bluuebunny/crossref_metadata_2025 huggingface dataset:
NK Cell Exhaustion in Wilson’s Disease Revealed by Single-cell RNA Sequencing Predicts the Prognosis of Cholecystitis
Authors: Jin Yong , Xing Jiayu , Dai Chenyu , Jin Lei , Zhang Wanying , Tao Qianqian , Hou Mei , Li Ziyi , Yang Wen , Feng Qiyu , Wang Hongyang , Yu Qingsheng
Published: December 2024

Metabolic abnormalities associated with liver disease have a significant impact on the risk and prognosis of cholecystitis. However, the underlying mechanism is complicated and remains to be elucidated. In particular, the effect of metabolic abnormalities on the progression of cholecystitis through the regulation of immune cell function is poorly understood. In this study, we investigated this issue using Wilson’s disease (WD) as a model. Wilson’s disease is a genetic disorder characterized by impaired mitochondrial function and abnormal copper metabolism. Our retrospective clinical study of over 600 patients with WD found that they have a significantly higher incidence of cholecystitis and a poorer prognosis. The immune cell landscape in the hepatic mesenchymal stromal microenvironment of WD patients was shown using single-cell RNA. A major change is the constitution and function of the innate immune system, including enhanced antigen presentation process, activation of the immune response, and activation of lymphocytes. The proportion of mononuclear phagocytes and natural killer (NK) cells is increased, and the primary characteristic and function of macrophage, Kupffer cell, neutrophil, and NK cell are altered. Exhaustion of NK cell is the fundamental factor, supported by an increase in the expression of the inhibitory receptors KLRC1 and TIGIT and a decrease in the expression of cytotoxic molecules. Clinical tissue and blood samples verified increased KLRC1
+
and TIGIT
+
NK cells and decreased IFNγ
+
NK cells in WD. Further bioinformatic analysis has confirmed a positive correlation between NK cell exhaustion and poor prognosis in cholecystitis and other inflammatory diseases. The study demonstrated abnormal function of liver mesenchymal immune cells triggered by specific metabolic dysfunction in WD, with a focus on the correlation between NK cell exhaustion and poor healing of cholecystitis. Our findings highlight the immune cell dysfunction due to metabolic changes in hepatocytes and provide new insights into the improvement of inflammatory diseases by assessing immune cell function.
Corpus-Based Research of Semantic Aspects of Laul-Stem Words in Estonian, Focused on Past Newspaper Texts and Folk Song Lyrics
Authors:   Estonian Folklore Archives, Estonian Literary Museum, Tartu, Estonia, Särg Taive , Veskis Kaarel ,   Estonian Folklore Archives, Estonian Literary Museum, Tartu, Estonia,   Institute of Estonian and General Linguistics, University of Tartu, Estonia
Published: December 2024

This study examines conceptions of singing across various Estonian cultural spheres through corpus-based analysis of the singing-related vocabulary. The words with the stem laul ‘song’/‘sing’ are analysed in five linguistic corpora, with a detailed focus on two of them: the Estonian Media Corpus (EMC), comprising 1890s newspaper texts from the Corpus of Written Estonian (Eesti Kirjakeele Korpus: 1890ndad; see CWE 2018), and the Regilaul corpus from the Estonian Runosongs’ Database (Eesti Regilaulude Andmebaas, ERAB). Our methodology combines quantitative word analysis with qualitative examination of lexical categories and semantic associations. The analysis reveals differences in the usage and frequency of the singing-related vocabulary between the two main corpora, offers new insights into singing in Estonian society and shows how distinct conceptualisations of singing and modes of expression in oral and written traditions are reflected in the vocabulary.
Exploring the Semantics and Structure of Vocatives in Ukrainian Folk Songs
Authors:   Estonian Folklore Archives, Estonian Literary Museum, Tartu, Estonia, Petrovych Olha ,   Department of Ukrainian Literature, Vinnytsia Mykhailo Kotsiubynskyi State Pedagogical University, Ukraine, Zavalniuk Inna ,   Department of Ukrainian Literature, Vinnytsia Mykhailo Kotsiubynskyi State Pedagogical University, Ukraine, Bohatko Valentyna ,   Department of Ukrainian Literature, Vinnytsia Mykhailo Kotsiubynskyi State Pedagogical University, Ukraine
Published: December 2024

Ukrainian folk songs, as repositories of national cultural heritage, contain a significant collection of linguistic features, particularly in the realm of vocatives. Utilizing computational methods, this study examines the semantics and structure of the vocative case in Ukrainian folk songs to explore its role in social communication, shaping interpersonal relationships, conveying emotional nuances, and reinforcing cultural identity within lyrical narratives. Through the analysis of vocative structures in the corpus of folk songs from Podillia region, this research reveals their linguistic functions in folk songs – naming the addressee, expressing emotions, and evaluating various aspects of the addressee’s identity. The study identifies common structural types across semantic groups, showcasing the skilful use of repetition, interjections, and parallelism to enhance emotional intensity and stylistic dimensions.
Kama-taguste udmurtide kevadise suure päeva (bõddzh’õnal) kombetalituse laulufolkloor
Authors:   Department of Research in Philology, Udmurt Institute of History, Language and Literature, UdmFRC UB RAS, Izhevsk, Russia, Pchelovodova Irina , Anisimov Nikolai ,   Department of Folkloristics, Estonian Literary Museum, Tartu, Estonia,   Department of Research in Philology, Udmurt Institute of History, Language and Literature, UdmFRC UB RAS, Izhevsk, Russia
Published: December 2024

The article is dedicated to the analysis of musical motifs performed by Eastern Udmurts within the framework of the spring ritual complex Bydzhynnal (The Great Day). The relevance of this study is justified by the limited exploration of the musical folklore of this local group. The primary sources for the analysis include field materials collected during the period from 2016 to 2023, as well as materials from the Scientific Archive of the Institute of Udmurt Philology, Ethnography, and Arts of the Ural Branch of the Russian Academy of Sciences, along with expedition records by Udmurt ethnographer Ranus Sadikov. The research methodology is based on philological and musicological approaches, involving a plot-thematic analysis of poetic texts and the identification of features in the development of melodies in the context of their modal, rhythmic, and melodic characteristics. The results of the analysis indicate the diversity of motifs used in the examined tunes. The identified anhemitonic tonal systems suggest similarities between the calendar musical compositions of Eastern Udmurts and the musical tradition of Southern and Western Udmurts. The rhythmic structures are presented in two main types. The presence of melisma in the melodies has also been identified, which is explained by the influence of Turkic culture.
THE NEW EDUCATION SPACE THROUGH THE EYES OF USERS AND DESIGNERS
Authors: Hanna Hrehorowicz-Gaber  , Rafał Blazy  , Alicja Hrehorowicz-Nowak  , Jakub Błachut  , Mariusz Łysień  , Agnieszka Ciepiela  , Jakub Dudek  , Felicjan Lewandowski  , Wiktor Hładki
Published: December 2024

The space in which young people learn undoubtedly has an impact on the quality and effectiveness of learning. Following this lead, the project team, supported by participatory activities, created the concept of a modular mobile classroom that responds to contemporary environmental and social challenges.
Efficacy of High Dose Pulse Methylprednsiolone (Somidex) vs Oral Prednisolone for Treatment of Newly Diagnosed Idiopathic Thrombocytopenic Purpura in Rajavithi Hospital: Open Labelled Randomized Controlled Trial
Authors: Nakhakes Chajchawan
Published: December 2024

Background: ITP is a disease which develops as a result of increased activity of the reticuloendothelial system (mainly the liver and spleen). The role of high-dose short- acting corticosteroids in the treatment of immune thrombocytopenic purpura in adults is controversial. We assessed the effectiveness of high-dose corticosteroids, compared with that of standard oral prednisolone therapy, for initial treatment of adults with immune thrombocytopenic purpura.
Methods: 52 patients were randomized to receive pulse methylprednisolone (1gm/day) for 3 days, or oral prednisolone 1 mg/kg/day for 84 days. Response was evaluated at D10/D14/D28 and at the end of treatment on D84. Degree of response was evaluated in term of platelet count number and duration of response.
Results: The mean initial platelet count was 28,031.58+ 23,663.61 per cubic millimeter. Of these 52 eligible patients, about two thirds had an initial response to pulse methylprednisolone. Seventeen of the 26 patients (65%) on oral prednisolone responded to steroids on D10, and this was identical to the number of initial response patients in the methylprednisolone arm. At the end of the 3rd month of therapy, 20/26 (76.9%) those with methylprednisolone were still in complete response (platelet count more than 100,000/uL) compared with 20/24 (83.3%) patients in the oral prednisolone arm. Although mean platelet count in oral prednisolone group were slightly significantly higher than those of methylprednisolone group on D10, D14, D28 and at the end of study after treatment, platelet count was in complete remission in both arms. Life threatening side effects were more in those with oral prednisolone arm (4 cases), as compared with high dose pulse methylprednisolone, which is no grade 3,4 side effects.
Conclusion: The high-dose pulse methylprednisolone is not more effective than standard-dose oral medication during the study period. It is worth considering high dose pulse methylprednisolone for newly diagnosed chronic ITP patients who seem to be unable to tolerate the long-term side effects of standard oral corticosteroids and need a short response time.
Spatial Assessment of Soil Erosion and Aridity in Somalia Using the CORINE Model
Authors: Nur Abdiaziz Hassan , Mohamed Abdinasir Abdullahi , Ahmed Ali Hussein
Published: December 2024

This study analyzed precipitation patterns, drought conditions, erosivity indices, and arid periods in Somalia using the CORINE model. Utilizing rainfall and temperature data from 50 meteorological stations collected between 2011 and 2019, the study calculated key indices: The Fournier Precipitation Index (35.70%), the Bagnouls-Gaussen Drought Index (61.36), and the erosivity index. The results revealed notable spatial variability in erosivity and aridity across Somalia. Northwestern regions, encompassing 204,978.65 km² (32.14% of the total area), exhibit low erosivity due to reduced rainfall intensity, while southern regions, spanning 252,341.11 km² (39.56%), face high erosivity driven by frequent and intense rainfall events. The study also identified significant arid conditions, with 61.36% of Somalia’s land classified as "dry" and 38.64% as "very dry," highlighting widespread water scarcity and vulnerability. These findings underscore Somalia's environmental challenges, including severe soil degradation, reduced agricultural productivity, and the exacerbation of droughts due to climate change. The integration of the Modified Fournier Index and the Bagnouls-Gaussen Index within the CORINE model provides a comprehensive assessment of the country's susceptibility to erosion and aridity. This research offers critical insights for prioritizing areas that require urgent soil conservation and improved land-use management. It also serves as a vital tool for policymakers and international organizations aiming to mitigate the adverse impacts of climate change, enhance agricultural sustainability, and promote ecological resilience in Somalia’s diverse landscapes.
Establishment and Evaluation of Soil Fertility Gradient on the Basis of Sorghum Fodder Yield, Nutrient Uptake and Post-Harvest Soil Test Values
Authors: Isha  , Gautam Poonam , Pareek Navneet , Chandra Subhash , Paul Jai , Singh A.P.
Published: December 2024

Field experiment was carried out with fodder sorghum at N.E. Borlaug Crop Research Centre, G.B.U.A.&T., Pantnagar during kharif, 2022 under AICRP on Soil Test Crop Response (STCR) approach aimed to establish and evaluate soil fertility gradient on the basis of sorghum fodder yield, nutrient uptake and post-harvest soil test values. The experimental field was divided into three plots, each receiving graded levels of N, P2O5 and K2O: N0P0K0 (Plot A), N100P100K100 (Plot B) and N200P200K200 (Plot C). Thereafter, fodder sorghum was grown and fodder yield was recorded from each plot. Chemical analysis of plant samples was performed to estimate nitrogen, phosphorus and potassium content and total nutrient uptake was worked out. Post-harvest soil samples were collected across the three plots and analysed for available N, P and K. Findings revealed wide variation in sorghum fodder yield, nutrient uptake and post-harvest soil fertility status for available N, P and K in different plots confirming the establishment of soil fertility gradient for the respective nutrients. The establishment of soil fertility gradient is necessary and serves as a pre-requisite for developing improved nutrient management strategies i.e. STCR-based fertilizer recommendations to sustain crop yield and optimize fertilizer requirements.
Determinants of Work Engagement in the Public Sector: A Systematic Literature Review and Future Research Agenda
Authors: Darmawan I Made , Riana I Gede , Dewi I Gusti Ayu Manuati , Putra Made Surya
Published: December 2024

Aims: This systematic literature review describes recent research on factors determining work engagement, especially within the public sector, and explores possible agendas for upcoming studies.
Methodology: This systematic literature review includes 30 articles published from 2000 to 2023, indexed in Scopus Q1. The databases accessed include API Key Scopus from Harzing's Publish or Perish, Science Direct, and Emerald. Articles were chosen according to predefined inclusion and exclusion criteria to analyze and synthesize information to achieve the research objectives.
Findings: Factors influencing work engagement among public sector employees include job/task-related, individual/personal, and organizational/contextual factors. Leadership factors are also essential for enhancing work engagement across different sectors. Regardless, only a few pieces of literature published in Q1-indexed journals have investigated how leadership influences work engagement.
Research Limitations/Implications: This study highlights the contributions and analyses of several research articles focused on public-sector work engagement. Nevertheless, the sources reviewed are limited in scope. Additionally, identifying research areas that require further exploration can offer a more thorough insight into this topic.
Originality/Value: This research seeks to clarify the development of studies on the public sector that focus on the factors affecting work engagement. It highlights a partial understanding of factors from the perspectives of researchers and the public sector. This study can contribute to the in-depth understanding of public sector research on the determinants of work engagement, thus offering valuable insights for future research.
Tuberculose Pulmonaire Pseudotumorale : A Propos De 4 Cas
Authors: Amrani H.Naji , Belgho R. , Bougrini Y. , Traibi A. , Atoini F. , Ouarssani A.
Published: December 2024

La tuberculose pulmonaire dans sa forme pseudotumorale est une entité rare qui peut simuler un cancer
broncho-pulmonaire, causant ainsi un retard diagnostique et thérapeutique. Les auteurs rapportent quatre cas de tuberculose pseudotumorale à localisation pulmonaire et à travers une revue de littérature ils discutent ses aspects cliniques, radiologiques et conduites diagnostic
Anchorage In Primary Vs. Permanent Teeth For Rapid Maxillary Expansion In Children: Systematic Review And Meta-Analysis
Authors: Tonial Fernanda Guzzo , Moreira Kelly Maria Silva , Lima Marcelo Da Luz Silva , Imparato José Carlos Petorossi , Gimenez Thais
Published: December 2024

Background: Rapid maxillary expansion (RME) is a widely used orthodontic technique to correct transverse
maxillary deficiencies. Both primary and permanent teeth are commonly used as anchorage for this procedure.
However, there is limited evidence regarding differences in skeletal and dental effects or buccal alveolar bone
preservation between these anchorage types.
Materials and Methods: A systematic review was conducted to compare the skeletal and dental effects of RME
using primary or permanent teeth as anchorage. Searches were performed in the following databases: PubMed,
Web of Science, Scopus, LILACS, and OpenGrey. The risk of bias was assessed using the Rob 2.0 and Robins I
tools. The certainty of evidence was evaluated according to the GRADE system, and meta-analysis was
performed with R software.
Results: Eight studies were included in the qualitative analysis and five in the quantitative analysis. The risk of
bias was low in two studies, moderate in five studies, and high in one study. The certainty of evidence was very
low. It was not possible to perform a meta-analysis for the outcome "buccal alveolar bone thickness" due to the
lack of available studies, which was limited to only one study. The intermolar width was greater when the
anchorage used permanent teeth SMD= -1.24; 95% CI (-2.14; -0.33); p<0.01]. However, this difference may
not be clinically relevant.
Conclusion: The evidence does not support a clear recommendation for the use of primary or permanent teeth
as anchorage in RME, as no clinically relevant differences were observed in skeletal or dental effects. Primary teeth may be preferred when buccal alveolar bone preservation is a priority. Further studies are required to enhance evidence and support clinical decisions.
Alimentação E Agrotóxicos: Impactos Sobre A Saúde Humana E O Meio Ambiente
Authors: Morais Danilo Farias De , Farias Sidinei , Rempel Claudete , Marques Francisco Roldineli Varela , Júnior Ailton Santos Sena
Published: December 2024

Esta pesquisa teve como objetivo explorar as percepções e opiniões de ambientalistas sobre os impactos dos
agrotóxicos na saúde humana e no meio ambiente, além de identificar soluções e alternativas sustentáveis para
mitigar esses danos. Adotando uma abordagem qualitativa e exploratória, a pesquisa envolveu entrevistas
semiestruturadas com 20 ambientalistas, cujos relatos foram analisados por meio da técnica da Análise do
Discurso. Os resultados revelaram uma forte preocupação com os efeitos dos agrotóxicos na saúde, como o
aumento de câncer, malformações congênitas e doenças neurodegenerativas, além dos danos ambientais, como
a contaminação do solo e da água e a perda de biodiversidade. A pesquisa também destacou a insatisfação com
a falta de fiscalização e a influência do lobby agropecuário nas políticas públicas, além de defender alternativas
como a agricultura orgânica e de precisão. Embora essas alternativas apresentem benefícios, os desafios incluem custos elevados e resistência ao modelo convencional. A conclusão aponta que, para reduzir os impactos dos
The Effect Of Non-Monetary Benefits On Employee Retention
Authors: Alshaidhani Abdullah Saud Nasser , Musallami Salim Ali Nasser Al , Balushi Faisal Maqbool Bashir Al , Roy Dr Nirmala
Published: December 2024

The aim of this study is to identify the effect of non-monetary benefit on the employee retention. This research has
been done to see the non-monetary and its aspect also in this article, the researcher will discuss more about the
effect of non-monetary benefits on the employee retention and how it effects on total quality of the organization.
This project is to identify the non-monetary factors on employee retention and examines the effects of nonmonetary factors on employee retention. This study was undertaken with the employees working in different
organization. The sample size for the study is 77 employees and the researcher used the descriptive research.
Non-random sampling method was used, and the data was collected through convenience sampling techniques.
The primary data was collected from the respondents through the questionnaire.
The outcomes revealed that the effect of non-monetary benefits has an impact on employee retention of employees work performance in the organization
Abnormal Stock Returns In Stability And Crisis Scenarios: An Analysis Of The Brazilian Market
Authors: Santana Karine De Jesus Rodrigues , Silva Victor
Published: December 2024

This article aimed to analyze the abnormal return on stocks in the Brazilian market, in periods of stability and
national crisis, considering the variables profit, dividend distribution, company size and level of corporate debt.
A documentary research with a quantitative approach and descriptive purpose was carried out. The data were
obtained from the Economática database and analyzed through multiple linear regression. The results showed
that, in the Brazilian scenario, the distribution of dividends, profit and level of corporate debt had a positive
relationship with the abnormal return on stocks. However, the distribution of dividends and profits tend to decrease and the level of debt tends to increase in periods of crisis. On the other hand, size had a negative relationship with the abnormal return on stocks
O Impacto Da Virtualização Processual Na Otimização E Satisfação Com O Trabalho De Servidores Do Tjam
Authors: Almeida Eloane Lima De , Breves Ricardo De Almeida , Lima Orlem Pinheiro De , Filho Wlademir Leite Correia , Araújo Paulo César Diniz De
Published: December 2024

A transição do Tribunal de Justiça do Amazonas (TJAM) do modelo analógico para o digital tem como objetivo
aumentar a eficiência, agilidade e segurança nos processos administrativos. A implementação do Sistema
Eletrônico de Informações (SEI) substitui documentos físicos por versões digitais, promovendo um acesso mais
rápido e reduzindo a burocracia. Contudo, a transformação digital afeta o clima organizacional, principalmente
em uma região extensa como a Amazônia, onde a resistência dos servidores às novas tecnologias representa um desafio. A superação desse obstáculo depende de uma comunicação clara sobre os benefícios, treinamento contínuo e suporte adequado
Association of Sjögren's Syndrome With Reduced Lifetime Sex Hormone Exposure: A Case–Control Study
Authors: McCoy Sara S. , Sampene Emmanuel , Baer Alan N.
Published: June 2019

Objective

To test whether cumulative estrogen exposure, as determined by age at menarche, age at menopause, female hormone use, hysterectomy, and parity, have an effect on the development of primary Sjögren's syndrome (SS).

Methods

We performed a case–control study of 2,680 women from the Sjögren's International Collaborative Clinical Alliance registry, including 1,320 registrants with primary SS and 1,360 with sicca symptoms but no key features of primary SS (sicca controls). The composite estrogen score (CES) was calculated by point assignment for early menarche (age ≤10 years), high parity (>3 pregnancies), hysterectomy, female hormone use, and late menopause (age ≥53 years). Cumulative menstrual cycling (CMC) was calculated as years menstruating minus time pregnant.

Results

Using a regression model that adjusted for age, recruitment site, ethnicity, education, employment status, and smoking, we observed a progressive inverse trend between primary SS and CES. The odds ratio (OR) and 95% confidence interval (95% CI) were as follows for the sicca control group: CES 1, OR 0.81 (95% CI 0.67–0.99); CES 2, OR 0.74 (95% CI 0.57–0.97); CES 3, OR 0.50 (95% CI 0.30–0.86). This trend was corroborated by analysis of CMC. At the highest level of CMC within the postmenopausal group there was a 24% reduction in cumulative sex hormone exposure among primary SS participants relative to controls.

Conclusion

Women with primary SS have lower estrogen exposure and CMC compared to sicca controls. Increasing estrogen exposure was negatively associated with development of primary SS. Further longitudinal studies of sex hormone exposure in primary SS are needed to confirm these findings.
An adaptive learning and control architecture for mitigating sensor and actuator attacks in connected autonomous vehicle platoons
Authors: Jin Xu , Haddad Wassim M. , Jiang Zhong‐Ping , Kanellopoulos Aris , Vamvoudakis Kyriakos G.
Published: June 2019

In this paper, we develop an adaptive control algorithm for addressing security for a class of networked vehicles that comprise a formation of
human‐driven vehicles sharing kinematic data and an autonomous vehicle in the aft of the vehicle formation receiving data from the preceding vehicles through wireless vehicle‐to‐vehicle communication devices. Specifically, we develop an adaptive controller for mitigating time‐invariant state‐dependent adversarial sensor and actuator attacks while guaranteeing uniform ultimate boundedness of the closed‐loop networked system. Furthermore, an adaptive learning framework is presented for identifying the state space model parameters based on input‐output data. This learning technique utilizes previously stored data as well as current data to identify the system parameters using a relaxed persistence of excitation condition. The effectiveness of the proposed approach is demonstrated by an illustrative numerical example involving a platoon of connected vehicles.
Predictive value of computed tomography in the recurrence of chronic rhinosinusitis with nasal polyps
Authors: Meng Yifan , Zhang Luo , Lou Hongfei , Wang Chengshuo
Published: June 2019

Background

Chronic rhinosinusitis with nasal polyps (CRSwNP) is a nasal disease with a high tendency for recurrence. The aim of this study was to compare the use of computed tomography (CT) scan with other clinical parameters in predicting the recurrence of CRSwNP.

Methods

A total of 272 consecutive CRSwNP patients undergoing endoscopic functional sinus surgery were recruited. The demographic characteristics and clinical parameters, including CT scores, level of exhaled nitric oxide, and peripheral eosinophilia, were recorded. The degree of infiltration of inflammatory cells in the sinus mucosa was evaluated.

Results

Two hundred thirty of the 272 patients completed the study (118 patients with recurrence and 112 patients with no recurrence). The average follow‐up time was 24 months after the first surgery. The 2 groups were not significantly different with respect to age, gender distribution, comorbid allergy, exhaled oral fractional exhaled nitric oxide levels, nasal obstruction/runny nose/headache/facial pain scores, Lund‐Mackay score, peripheral eosinophil percentage, and peripheral eosinophil absolute count. The onset of surgical history and asthma, visual analog scores of CRS, anosmia score, ratio of total ethmoid sinus scores for both sides and maxillary sinus score for both sides (E/M ratio), Lund‐Kennedy score, tissue eosinophil percentage, and tissue eosinophil absolute count were significantly higher in the recurrence group. The E/M ratio showed high accuracy as a predictor for CRSwNP recurrence. The cut‐off point of 2.55 for E/M ratio indicated the highest predictive value of CRSwNP recurrence.

Conclusion

The E/M ratio is a useful predictor for the recurrence of CRSwNP in the Chinese population.
A Nanozyme with Photo‐Enhanced Dual Enzyme‐Like Activities for Deep Pancreatic Cancer Therapy
Authors: Li Shanshan , Shang Lu , Xu Bolong , Wang Shunhao , Gu Kai , Wu Qingyuan , Sun Yun , Zhang Qinghua , Yang Hailong , Zhang Fengrong , Gu Lin , Zhang Tierui , Liu Huiyu
Published: June 2019

Nanozymes have attracted extensive interest owing to their high stability, low cost and easy preparation, especially in the field of cancer therapy. However, the relatively low catalytic activity of nanozymes in the tumor microenvironment (TME) has limited their applications. Herein, we report a novel nanozyme (PtFe@Fe3O4) with dual enzyme‐like activities for highly efficient tumor catalytic therapy. PtFe@Fe3O4 shows the intrinsic photothermal effect as well as photo‐enhanced peroxidase‐like and catalase‐like activities in the acidic TME, thereby effectively killing tumor cells and overcoming the tumor hypoxia. Importantly, a possible photo‐enhanced synergistic catalytic mechanism of PtFe@Fe3O4 was first disclosed. We believe that this work will advance the development of nanozymes in tumor catalytic therapy.
The First Observation of Hidden Hysteresis in an Iron(III) Spin‐Crossover Complex
Authors: Boonprab Theerapoom , Lee Seok J. , Telfer Shane G. , Murray Keith S. , Phonsri Wasinee , Chastanet Guillaume , Collet Eric , Trzop Elzbieta , Jameson Guy N. L. , Harding Phimphaka , Harding David J.
Published: June 2019

Molecular magnetic switches are expected to form the functional components of future nanodevices. Herein we combine detailed (photo‐) crystallography and magnetic studies to reveal the unusual switching properties of an iron(III) complex, between low (LS) and high (HS) spin states. On cooling, it exhibits a partial thermal conversion associated with a reconstructive phase transition from a [HS‐HS] to a [LS‐HS] phase with a hysteresis of 25 K. Photoexcitation at low temperature allows access to a [LS‐LS] phase, never observed at thermal equilibrium. As well as reporting the first iron(III) spin crossover complex to exhibit reverse‐LIESST (light‐induced excited spin state trapping), we also reveal a hidden hysteresis of 30 K between the hidden [LS‐LS] and [HS‐LS] phases. Moreover, we demonstrate that FeIII spin‐crossover (SCO) complexes can be just as effective as FeII systems, and with the advantage of being air‐stable, they are ideally suited for use in molecular electronics.
Anisotropic Conductivity at the Single‐Molecule Scale
Authors: Afsari Sepideh , Yasini Parisa , Peng Haowei , Perdew John P. , Borguet Eric
Published: June 2019

In most junctions built by wiring a single molecule between two electrodes, the electrons flow along only one axis: between the two anchoring groups. However, molecules can be anisotropic, and an orientation‐dependent conductance is expected. Here, we fabricated single‐molecule junctions by using the electrode potential to control the molecular orientation and access individual elements of the conductivity tensor. We measured the conductance in two directions, along the molecular plane as the benzene ring bridges two electrodes using anchoring groups (upright) and orthogonal to the molecular plane with the molecule lying flat on the substrate (planar). The perpendicular (planar) conductance is about 400 times higher than that along the molecular plane (upright). This offers a new method for designing a reversible room‐temperature single‐molecule electromechanical switch that controllably employs the electrode potential to orient the molecule in the junction in either “ON” or “OFF” conductance states.
Ultrafast and Highly Selective Uranium Extraction from Seawater by Hydrogel‐like Spidroin‐based Protein Fiber
Authors: Yuan Yihui , Yu Qiuhan , Wen Jun , Li Chaoyang , Guo Zhanhu , Wang Xiaolin , Wang Ning
Published: June 2019

For the practical extraction of uranium from seawater, adsorbents with high adsorption capacity, fast equilibrium rate, high selectivity, and long service life are needed. Herein, a chimeric spidroin‐based super uranyl‐binding protein (SSUP) fiber was designed by fusing the gene of super uranyl‐binding protein (SUP) with the gene of spidroin. SUP endowed the SSUP fiber with high affinity and selectivity to uranium, and spidroin gave the SSUP fiber with high mechanical strength and high reusability. The wet SSUP fiber is a water‐rich hydrogel‐like structure, which provided abundant hydrophilic intermolecular space for the entrance of uranyl ions, and could accelerate the rate for uranium adsorption. In seawater, the SSUP fiber achieved a breakthrough uranium extraction capacity of 12.33 mg g−1 with an ultrashort equilibration time of 3.5 days, suggesting that SSUP fiber might be a promising adsorbent for uranium extraction from the natural seawater.
Derivatization of valproic acid using ferrocene derivatives: Synthesis, characterization and investigation of optical and electrochemical properties
Authors: Rahimpour Keshvar , Jouyban Abolghasem , Teimuri‐Mofrad Reza
Published: June 2019

New ferrocenyl‐based valproic acid (VPA) ester derivatives were designed and synthesized according to the reaction of appropriate haloalkylferrocene derivatives with VPA in the presence of K2CO3 and a catalytic amount of 18‐crown‐6 ether. Elemental analyses and Fourier transform infrared, 1H NMR, 13C NMR and mass spectra all well confirmed the predicted molecular structure. This is the first report in which ferrocene has been applied in derivatization of VPA as a chromogenic group. The electrochemical properties of the synthesized compounds were studied using cyclic voltammetry measurements, and energies of the frontier molecular orbitals were determined. In addition, the solubilities of the final compounds were studied in distilled water, phosphate buffer (pH = 7.4) and 0.9% (w/v) NaCl solution.
Neutral and Anionic Monomeric Zirconium Imides Prepared via Selective C=N Bond Cleavage of a Multidentate and Sterically Demanding β‐Diketiminato Ligand
Authors: Kurogi Takashi , Chu Jiaxiang , Chen Yaofeng , Mindiola Daniel J.
Published: June 2019

A sterically encumbering multidentate β‐diketiminato ligand, tBuL2 (tBuL2=[ArNC(tBu)CHC(tBu)NCH2CH2N(Me)CH2CH2NMe2]−, Ar=2,6‐iPr2C6H3), is reported in this study along with its coordination chemistry to zirconium(IV). Using the lithio salt of this ligand, Li(tBuL2) (4), the zirconium(IV) precursor (tBuL2)ZrCl3 (6) could be readily prepared in 85 % yield and structurally characterized. Reduction of 6 with 2 equiv of KC8 resulted in formation of the terminal and mononuclear zirconium imide‐chloride [C(tBu)CHC(tBu)NCH2CH2N(Me)CH2CH2NMe2]Zr(=NAr)(Cl) (7) as the result of reductive C=N cleavage of the imino fragment in the multidentate ligand tBuL2 by an elusive ZrII species (tBuL2)ZrCl (A). The azabutadienyl ligand in 7 can be further reduced by 2 e− with KC8 to afford the anionic imide [K(THF)2]{[CH(tBu)CHC(tBu)NCH2CH2N(Me)CH2CH2N(Me)CH2]Zr=NAr} (8‐2THF) in 42 % isolated yield. Complex 8‐2THF results from the oxidative addition of an amine C−H bond followed by migration to the vinylic group of the formal [C(tBu)CHC(tBu)NCH2CH2N(Me)CH2CH2NMe2]− ligand in 7. All halides in 6 can be replaced with azides to afford (tBuL2)Zr(N3)3 (9) which was structurally characterized, and reduction with two equiv of KC8 also results in C=N bond cleavage of tBuL2 to form [C(tBu)CHC(tBu)NCH2CH2N(Me)CH2CH2NMe2]Zr(=NAr)(N3) (10), instead of the expected azide disproportionation to N3− and N2. Solid‐state single crystal structural studies confirm the formation of mononuclear and terminal zirconium imido groups in 7, 8‐Et2O, and 10 with Zr=NAr distances being 1.8776(10), 1.9505(15), and 1.881(3) Å, respectively.
Multicentre randomized clinical trial of colonic J pouch or straight stapled colorectal reconstruction after low anterior resection for rectal cancer
Authors: Pucciarelli S , Del Bianco P , Pace U , Bianco F , Restivo A , Maretto I , Selvaggi F , Zorcolo L , De Franciscis S , Asteria C , Urso E D L , Cuicchi D , Pellino G , Morpurgo E , La Torre G , Jovine E , Belluco C , La Torre F , Amato A , Chiappa A , Infantino A , Barina A , Spolverato G , Rega D , Kilmartin D , De Salvo G L , Delrio P
Published: June 2019

Background

Colonic J pouch reconstruction has been found to be associated with a lower incidence of anastomotic leakage than straight anastomosis. However, studies on this topic are underpowered and retrospective. This randomized trial evaluated whether the incidence of anastomotic leakage was reduced after colonic J pouch reconstruction compared with straight colorectal anastomosis following anterior resection for rectal cancer.

Methods

This multicentre RCT included patients with rectal carcinoma who underwent low anterior resection followed by colorectal anastomosis. Patients were assigned randomly to receive a colonic J pouch or straight colorectal anastomosis. The main outcome measure was the occurrence of major anastomotic leakage. The incidence of global (major plus minor) anastomotic leakage and general complications were secondary outcomes. Risk factors for anastomotic leakage were identified by regression analysis.

Results

Of 457 patients enrolled, 379 were evaluable (colonic J pouch arm 190, straight colorectal arm 189). The incidence of major and global anastomotic leakage, and general complications was 14·2, 19·5 and 34·2 per cent respectively in the colonic J pouch group, and 12·2, 19·0 and 27·0 per cent in the straight colorectal anastomosis group. No statistically significant differences were observed between the two arms. In multivariable logistic regression analysis, male sex (odds ratio 1·79, 95 per cent c.i. 1·02 to 3·15; P = 0·042) and high ASA fitness grade (odds ratio 2·06, 1·15 to 3·71; P = 0·015) were independently associated with the occurrence of anastomotic leakage.

Conclusion

Colonic J pouch reconstruction does not reduce the incidence of anastomotic leakage and postoperative complications compared with conventional straight colorectal anastomosis. Registration number NCT01110798 (http://www.clinicaltrials.gov).
Significantly increased anti‐tumor activity of carcinoembryonic antigen‐specific chimeric antigen receptor T cells in combination with recombinant human IL‐12
Authors: Chi Xiaowei , Yang Peiwei , Zhang Erhao , Gu Jieyi , Xu Hui , Li Mengwei , Gao Xinmei , Li Xin , Zhang Yinan , Xu Hanmei , Hu Jialiang
Published: June 2019

Background aims

Chimeric antigen receptor T cells (CAR‐T cells) have been successfully used in treatments of hematological tumors, however, their anti‐tumor activity in solid tumor treatments was limited. As IL‐12 increases T‐cell immune functions, we designed carcinoembryonic antigen (CEA) specific CAR‐T (CEA‐CAR‐T) cells and, for the first time, used them in combination with recombinant human IL‐12 (rhIL‐12) to treat several types of solid tumors.

Methods

In vitro anti‐tumor activity of CEA‐CAR‐T cells in combination with rhIL‐12 was confirmed by evaluation of CEA‐CAR‐T cell activation, proliferation, and cytotoxicity after co‐incubation with CEA‐positive or CEA‐negative human tumor cells. In vivo anti‐tumor activity of CEA‐CAR‐T cells in combination with rhIL‐12 was confirmed in a xenograft model in nude mice for treatments of several types of solid tumors.

Results

In vitro experiments confirmed that rhIL‐12 significantly increased the activation, proliferation, and cytotoxicity of CEA‐CAR‐T cells. Similarly, in vivo experiments found that CEA‐CAR‐T cells in combination with rhIL‐12 had significantly enhanced anti‐tumor activity than CEA‐CAR‐T cells in growth inhibition of newly colonized colorectal cancer cell HT‐29, pancreatic cancer cell AsPC‐1, and gastric cancer cell MGC803.

Conclusions

These works confirmed that simultaneous use of cytokines, for example, rhIL‐12, can increase the anti‐tumor activity of CAR‐T cells, especially for treatments of several types of solid tumors.
Psoriasis cases of same diagnosis but different phenotypes—Management through individualized homeopathic therapy
Authors: Mahesh Seema , Shah Viraj , Mallappa Mahesh , Vithoulkas George
Published: June 2019

This case series demonstrates that classical homeopathy may have a solution to psoriasis and its complications which goes beyond skin clearance and achieves general well‐being. The variety in clinical phenotypes and their response to treatment may be explained on the basis of the theory of “Levels of Health."
Versatile Ru‐Photoredox‐Catalyzed Functionalization of Dehydro‐Amino Acids and Peptides
Authors: Brandhofer Tobias , Mancheño Olga García
Published: June 2019

A versatile photoredox‐catalyzed synthesis of unnatural amino acids and peptides is presented. Commercially available Ru(bpy)3(PF6)2 was efficiently used as visible light photocatalyst in combination with a broad number of different types of radical precursors in the coupling with several dehydrogenated amino acid residues. This method provides new entries to the mild, selective and direct modification of both simple and complex peptide‐like compounds towards novel structures with improved or unusual properties. Hence, (fluorinated)alkyl halides, arylsulfonyl chlorides or various N‐(acyloxy)phthalimides (NHPI esters) were effectively reacted with a series of natural and unnatural α,β‐dehydroamino acids and dipeptides. Moreover, the applicability of the process was also proved by the late stage functionalization of the naturally occurring peptide thiostrepton.
Near UV‐Irradiation of CuOx‐Impregnated TiO2 Providing Active Species for H2 Production Through Methanol Photoreforming
Authors: Vitiello Giuseppe , Clarizia Laura , Abdelraheem Wael , Esposito Serena , Bonelli Barbara , Ditaranto Nicoletta , Vergara Alessandro , Nadagouda Mallikarjuna , Dionysiou Dionysios D. , Andreozzi Roberto , Luciani Giuseppina , Marotta Raffaele
Published: June 2019

Copper doped‐TiO2 (P25) nanomaterials have been intensively studied as promising catalysts for H2 production by photo‐reforming of selected organic compounds. However, the role of copper oxidation states on the improvement of photocatalytic activity is still debated. In this work, CuOx‐impregnated P25‐TiO2 catalysts were used for photocatalytic production of hydrogen from methanol. Copper species/oxidation states both in the as‐prepared catalysts and after the photocatalytic process were investigated. To this purpose, H2 production rates were correlated to physico‐chemical properties of the samples, both before and after photocatalytic process, by means of Raman, X‐Ray Diffraction, Electron Paramagnetic Resonance spectroscopy, X‐Ray Photoelectron Spectroscopy, Temperature‐Programmed Reduction and High Resolution Transmission Electron Microscope techniques. Results revealed the presence of both Cu2O and CuO deposits on the samples surface after calcination. Notably, under near‐UV irradiation, the fraction of highly dispersed CuO particles undergo a partial dissolution process, followed by reduction to metallic copper Cu(s) by photogenerated electrons, boosting H2 production rate. Our findings indicate that both Cu2O and Cu(s) act as co‐catalysts for H2 generation, yet by different mechanisms. Overall this study, provides the basis to enhance catalytic performance of red‐ox active systems through UV‐irradiation approach.
CoIICryptates Convert CO2into CO and CH4under Visible Light
Authors: Realista Sara , Almeida Janaína C. , Milheiro Sofia A. , Bandeira Nuno A. G. , Alves Luis G. , Madeira Filipe , Calhorda Maria José , Martinho Paulo N.
Published: June 2019

Three CoIIoctaazacryptates, with different substituents on the aromatic rings (Br, NO2, CCH), were synthesised and characterised. These and the already published non‐substituted cryptate catalysed CO2photoreduction to CO and CH4under blue visible light at room temperature. Although CO was observed after short irradiation times and a large range of catalyst concentrations, CH4was only observed after longer irradiation periods, such as 30 h, but with a small catalyst concentration (25 nm). Experiments with13C labelled CO2showed that CO is formed and reacts further when the reaction time is long. The CCH catalyst is deactivated faster than the others and the more efficient catalyst for CH4production is the one with Br. This reactivity trend was explained by an energy decomposition analysis based on DFT calculations.
Co3+‐Rich Na1.95CoP2O7 Phosphates as Efficient Bifunctional Catalysts for Oxygen Evolution and Reduction Reactions in Alkaline Solution
Authors: Gui Liangqi , Miao Xiaoyun , Lei Chengjun , Wang Kailin , Zhou Wei , He Beibei , Wang Qing , Zhao Ling
Published: June 2019

Implementing sustainable energy conversion and storage technologies is highly reliant on crucial oxygen electrocatalysis, such as the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). However, the pursuit of low cost, energetic efficient and robust bifunctional catalysts for OER and ORR remains a great challenge. Herein, the novel Na‐ion‐deficient Na2−xCoP2O7 catalysts are proposed to efficiently electrocatalyze OER and ORR in alkaline solution. The engineering of Na‐ion deficiency can tune the electronic structure of Co, and thus tailor the intrinsically electrocatalytic performance. Among the sodium cobalt phosphate catalysts, the Na1.95CoP2O7 (NCPO5) catalyst exhibits the lowest ΔE (EJ10,OER−EJ−1,ORR) of only 0.86 V, which favorably outperforms most of the reported non‐noble metal catalysts. Moreover, the Na‐ion deficiency can stabilize the phase structure and morphology of NCPO5 during the OER and ORR processes. This study highlights the Na‐ion deficient Na2−xCoP2O7 as a promising class of low‐cost, highly active and robust bifunctional catalysts for OER and ORR.
Cross‐Coupling of Secondary Amides with Tertiary Amides: The Use of Tertiary Amides as Surrogates of Alkyl Carbanions for Ketone Synthesis
Authors: Wang Shu‐Ren , Huang Pei‐Qiang
Published: June 2019

Summary of main observation and conclusion

In recent years, exciting progress has been made in the field of direct transformation of amides, nevertheless, the condensation between two amides remains rare and restricted to homo‐coupling reactions. Herein, we report the cross‐coupling of secondary amides with tertiary amides, which provides a synthesis of ketones under mild conditions, and features the use of tertiary amides as surrogates of alkyl carbanions. The method relies on the coupling of enamines, generated from tertiary amides by catalytic partial reduction of tertiary amides with Vaska's catalyst, with nitrilium ions, formed in situ from secondary amides via activation with trifluoromethanesulfonic anhydride, and on the subsequent deformylation.
Ransomware detection using machine learning algorithms
Authors: Bae Seong Il , Lee Gyu Bin , Im Eul Gyu
Published: June 2019

The number of ransomware variants has increased rapidly every year, and ransomware needs to be distinguished from the other types of malware to protect users' machines from ransomware‐based attacks. Ransomware is similar to other types of malware in some aspects, but other characteristics are clearly different. For example, ransomware generally conducts a large number of file‐related operations in a short period of time to lock or to encrypt files of a victim's machine. The signature‐based malware detection methods, which have difficulties to detect zero‐day ransomware, are not suitable to protect users' files against the attacks caused by risky unknown ransomware. Therefore, a new protection mechanism specialized for ransomware is needed, and the mechanism should focus on ransomware‐specific operations to distinguish ransomware from other types of malware as well as benign files. This paper proposes a ransomware detection method that can distinguish between ransomware and benign files as well as between ransomware and malware. The experimental results show that our proposed method can detect ransomware among malware and benign files.
Making Light Work of Material Design
Authors: Barner‐Kowollik Christopher
Published: June 2019

Christopher Barner‐Kowollik
is the Head of the Soft Matter Materials Laboratory at the Queensland University of Technology (QUT) and a Fellow of the Australian Academy of Science. He is a current member of the ChemPhotoChem Editorial Board.