aoki Yoshihiro , Kumazaki Hiroshi , Terakawa Ion , Hatachi Takeshi , Shiroto Kosuke , Miyauchi Naoto , Suganuma Kazuki
Published: May 2022

Aim

This study aims to elucidate the foreign patient‐specific factors associated with emergency department length of stay (EDLOS) in a regional core hospital emergency department (ED) in Japan.

Methods

This retrospective observational study included non‐Japanese patients who visited the ED in a Japanese regional core hospital between April 1, 2018, and March 31, 2020. The effects on EDLOS were assessed using multivariate linear regression analysis, which included factors such as age, sex, consultation language, interpreter usage, arrival time, day of visit, mode of arrival, underlying disease, triage level, diagnosis of injury/noninjury, diagnostic investigations, consultation with specialists, and treatments or procedures.

Results

Of 65,297 ED patients, there were 777 study patients, with a median age of 37 years (interquartile range [IQR], 24.0–50.0). The median EDLOS was 101 min (IQR, 63.0–153.0). Multivariate linear regression analysis indicated that an extended EDLOS was associated with: language apart from Japanese, Chinese, or English (51.7 min; 95% confidence interval [CI], 17.8–85.6), helicopter arrival (115.6 min; 95% CI, 48.8–182.5), blood testing (60.5 min; 95% CI, 34.6–86.4), computed tomography (23.8 min; 95% CI, 3.7–43.9), consultation with specialists (36.2 min; 95% CI, 11.8–60.6), intravenous fluid/medication (29.7 min; 95% CI, 3.3–56.1), and surgical procedure/reduction/fixation in the ED (38.8 min; 95% CI, 14.2–63.4).

Conclusions

Consultation in a language other than Japanese, English, or Chinese was associated with a longer EDLOS in a regional core hospital in Japan. Devising ways to accommodate patients who speak various languages could be important.
Lifestyle Affects Amyloid Burden and Cognition Differently in Men and Women
Authors: Bachmann Dario , Roman Zachary J. , Buchmann Andreas , Zuber Isabelle , Studer Sandro , Saake Antje , Rauen Katrin , Gruber Esmeralda , Nitsch Roger M. , Hock Christoph , Gietl Anton F. , Treyer Valerie
Published: May 2022

Objective

Evidence on associations of lifestyle factors with Alzheimer's pathology and cognition are ambiguous, potentially because they rarely addressed inter‐relationships of factors and sex effects. While considering these aspects, we examined the relationships of lifestyle factors with brain amyloid burden and cognition.

Methods

We studied 178 cognitively normal individuals (women, 49%; 65.0 [7.6] years) and 54 individuals with mild cognitive impairment (women, 35%; 71.3 [8.3] years) enrolled in a prospective study of volunteers who completed 18F‐Flutemetamol amyloid positron emission tomography. Using structural equation modeling, we examined associations between latent constructs representing metabolic/vascular risk, physical activity, and cognitive activity with global amyloid burden and cognitive performance. Furthermore, we investigated the influence of sex in this model.

Results

Overall, higher cognitive activity was associated with better cognitive performance and higher physical activity was associated with lower amyloid burden. The latter association was weakened to a nonsignificant level after excluding multivariate outliers. Examination of the moderating effect of sex in the model revealed an inverse association of metabolic/vascular risk with cognition in men, whereas in women metabolic/vascular risk trended toward increased amyloid burden. Furthermore, a significant inverse association between physical activity and amyloid burden was found only in men. Inheritance of an APOE4 allele was associated with higher amyloid burden only in women.

Interpretation

Sex modifies effects of certain lifestyle‐related factors on amyloid burden and cognition. Notably, our results suggest that the negative impact of metabolic/vascular risk influences the risk of cognitive decline and Alzheimer's disease through distinct paths in women and men. ANN NEUROL 2022;92:451–463
Polarization‐Dependent Ultrasensitive Dynamic Wrinkling on Floating Films Induced by Photo‐Orientation of Azopolymer
Authors: Liu Enping , Zhang Xiaoliang , Ji Haipeng , Li Qifeng , Li Lele , Wang Juanjuan , Han Xue , Yu Shixiong , Xu Fan , Cao Yanping , Lu Conghua
Published: May 2022

Ubiquitous surface wrinkling has been well‐studied theoretically and experimentally. How to modulate the stress state of a liquid‐supported system for the unexploited wrinkling capabilities remains a challenge. Here we report a simple linearly‐polarized‐light illumination to spatiotemporally trigger ultrasensitive in situ dynamic wrinkling on a floating azo‐film. The smart combination of the liquid substrate with photoresponsive azo‐moieties leads to the light‐induced ultrafast wrinkling evolution, accompanied by unprecedented sequential wrinkling orientation conversion (from polarization‐parallel to polarization‐perpendicular). The involved different polarization‐dependent sequential photo‐orientation for azo side chains and azo‐grafted main chains of azopolymers is disclosed experimentally for the first time. Meanwhile, programmable dynamic wrinkling with all‐optical switchable surface topographies is available, which has wide application potentials in photoresponsive soft photonics.
An endo‐Directing‐Group Strategy Unlocks Enantioselective (3+1+2) Carbonylative Cycloadditions of Aminocyclopropanes
Authors: Sokolova Olga O. , Bower John F.
Published: May 2022

An endo‐directing group strategy enables enantioselective (3+1+2) cycloadditions that are triggered by carbonylative C−C bond activation of cyclopropanes. These processes are rare examples of cycloadditions where C−C bond oxidative addition is enantiodetermining, and the first where this is achieved within the context of a multicomponent (higher order) reaction design.
Li−N Interaction Induced Deep Eutectic Gel Polymer Electrolyte for High Performance Lithium‐Metal Batteries
Authors: Pei Xiaopeng , Li Yiju , Ou Ting , Liang Xuechen , Yang Yun , Jia Erna , Tan Ying , Guo Shaojun
Published: May 2022

As emerging eutectic mixtures, deep eutectic electrolytes (DEEs) show unique properties for Li‐metal batteries (LMBs). However, the limited choice and inferior electrode compatibility hinder their further development in LMBs. Herein, we report a new 1,2‐dimethylimidazole (DMIm)‐based deep eutectic gel polymer electrolyte induced by Li−N interaction. We demonstrate that incorporating electron‐withdrawing polyvinylidene difluoride (PVDF) polymer into the DMIm‐based DEE changes the coordination environment of Li+ ions, leading to a high transference number of Li+ ions (0.65) and superior interface stability between the electrolyte and Li anode. The deep eutectic gel polymer electrolyte exhibits excellent non‐flammability, high ionic conductivity (1.67 mS cm−1 at 30 °C), and high oxidation voltage (up to 4.35 V vs. Li/Li+). The Li||LFP cell based on the newly developed deep eutectic gel polymer electrolyte can achieve superior long‐term cycling stability at a wide range of rates.
Small Molecule Inhibitors of Interferon‐Induced JAK‐STAT Signalling
Authors: Thoidingjam Leishemba K. , Blouin Cédric M. , Gaillet Christine , Brion Aurélien , Solier Stéphanie , Niyomchon Supaporn , El Marjou Ahmed , Mouasni Sara , Sepulveda Fernando E. , de Saint Basile Geneviève , Lamaze Christophe , Rodriguez Raphaël
Published: May 2022

Interferons (IFN) are cytokines which, upon binding to cell surface receptors, trigger a series of downstream biochemical events including Janus Kinase (JAK) activation, phosphorylation of Signal Transducer and Activator of Transcription protein (STAT), translocation of pSTAT to the nucleus and transcriptional activation. Dysregulated IFN signalling has been linked to cancer progression and auto‐immune diseases. Here, we report the serendipitous discovery of a small molecule that blocks IFNγ activation of JAK‐STAT signalling. Further lead optimisation gave rise to a potent and more selective analogue that exerts its activity by a mechanism consistent with direct IFNγ targeting in vitro, which reduces bleeding in model of haemorrhagic colitis in vivo. This first‐in‐class small molecule also inhibits type I and III IFN‐induced STAT phosphorylation in vitro. Our work provides the basis for the development of pan‐IFN inhibitory drugs.
Nickel‐Catalyzed Switchable Site‐Selective Alkene Hydroalkylation by Temperature Regulation**
Authors: Wang Jia‐Wang , Liu De‐Guang , Chang Zhe , Li Zhen , Fu Yao , Lu Xi
Published: May 2022

Regiodivergent alkene functionalization that produces either regioisomer starting from the same raw materials is desirable. Herein, we report a nickel‐catalyzed switchable site‐selective alkene hydroalkylation. The selection of reaction temperatures leads to protocols that provide regiodivergent hydroalkylated products starting from a single alkene substrate. This protocol allows the convenient synthesis of α‐ and β‐branched protected amines, both of which are important to the fields of pharmaceutical chemistry and biochemistry. In addition, enantioenriched β‐branched alkylamines can be accessed in a catalytic asymmetric variant. Preliminary mechanistic studies indicate that the formation of a more stable nickelacycle provides the driving force of migration. The thermodynamic and kinetic properties of different reduction elimination intermediates are responsible for the switchable site‐selectivity.
Enhanced Photocatalytic CO2 Reduction through Hydrophobic Microenvironment and Binuclear Cobalt Synergistic Effect in Metallogels
Authors: Yang Gengxiang , Li Senzhi , Li Ning , Zhang Pianpian , Su Chaorui , Gong Lei , Chen Baotong , Qu Chen , Qi Dongdong , Wang Tianyu , Jiang Jianzhuang
Published: May 2022

Assemblies that mimic natural lipid bilayers are theoretically efficient for photocatalytic CO2 reduction; however, such an approach has not been yet explored. Herein, metallogels (LG/Nico‐Co) based on the co‐assembly of L‐glutamic acid lipid (LG/Nico) and cobalt ions exhibited excellent photocatalytic CO2 reduction, with 208 724 μmol g−1 CO production within 24 h and 90 % CO/H2 selectivity, or 166 826 μmol g−1 CO production within 12 h and 46 % CO/H2 selectivity, depending on the water content of the solvent. The alkyl chains of LG/Nico provide a hydrophobic microenvironment for efficient gas transfer, and the assembled bilayers induce a synergistic effect between two adjacent Co ions for catalyzing the CO2 reduction reaction. These architectures present new alternatives for the development of highly efficient photocatalytic soft matter based on the assembly of small amphiphilic molecules.
Oxidation Potential Gap (ΔEox): The Hidden Parameter in Redox Chemistry
Authors: Okamoto Kazuhiro , Shida Naoki , Morizumi Haruka , Kitano Yoshikazu , Chiba Kazuhiro
Published: May 2022

Oxidative biaryl coupling of aryls with different electronic features generally fails. However, this has not been systematically studied via theoretical analysis, and thus, the crucial factor governing coupling efficiency remains unclear. Herein, we propose that the “oxidation potential gap (ΔEox)” is a key parameter in predicting the efficiency of an intramolecular oxidative coupling reaction, with ΔEox defined as a difference in the oxidation potentials of the relevant aromatic rings. Our experimental and computational analyses revealed that the efficiency of an aromatic intramolecular coupling reaction correlates with the activation energy (ΔE≠) of C−C bond formation of the radical cation intermediates. Furthermore, ΔE≠ correlates with ΔEox. Therefore, we demonstrate the tuning of ΔEox by attaching cleavable extra electron‐donating/‐withdrawing groups, enabling the rational synthesis of a phenanthridone skeleton using aromatic rings with an electronic gap.
Eutectic Electrolyte with Unique Solvation Structure for High‐Performance Zinc‐Ion Batteries
Authors: Geng Lishan , Meng Jiashen , Wang Xuanpeng , Han Chunhua , Han Kang , Xiao Zhitong , Huang Meng , Xu Peng , Zhang Lei , Zhou Liang , Mai Liqiang
Published: May 2022

Zinc‐ion batteries (ZIB) present great potential in energy storage due to low cost and high safety. However, the poor stability, dendrite growth, and narrow electrochemical window limit their practical application. Herein, we develop a new eutectic electrolyte consisting of ethylene glycol (EG) and ZnCl2 for dendrite‐free and long‐lifespan ZIBs. The EG molecules participate in the Zn2+ solvation via coordination and hydrogen‐bond interactions. Optimizing the ZnCl2/EG molar ratio (1 : 4) can strengthen intermolecular interactions to form [ZnCl(EG)]+ and [ZnCl(EG)2]+ cations. The dissociation–reduction of these complex cations enables the formation of a Cl‐rich organic–inorganic hybrid solid electrolyte interphase film on a Zn anode, realizing highly reversible Zn plating/stripping with long‐term stability of ≈3200 h. Furthermore, the polyaniline||Zn cell manifests decent cycling performance with ≈78 % capacity retention after 10 000 cycles, and the assembled pouch cell demonstrates high safety and stable capacity. This work opens an avenue for developing eutectic electrolytes for high‐safety and practical ZIBs.
VPO4F Fluorophosphates Polyanion Cathodes for High‐Voltage Proton Storage
Authors: Liao Mochou , Cao Yongjie , Li Ziyue , Xu Jie , Qi Yae , Xie Yihua , Peng Yu , Wang Yonggang , Wang Fei , Xia Yongyao
Published: May 2022

Proton batteries are emerging in electrochemical energy storage because of the associated fast kinetics, low cost and high safety. However, their development is hindered by the relatively low energy density due to the limited choice of cathode materials. Herein, metal phosphate polyanion cathodes are proposed as the proton cathode for the first time. Combining experimental results and theoretical simulations, a universal criterion for the proton cathode was put forward. Vanadium fluorophosphate (VPO4F) was demonstrated as a promising high‐voltage proton cathode material with a specific capacity of 116 mAh g−1 at a high potential of 1.0 V (vs. SHE). The proton insertion/extraction mechanism in the VPO4F electrode was also verified through X‐ray diffraction (XRD) and photoelectron spectroscopy (XPS). Furthermore, the stability of VPO4F was investigated in various electrolytes and the optimized electrolyte enabled the stable operation of VPO4F for 300 cycles. This work provides new inspiration in the exploitation of new electrode materials for electrochemical proton storage devices.
Access to Unexplored 3D Chemical Space: cis‐Selective Arene Hydrogenation for the Synthesis of Saturated Cyclic Boronic Acids
Authors: Kaithal Akash , Wagener Tobias , Bellotti Peter , Daniliuc Constantin G. , Schlichter Lisa , Glorius Frank
Published: May 2022

A new class of saturated boron‐incorporated cyclic molecules has been synthesized employing an arene‐hydrogenation methodology. cis‐Selective hydrogenation of easily accessible, and biologically important molecules comprising benzoxaborole, benzoxaborinin, and benzoxaboripin derivatives is reported. Among the various catalysts tested, rhodium cyclic(alkyl)(amino)carbene [Rh‐CAAC] (1) pre‐catalyst revealed the best hydrogenation activity confirming turnover number up to 1400 with good to high diastereoselectivity. A broad range of functional groups was tolerated including sensitive substituents such as −F, −CF3, and −silyl groups. The utility of the synthesized products was demonstrated by the recognition of diols and sugars under physiological conditions. These motifs can have a substantial importance in medicinal chemistry as they possess a three‐dimensional structure, are highly stable, soluble in water, form hydrogen bonds, and interact with diols and sugars.
Psychometric properties of the Chinese version of the children's empathy quotient and systemizing quotient: 4–12 years
Authors: Wang Xin , Dai Mei‐Xia , Murray Aja , Liu Si‐Yu , Chen Jia‐Jie , Lin Li‐Zi , Jing Jin , Auyeung Bonnie
Published: May 2022

We aimed to validate the Children's Empathy Quotient (EQ‐C) and Systemizing Quotient (SQ‐C) in Mainland China, which can reflect the profiles of empathizing and systemizing, and describing specific characteristics of autism spectrum disorder (ASD) and gender‐typical behaviors in general population. A total of 800 typically developing (TD) children, aged 4–12 years was recruited initially with whose parents/guardians complete the measurements, and 782 TD children who met inclusion criteria were finally included. A 23‐item three‐factor EQ‐C and a 22‐item four‐factor SQ‐C was developed with good internal consistency (Omega total values of 0.87 and 0.86) and test–retest reliability (Pearson correlation coefficients of 0.82 and 0.69). In TD children, girls scored significantly higher on EQ‐C (31.4 ± 7.8 vs. 28.2 ± 7.7) but there were no gender differences in SQ‐C scores. TD children showed different cognitive styles (empathizing‐dominant for girls with 42.6% identified as Type E; systemizing‐dominant for boys with 40.7% identified as Type S). A further sample of 222 children with ASD indicated that they scored lower on EQ/SQ‐C compared to TD children (13.2 ± 5.1 vs. 29.7 ± 7.9, 12.4 ± 5.8 vs. 23.5 ± 8.3) and were generally systemizing‐dominant (Type S: 50.8% for boys and 64.0% for girls). Autistic children scored higher on the SQ‐C in those without intellectual disability and with higher paternal education level and family income (14.2 ± 6.1 vs. 10.9 ± 5.0, 13.3 ± 6.2 vs. 11.5 ± 5.1, 13.7 ± 5.6 vs. 11.9 ± 5.8), while there were no differences in the EQ‐C. This study indicated good reliability and validity of the Chinese version of EQ/SQ‐C, which can be used in Chinese children with and without ASD.

Lay Summary

We developed the Chinese version of the Children's Empathy Quotient (EQ‐C) and Systemizing Quotient (SQ‐C) in 782 typically developing (TD) children aged 4–12 years in Mainland China, yielding a 23‐item, 3‐factor EQ‐C and a 22‐item, 4‐factor SQ‐C with good psychometric properties. In TD children, we found gender difference only in scores of EQ‐C. Further analyses of 222 autistic children indicated that differences were found in scores of SQ‐C when considering their gender, intelligence and socio‐economic status.
Clinicopathological characteristics and prognosis of microinvasive breast cancer: A population‐based analysis
Authors: Xu Hangcheng , Han Yiqun , Wu Yun , Wang Yan , Wang Jiayu , Xu Binghe
Published: May 2022

Objectives

Microinvasive breast cancer (MIBC) is a special type of breast cancer with a relatively low prevalence, of which the understanding remains controversial. In this article, we aimed to clarify the clinicopathological characteristics and prognosis of MIBC in the setting of different molecular subtypes and give feasible suggestions on clinical practice in MIBC.

Methods

This study utilized the data from Surveillance, Epidemiology, and End Results (SEER) database. Patients were divided into subgroups based on the molecular subtypes, of which the clinicopathological characteristics were further undergone comparative analyses. Kaplan–Meier method and Cox proportional hazard regression analysis were employed to determine the prognosis of the subtypes, and to explore the prognostic factors. Patients were randomly assigned in a 7:3 ratio to the training and validation cohorts. The independent risk variables were then adopted to generate a nomogram to predict the 3‐ and 5‐year survival probability.

Results

A total of 4301 MIBC patients between 2010 and 2016 were obtained from the SEER database, which were subsequently separated into HR+/HER2‐ (n = 2598), HR+/HER2+ (n = 723), HR‐/HER2+ (n = 633), and HR‐/HER2‐ (n = 347) groups. The HR+/HER2+ group showed the best overall survival (OS) (81.28 months, 95% CI 80.45–82.11) compared with other groups (p = 0.0089). The application of radiotherapy in HR+/HER2‐ and HR+/HER2+ MIBC patients brought out additional survival benefit compared with those without radiotherapy (p < 0.0001 and p = 0.024, respectively). The prognosis among four subgroups with or without chemotherapy showed no statistical difference. Based on the curated nomogram, the high‐score group exhibited a better OS compared with patients from the low‐score group.

Conclusions

Profound heterogeneity was detected among different molecular subtypes in MIBC patients, of which HR+/HER2+ subtype presented the best prognosis. For HR‐positive MIBC patients, increasing survival benefits could be retrieved from radiotherapy. Chemotherapy was not recommended for patients with MIBC. Individual‐based protocols were introduced based on the nomogram which warranted further validation.
Seeking Citius: Photochemical Access of Reactive Intermediates for Faster Bioorthogonal Reactions
Authors: Kumar Gangam Srikanth , Lin Qing
Published: May 2022

Fast bioorthogonal reactions are sought after because of their superior performance in labeling low‐abundance biomolecules in native cellular environments. An attractive strategy to increase reaction kinetics is to access the reactive intermediates through photochemical activation. To this end, significant progress was made in the last few years in harnessing two highly reactive intermediates—nitrile imine and tetrazine—generated through photoinduced ring rupture and catalytic photooxidation, respectively. The efficient capture of these reactive intermediates by their cognate reaction partners has enabled bioorthogonal fluorescent labeling of biomolecules in live cells.
Theory‐Guided Machine Learning to Predict the Performance of Noble Metal Catalysts in the Water‐Gas Shift Reaction
Authors: Chattoraj Joyjit , Hamadicharef Brahim , Kong Jian Feng , Pargi Mohan Kashyap , Zeng Yingzhi , Poh Chee Kok , Chen Luwei , Gao Fei , Tan Teck Leong
Published: May 2022

Machine learning (ML) has widespread applications in catalyst discovery and reaction optimization. We present a theory‐guided machine learning framework to evaluate the carbon monoxide (CO) conversion performance of noble metal catalysts in water‐gas shift (WGS) reaction. Our study is based on an open source WGS dataset, which we modify significantly to be consistent with the chemical reaction principles. We apply state‐of‐the‐art ML models including artificial neural networks, extreme gradient boosting to predict CO conversion percentage. These models show superior regression performance than the previously reported results in the literature. We further generalize the existing data structure by including physical, chemical and surface chemistry properties as fingerprint features that rationalize the importance of all the input features for CO conversion. We noticed that purely data‐driven ML models frequently violate the thermodynamic equilibrium principle and predict unphysical CO conversion percentage. We address these two problems by developing a custom loss function and an additional activation function in our neural networks architecture. Our proposed theory‐guided ML model displays high accuracy (R2 score is 0.95 and root mean square error is 6.87) and physically robust predictions. The model also opens up promising possibilities to improve CO conversion percentage, which were previously unexplored in experiments.
The Role of Packing, Dispersion, Electrostatics, and Solvation in High‐Affinity Complexes of Cucurbit[n]urils with Uncharged Polar Guests
Authors: Grimm Laura M. , Spicher Sebastian , Tkachenko Boryslav , Schreiner Peter R. , Grimme Stefan , Biedermann Frank
Published: May 2022

The rationalization of non‐covalent binding trends is both of fundamental interest and provides new design concepts for biomimetic molecular systems. Cucurbit[n]urils (CBn) are known for a long time as the strongest synthetic binders for a wide range of (bio)organic compounds in water. However, their host‐guest binding mechanism remains ambiguous despite their symmetric and simple macrocyclic structure and the wealth of literature reports. We herein report experimental thermodynamic binding parameters (ΔG, ΔH, TΔS) for CB7 and CB8 with a set of hydroxylated adamantanes, di‐, and triamantanes as uncharged, rigid, and spherical/ellipsoidal guests. Binding geometries and binding energy decomposition were obtained from high‐level theory computations. This study reveals that neither London dispersion interactions, nor electronic energies or entropic factors are decisive, selectivity‐controlling factors for CBn complexes. In contrast, peculiar host‐related solvation effects were identified as the major factor for rationalizing the unique behavior and record‐affinity characteristics of cucurbit[n]urils.
Micro‐CT visualization of the CNS: Performance of different contrast‐enhancing techniques for documenting the spider brain
Authors: Rivera‐Quiroz Francisco Andres , Miller Jeremy A.
Published: May 2022

Spider brain and central nervous system (CNS) have remained unexplored, due in part to the difficulty of observing these organs, usually only possible through histological preparations. Recently, internal anatomy studies have been supplemented by the inclusion of X‐ ray micro‐CT. Unmineralized tissue such as the body of invertebrates requires a staining process to enhance tissue X‐ray absorption and improve contrast during observation. Many current protocols are based on iodine staining requiring critical point drying (CPD) of the sample for optimal contrast. This process induces shrinking of the soft tissue generating artifacts in the morphology, volume, and even position of internal structures. Phosphotungstic acid (PTA) is an alternative staining agent recently used in marine invertebrate and plant studies. Here, we used several specimens of the common spider Araneus diadematus to visualize the spider brain and compare both contrast‐enhancing ethanol‐based solutions. We assessed a gradient of staining times, observed and tested the repercussions of CPD, and examined the use of vacuum to accelerate PTA diffusion. We show that PTA provides the best contrast on micro‐CT scans in ethanol eliminating the need for CPD, and offering more realistic in situ visualizations of the internal organs. In combination with different scanning settings, PTA allowed observation of internal organs like the CNS, digestive system, muscles, and finer structures like the retina, visual nerves, and optic neuropiles. This fast and less invasive method could facilitate the proper documentation of the internal anatomy in the context of evolutionary, developmental and functional studies.