bluuebunny/crossref_metadata_2025 huggingface dataset:
An Overview of Computer Operating Systems and Emerging Trends
Authors: Bazuku Robert , Anab Anaamotulim , Gyemerah Seth , Daabo Mohammed I.
Published: October 2023

This article presents an overview of computer operating systems (OS) and emerging trends. OS is simply defined as an interface between computer hardware and the user. The objective of the study is to investigate the emerging trends of OS and to find out the direction of OS for modern computing systems. To achieve this goal the paper looks at the concepts of OS, its underlying architectures and evolution. The papers also outline the components of the OS provide knowledge on security issues with OS architectures and provide best practices to secure OS. The paper found out that the current trends in OS include IoT OS, Cloud OS, AI-powered OS, Blockchain OS, Hybrid OS and Container OS. The paper compares the strengths and weaknesses of the major OS. The Paper proposes a double-layer security approach where the OS is hardened with security policies and embedding security protocols in the Hardware architecture of the OS. It was discovered that every technology comes with its unique architecture and OS. This makes it worrisome for engineers to crack their brains to develop such a system. The paper further proposes the development of a universal OS for all architectures leaving room for further expansion while mitigating power consumption issues by incorporating green computing technology in the design architecture.
Effect of Predominant Mycoflora (A. alternata and M. phaseolina) on Seed Quality Parameters of Sesamum
Authors: Greeshma S. , Rajeswari B. , Babu T. Kiran , Sujatha P.
Published: October 2023

Sesamum is an important oilseed crop affected by toxigenic fungal pathogens viz., Alternaria, Macrophomina, Fusarium and Aspergillus spp. Among these, A. alternata and M. phaseolina are seed borne pathogens causing yield loss to an extent of 20 to 40 per cent. The effect of A. alternata and M. phaseolina on seed quality parameters of susceptible cv. Swetha was investigated during 2022-2023. The A. alternata and M. phaseolina inoculated and uninoculated seeds of both test pathogens were tested for germination and seedling growth by rolled paper method and pot culture studies. Significant differences in seed germination, seedling length, seedling dry mass, seedling vigour index (SVI) - I and II and seed moisture content were observed in susceptible cv. Swetha. The results indicated that A. alternata recorded lower seed germination percentage (60.50%), seedling length (6.56 cm), dry mass (9.12 mg) and SVI-I and II (656 and 552 respectively) over untreated seeds recording high germination (82.25%), seedling length (14.84 cm), dry mass (13.17 mg) and SVI-I and II (1221 and 1116 respectively). Similar results were observed in M. phaseolina treated seeds where the pathogen treated seeds recorded lower seed germination percentage (70.75%), seedling length (9.42 cm), dry mass (8.71 mg) and SVI-I and II (667 and 599 respectively) than pathogen untreated seeds recording high seed germination (82.50%), seedling length (14.25 cm), dry mass (13.30 mg) and SVI-I and II (1175 and 1097 respectively).
The Trends and Growth Analysis in the Area, Production and Productivity of Turmeric in Surguja District of Chhattisgarh, India
Authors: Ram Siya , Chandrakar M. R. , Atree Narottam , Patel Pradip Kumar , Gauraha A. K. , Minj Shashi Kiran
Published: October 2023

Turmeric is an important spice crop grown in Chhattisgarh. The present study is mainly based on time series data. The secondary data on area, production and productivity of Turmeric in Chhattisgarh, were collected for the period 2001-02 to 2020-21from various publications. To analyze the trends and growth rate in the area, production and productivity of turmeric in Surguja district of Chhattisgarh state. The performance of turmeric was examined by estimating the growth rates and instability index of area, production and productivity of turmeric. Growth analysis for area, production and productivity. Focus on the Surguja district. It was positive and non-significant in the area of compound and linear growth rate, but it was positive and significant in the case of production. In terms of productivity, both compound and linear growth rate showed negatively significance. In the case of Chhattisgarh, the linear and compound growth rates in the area and production of turmeric were observed as positive and non-significant. While the growth rate in productivity in Chhattisgarh was found negatively and significant over the period.  The major of constraints faced by the selected area, unavailability of improved and high yielding varieties, package and practices and Weather fluctuation. Ensure to availability of Improved and high yielding varieties for good production, productivity and good quality and Weather based information should provide for turmeric grower region.
Molecular Variations in Rabi Sorghum Varieties Using SSR Markers
Authors: Gadakh S. S.  , Khalekar G. D.  , Dalvi U. S.  , Kulwal P. L.  , Kale A. A.  , Shinde M. S.
Published: October 2023

Genetic diversity was assessed for 2 popular varieties and 5 promising lines of rabi sorghum by using11 SSR markers. The marker Xiabt312 reported 100% polymorphism rate followed by Xtxp15 (85.70%) and mSbCIR300 (85.71%). The sorghum varieties studied for this analysis showed the polymorphism information content (PIC) ranged from 0.25 to 0.87 with a mean of 0.67 indicates higher diversity within them. Clustering analysis based on the genetic dissimilarity grouped the 7 lines into 2 major and 4 sub clusters and grouping was in good agreement with pedigree. Cluster II was the largest cluster with 4 genotypes followed by cluster I with 3 genotypes. The rabi sorghum genotypes viz., M35-1, RSV-1876 and RSLG-2422 were placed in cluster I and Phule Anuradha, RSV-2371, RSV-1910 and RSV-1988 placed in cluster II. Clustering based on SSR molecular profile of the genotypes shows that there is a distinct variability among the genotypes under this study. The selected markers have great potential in DNA fingerprinting in sorghum which in future could be integrated with DUS data descriptors for effective cultivar identification and differentiation.
Effect of Different Rice Establishment Methods on Soil Nutrient Status and Carbon Stock in Paddy Growing Soils of Jagtial, Telangana, India
Authors: Amulya D. , Chaitanya A. Krishna , Kumar R. Sai , Rajanikanth E.
Published: October 2023

The study was conducted to know the nutrient status, yield, straw and harvest index in 4 different cropping systems viz., (i) manual transplanting; (ii) dry direct seeding; (iii) drum seeding and (iv) machine transplanting 120 soil samples were analysed, 30 from each establishment method. The soil fertility status from different establishment methods was studied by analysing the samples for pH, EC, bulk density, organic carbon, available nitrogen, phosphorous, potassium, iron, zinc, total organic carbon and carbon stock. The study revealed that there is a significant difference in bulk density ranged high in machine transplanting (1.48 Mg m-3) and low in dry direct seeding (1.45Mg m-3). pH of soils was neutral to slightly alkaline in nature and iron content of soils ranged from 5.75 to 8.97 mg kg-1.
Effect of Foliar Application of Water-Soluble Fertilizers on Growth and Yield of Wheat (Triticum aestivum L.)
Authors: Ninama A. R. , Vala G. S. , Choudhary R. , Chudasma S. D. , Jadeja J. P. , Ram K. V.
Published: October 2023

Direct fertilizer application to leaves stimulates leaf activity, which directly affects the plant's water uptake and promotes root growth. Foliar fertilizers can therefore hasten the uptake of nutrients from the soil, which is advantageous for plants that need urgent nutrient intervention. A field experiment was carried out at Junagadh Agricultural University, Junagadh during rabi season of 2019-20 to evaluate effect of foliar spray of water-soluble fertilizers on wheat (Triticum aestivum L.) growth and yield. The experimental trial consists of 12 treatments with 3 replication and randomized block design. The results of the experiment revealed that the growth parameters viz., plant height and number of effective tillers metre-1 row length at harvest increased significantly with the application of T2 + foliar spray of 19:19:19 @ 0.5% at 60 DAS & 90 days after sowing (DAS) whereas plant population were not affect significantly by application of different treatments. There was also significant improvement in grain and straw yields were observed with the application of T8 over 75% recommended dose of fertilizer (RDF) and 100% RDF.
Index-Based Change Detection, Spatial Zoning and Environmental Criticality of Urban Land Cover: A Spatiotemporal Study on Gazipur Sadar Upazila of Bangladesh
Authors: Parvin Most. Atia , Haque Md. Inzamul , Hossain Md. Anik , Bashar Abul
Published: October 2023

Urbanization has become a comprehensive phenomenon worldwide as well as in Bangladesh. This study has tried to analyze the urban land cover change pattern of Gazipur Sadar Upazila between 2001 and 2021. This study also has made an investigation to classify the urban land cover of Gazipur Sadar Upazila based on categorical spatial zoning and analyze how urbanization affects nearby green spaces to monitor environmental criticality. Multispectral Landsat satellite imageries, population census data, air quality index, and open-ended questionnaire data were used as the operational data. Spectral indices such as NDVI, and IBI, were performed from remotely sensed satellite data. NDVI was used to extract green cover and IBI was used to extract the built-up area. Spatial zoning was done based on existing literature, expert interviews, and RS analysis. Environmental criticality was analyzed by correlating population density and air quality data with the extracted green cover. Between 2001 and 2021, the built-up area expanded by around 77.7 km2 and green cover by about 74.79 km2. Although the green cover flourished, it decreased in Tongi and Konabari. Besides, the south-western region of Gazipur experiences rapid growth in built-up areas. Three classified zones e.g., industrial and manufacturing zone, forested zone, and neutral zone were extracted from criteria-based spatial zoning. The results of green space per capita analysis showed that from 2001 to 2021, green space in the study area decreased by 10-713 m2. Environmental criticality analysis illustrated that in 2001, two regions (Tongi and Konabari) were classified as highly critical, and by 2021, this number had escalated to five (Tongi, Konabari, Kasimpur, Basan, Gaccha). Furthermore, the study uncovered that the criticality in urbanized areas is growing rapidly.
The Supreme Court’s 303 Creative Decision and the Threat to LGBTQ+ Health Care
Authors: Sepper Elizabeth W. , Romero Joshua B. , Aaron Daniel G.
Published: October 2023

This Viewpoint examines the importance of the Supreme Court decision in 303 Creative and its possible effects on legislation safeguarding nondiscriminatory health care.
County-Level Trends in Cervical Cancer Incidence, Stage at Diagnosis, and Mortality in Kentucky
Authors: Damgacioglu Haluk , Burus Todd , Sonawane Kalyani , Hill Elizabeth , Lang Kuhs Krystle A. , Deshmukh Ashish A.
Published: October 2023

This cross-sectional study evaluates recent trends in rates of cervical cancer incidence and incidence-based mortality among women in Appalachian and non-Appalachian Kentucky counties.
Developmental Trajectory of Body Weight in Youths at Risk for Major Mood Disorders
Authors: Adepalli Nitya , Cumby Jill , Campbell Niamh , Pavlova Barbara , Alda Martin , Cahill Leah E. , Uher Rudolf
Published: October 2023

Importance

Mood disorders are associated with increased body weight, especially in females, but it remains unknown when the weight increase starts.

Objectives

To examine sex-specific weight trajectories associated with familial mood disorder risk and determine the age at which youth at familial risk for mood disorders begin to diverge in weight from controls.

Design, Setting, and Participants

This community-based, single-center, acceleration cohort study of youth at familial risk for mood disorders and controls with yearly follow-ups (mean [SD], 5 [2.1] years) from January 1, 2014, to December 31, 2022, assessed 394 unaffected female and male offspring (aged 3 to 20 years) of parents with or without a mood disorder. Parents with mood (depressive or bipolar) disorders were recruited through adult mental health services. Parents of control participants were matched on age and socioeconomic factors and recruited through acquaintance referrals or schools.

Exposures

The youth in the familial mood risk group had at least 1 parent with a major mood disorder, whereas control youth did not have a parent with a mood disorder.

Main Outcomes and Measures

Body mass indexes (BMIs) were calculated as weight in kilograms divided by height in meters squared from measured weight and height at annual assessments and then converted to age- and sex-adjusted z scores (zBMIs). Repeated-measure regressions examined the association between zBMI and age in youth at familial risk of mood disorders and controls while accounting for sex. Sensitivity analyses accounted for socioeconomic status, prematurity, and birth weight.

Results

Of 394 participants (mean [SD] age, 11.5 [3.6] years; 203 [51.5%] female), youths at familial risk for mood disorders showed overall no difference in body weight (β = 0.12; 95% CI, 0.01-0.24) from controls. A sex-specific difference was detected, with females at familial risk showing a rapid peripubertal increase in body weight, leading to significantly increased zBMIs at 12 years and older compared with controls (β = 0.57; 95% CI, 0.31-0.82) independent of socioeconomic status, prematurity, or birth weight. Males did not differ from controls at any age.

Conclusions and Relevance

In this cohort study, females with a family history of mood disorders were prone to weight gain starting around puberty and predating mood disorder onset. Early interventions aiming to prevent adverse mental and physical outcomes in this vulnerable group need to start in childhood.
A Young Man With a Neck Mass and Hypereosinophilia
Authors: Hameed Maha , Bakshi Nasir , Alfayez Mansour
Published: October 2023

A 31-year-old man presented with left cervical and left inguinal masses and intermittent itching and night sweats for 2 years. What is your diagnosis?
Considerations in Narrowing the Breast Cancer Mortality Gap Between Black and White Women
Authors: McCullough Lauren E. , Maliniak Maret L. , Moubadder Leah
Published: October 2023

This Viewpoint discusses 3 key measures of population-based surveillance along with areas for future investigation to reduce racial disparities in breast cancer mortality.
Progressive Retinal Medullated Nerve Fiber Layer in a Young Boy
Authors: Ma Mingming , Sun Tao
Published: October 2023

This case report documents progression of myelinated retinal nerve fibers in a young boy from age 6 months to 2 years.
Punctal Plug Granuloma After Blepharoplasty
Authors: Goodyear Kendall , Pirakitikulr Nathan , Rootman Daniel B.
Published: October 2023

This case report discusses a diagnosis of foreign body granuloma resulting from a punctal plug in a patient aged 66 years with chronic dry eye and a history of blepharoplasty.
A Rare Case of Idiopathic Lymphadenopathy
Authors: Goehring Lexi , King Joy , Pleitz Jordan
Published: October 2023

A 28-year-old woman had a 5-day history of painful cervical lymphadenopathy along with fever, nausea, and vomiting. Treatment with antibiotics and corticosteroids did not improve her symptoms. What is your diagnosis?
Promoting Surgeon-Scientists in Otolaryngology–Head and Neck Surgery—From Bench to Bedside
Authors: Kosaraju Nikitha , Keating Donald P. , Kim Grace S. , Moore Lindsay S. , Stankovic Konstantina M.
Published: October 2023

Importance

Surgeon-scientists (defined as principal investigators [PIs] with a Doctor of Medicine [MD] degree or a combined MD and Doctor of Philosophy [PhD] degree) in otolaryngology–head and neck surgery (OHNS) are imperative for achieving clinical translation in the OHNS field.

Objective

To (1) raise awareness about the current state of surgeon-scientists in OHNS, (2) contextualize the landscape of surgeon-scientists in OHNS by comparing it to those of neurosurgery and ophthalmology, and (3) identify strategies for attracting and retaining surgeon-scientists in OHNS.

Evidence Review

Research funding data from fiscal years 2015 to 2021 among surgeon-scientists in OHNS, neurosurgery, and ophthalmology were obtained from the National Institutes of Health (NIH) Research Portfolio Online Reporting Tools Expenditures and Results and the US Department of Defense (DOD) Congressionally Directed Medical Research Programs awards database. The Association of American Medical Colleges provided the total number of active physicians in each specialty per year and the number and percentage of residents with an MD-PhD degree in each specialty per year. Cohen d was used to express the standardized value of the magnitude of the mean difference between compared groups.

Findings

From 2015 to 2021, on average, there were 9566 active physicians in OHNS, 5559.8 in neurosurgery, and 18908.8 in ophthalmology. In OHNS, a greater number of NIH K (research career development) grants were held by surgeon-scientists than by PIs with a PhD degree (21.4 vs 5.1; mean difference, 16.3; 95% CI, 14.3-18.3; Cohen d = 9.6), whereas most NIH R (research) and U (cooperative agreement) grants (144.1 vs 81.6; mean difference, 62.6; 95% CI, 46.3-78.9; Cohen d = 4.5) and DOD grants (9.9 vs 4.1; mean difference, 5.7; 95% CI, 1.0-10.4; Cohen d = 1.4) were held by PIs with a PhD degree. In a comparison of OHNS to neurosurgery and ophthalmology, after the number of R and U grants was scaled by the number of physicians in each field, neurosurgery had a much greater number of grants per surgeon than OHNS (0.02 vs 0.01; mean difference, 0.01; 95% CI, 0.01-0.02; Cohen d = 4.2). Additionally, neurosurgeons received a much larger R and U grant amount per physician than otolaryngologists ($10 630.20 vs $4511.80; mean difference, $6118.40; 95% CI, $2625.90-$9610.80; Cohen d = 2.0). For the R and U grant metrics, there were no meaningful differences between OHNS and ophthalmology.

Conclusions and Relevance

Results of this database study showed that from 2015 to 2021, the number of governmental grants held by surgeon-scientists in OHNS increased, but there is room for improvement given the metrics of neurosurgeons, a population smaller than otolaryngologists. Possible strategies include intramural research grants, surgeon-scientist training programs, and partnerships between specialty societies and NIH administering institutes and centers.
Dental Extractions Before Radiation Therapy and the Risk of Osteoradionecrosis in Patients With Head and Neck Cancer
Authors: Lee Junhyung , Hueniken Katrina , Cuddy Karl , Pu Jiajie , El Maghrabi Amr , Hope Andrew , Hosni Ali , Glogauer Michael , Watson Erin
Published: October 2023

Importance

Patients with head and neck cancer undergo extraction of teeth with poor prognoses to minimize post-radiation therapy (RT) extractions, which are known to cause osteoradionecrosis (ORN). However, many patients are required to start RT before the extraction sites are completely healed. The role of pre-RT extractions in the development of ORN has been disputed in literature.

Objective

To determine whether the timing of pre-RT dental extractions is associated with ORN development in patients with head and neck cancer.

Design, Setting, and Participants

This retrospective cohort study was conducted at a single institution (Princess Margaret Cancer Centre, Toronto, Canada) between January 1, 2011, and January 1, 2018, and included 879 patients with head and neck cancer who underwent pre-RT dental extractions before curative RT of 45 Gy or greater. Patient demographic information and clinical characteristics (eg, primary cancer site, nodal involvement, chemotherapy, smoking status, dental pathology) were considered. Data analyses were performed from July to December 2022.

Main outcomes and measures

Timing (number of days) from dental extractions to RT start date and pre-RT extractions categorized as healed, minor bone spicules (MBS), or ORN.

Results

The study population consisted of 879 patients with a median (range) age of 62 (20-96) years, with 685 men (78%) and 194 women (22%). Of these, 847 (96.3%) healed from pre-RT dental extractions, 16 (1.8%) developed MBS, and 16 (1.8%) developed ORN. The median (range) time in number of days from pre-RT extraction(s) to start of RT was 9 (0-98) days in the healed cohort, 6 (3-23) days in the MBS cohort, and 6 (0-12) days in the ORN cohort. There was a large difference in the timing of pre-RT extractions between the healed and the MBS cohorts (mean 11.9 vs 7.4 days to radiation; difference 4.4; 95% CI, 1.5-7.3), and the healed and the ORN cohorts (mean 11.9 vs 7.1 days; difference 4.8 days; 95% CI, 2.6-7.1).

Conclusion

The findings of this retrospective cohort study suggest that there was an important association between the timing of pre-RT dental extractions and ORN when extractions occurred within 7 days of the RT start date. Despite this, ORN after pre-RT extractions is relatively rare. These findings indicate that patients with head and neck cancer who are to undergo RT should not delay treatment for extractions when it might compromise oncologic control.
Proteomics on malignant pleural effusions reveals ERα loss in metastatic breast cancer associates with SGK1–NDRG1 deregulation
Authors: Mayayo‐Peralta Isabel , Debets Donna O. , Prekovic Stefan , Schuurman Karianne , Beerthuijzen Suzanne , Almekinders Mathilde , Sanders Joyce , Moelans Cathy B. , Saleiro Sandra , Wesseling Jelle , van Diest Paul J. , Henrique Rui , Jerónimo Carmen , Altelaar Maarten , Zwart Wilbert
Published: October 2023

Breast cancer (BCa) is a highly heterogeneous disease, with hormone receptor status being a key factor in patient prognostication and treatment decision‐making. The majority of primary tumours are positive for oestrogen receptor alpha (ERα), which plays a key role in tumorigenesis and disease progression, and represents the major target for treatment of BCa. However, around one‐third of patients with ERα‐positive BCa relapse and progress into the metastatic stage, with 20% of metastatic cases characterised by loss of ERα expression after endocrine treatment, known as ERα‐conversion. It remains unclear whether ERα‐converted cancers are biologically similar to bona fide ERα‐negative disease and which signalling cascades compensate for ERα loss and drive tumour progression. To better understand the biological changes that occur in metastatic BCa upon ERα loss, we performed (phospho)proteomics analysis of 47 malignant pleural effusions derived from 37 BCa patients, comparing ERα‐positive, ERα‐converted and ERα‐negative cases. Our data revealed that the loss of ERα‐dependency in this metastatic site leads to only a partial switch to an ERα‐negative molecular phenotype, with preservation of a luminal‐like proteomic landscape. Furthermore, we found evidence for decreased activity of several key kinases, including serum/glucocorticoid regulated kinase 1 (SGK1), in ERα‐converted metastases. Loss of SGK1 substrate phosphorylation may compensate for the loss of ERα‐dependency in advanced disease and exposes a potential therapeutic vulnerability that may be exploited in treating these patients.
Scalable Production of Transition Metal Chalcogenides/Ultrathin 2D Carbon Nanosheets Composites with a Universal “All‐in‐One” Blowing Strategy
Authors: Li Jianyu , Pang Zimo , Gao Chao , Zhang Guangyue , Dai Jianhong , Chen Tao , Su Xin , Zhou Weiwei
Published: October 2023

Transition metal chalcogenides (TMCs) belongs to the most promising class of materials with unique properties and widespread applications. Coupling with carbon materials allows further enhancement of the specific performance of TMCs by mitigating their intrinsic deficiencies. However, the synthesis of a wide variety of TMCs/carbon composites with a universal strategy especially in a scalable manner remains challenging. In this work, by utilizing the gas‐liquid interfaces in viscous gel precursors, an “all‐in‐one” blowing strategy is proposed to achieve the synchronous growth of TMCs and carbon nanosheets, obviating the additional chalcogenization process. The generality of the proposed blowing strategy is validated by the fabrication of 32 different TMCs/carbon composites, including 24 binary TMCs, 4 ternary TMCs and 4 high‐entropy sulfides. In‐depth mechanistic study is accomplished by investigating the physical evolution of blowing process and accompanying chemical reactions systematically. Also, the structure of the resulting foam is adjustable by controlling the heating rate and viscosity of the precursors is demonstrated. As an illustrative example for the application of energy storage, MoS2xSe2(1‐x)@CNS exhibits great Li+ storage capacity and cycling stability. Overall, this methodology serves as an effective general strategy for the rational discovery of TMCs/carbon composites and inorganic solid foams.
Perovskite BaTaO2N: From Materials Synthesis to Solar Water Splitting
Authors: Hojamberdiev Mirabbos , Vargas Ronald , Zhang Fuxiang , Teshima Katsuya , Lerch Martin
Published: October 2023

Barium tantalum oxynitride (BaTaO2N), as a member of an emerging class of perovskite oxynitrides, is regarded as a promising inorganic material for solar water splitting because of its small band gap, visible light absorption, and suitable band edge potentials for overall water splitting in the absence of an external bias. However, BaTaO2N still exhibits poor water‐splitting performance that is susceptible to its synthetic history, surface states, recombination process, and instability. This review provides a comprehensive summary of previous progress, current advances, existing challenges, and future perspectives of BaTaO2N for solar water splitting. A particular emphasis is given to highlighting the principles of photoelectrochemical (PEC) water splitting, classic and emerging photocatalysts for oxygen evolution reactions, and the crystal and electronic structures, dielectric, ferroelectric, and piezoelectric properties, synthesis routes, and thin‐film fabrication of BaTaO2N. Various strategies to achieve enhanced water‐splitting performance of BaTaO2N, such as reducing the surface and bulk defect density, engineering the crystal facets, tailoring the particle morphology, size, and porosity, cation doping, creating the solid solutions, forming the heterostructures and heterojunctions, designing the photoelectrochemical cells, and loading suitable cocatalysts are discussed. Also, the avenues for further investigation and the prospects of using BaTaO2N in solar water splitting are presented.
Normal B cells express ZAP70 in chronic lymphocytic leukemia: A link between autoimmunity and lymphoproliferation?
Authors: Ghergus Dana , Martin Mickaël , Knapp Anne‐Marie , Delmotte Fabien , Joublin‐Delavat Aurélie , Jung Sophie , Schickel Jean‐Nicolas , Mendel Isabelle , Dupuis Arnaud , Drénou Bernard , Ghesquières Hervé , Salles Gilles , Baseggio Lucile , Herbrecht Raoul , Korganow Anne‐Sophie , Vallat Laurent , Soulas‐Sprauel Pauline , Meffre Eric , Martin Thierry
Published: October 2023

ZAP70 has a prognostic value in chronic lymphocytic leukemia (CLL), through altered B‐cell receptor signaling, which is important in CLL pathogenesis. A good correlation between ZAP70 expression in CLL cells and the occurrence of autoimmune phenomena has been reported. Yet, the great majority of CLL‐associated autoimmune cytopenia is due to polyclonal immunoglobulin (Ig) G synthesized by nonmalignant B cells, and this phenomenon is poorly understood. Here, we show, using flow cytometry, that a substantial percentage of CD5‐ nonmalignant B cells from CLL patients expresses ZAP70 compared with CD5‐ B cells from healthy subjects. This ZAP70 expression in normal B cells from CLL patients was also evidenced by the detection of ZAP70 mRNA at single‐cell level with polyclonal Ig heavy‐ and light‐chain gene transcripts. ZAP70+ normal B cells belong to various B‐cell subsets and their presence in the naïve B‐cell subset suggests that ZAP70 expression may occur during early B‐cell development in CLL patients and potentially before malignant transformation. The presence of ZAP70+ normal B cells is associated with autoimmune cytopenia in CLL patients in our cohort of patients, and recombinant antibodies produced from these ZAP70+ nonmalignant B cells were frequently autoreactive including anti‐platelet reactivity. These results provide a better understanding of the implication of ZAP70 in CLL leukemogenesis and the mechanisms of autoimmune complications of CLL.
Enhancing Local CO2 Adsorption by L‐histidine Incorporation for Selective Formate Production Over the Wide Potential Window
Authors: Li Yicheng , Delmo Ernest Pahuyo , Hou Guoyu , Cui Xianglong , Zhao Ming , Tian Zhihong , Zhang Yu , Shao Minhua
Published: October 2023

Electrochemical carbon dioxide reduction reaction (CO2RR) to produce valuable chemicals is a promising pathway to alleviate the energy crisis and global warming issues. However, simultaneously achieving high Faradaic efficiency (FE) and current densities of CO2RR in a wide potential range remains as a huge challenge for practical implements. Herein, we demonstrate that incorporating bismuth‐based (BH) catalysts with L‐histidine, a common amino acid molecule of proteins, is an effective strategy to overcome the inherent trade‐off between the activity and selectivity. Benefiting from the significantly enhanced CO2 adsorption capability and promoted electron‐rich nature by L‐histidine integrity, the BH catalyst exhibits excellent FEformate in the unprecedented wide potential windows (>90 % within −0.1–−1.8 V and >95 % within −0.2–−1.6 V versus reversible hydrogen electrode, RHE). Excellent CO2RR performance can still be achieved under the low‐concentration CO2 feeding (e.g., 20 vol.%). Besides, an extremely low onset potential of −0.05 VRHE (close to the theoretical thermodynamic potential of −0.02 VRHE) was detected by in situ ultraviolet‐visible (UV‐Vis) measurements, together with stable operation over 50 h with preserved FEformate of ≈95 % and high partial current density of 326.2 mA cm−2 at −1.0 VRHE.
Catalyst‐Controlled Divergent Generations and Transformations of α‐Carbonyl Cations from Alkynes**
Authors: Zhou Junrui , Wang Weilin , Zuo Fenfang , Liu Shupeng , Mosim Amin Pathan , Zhong Kangbao , Bai Ruopeng , Wang Youliang
Published: October 2023

α‐Carbonyl cations are the umpolung forms of the synthetically fundamental α‐carbonyl carbanions. They are highly reactive yet rarely studied and utilized species and their precursors were rather limited. Herein, we report the catalyst‐controlled divergent generations of α‐carbonyl cations from single alkyne functionalities and the interception of them via Wagner–Meerwein rearrangement. Two chemodivergent catalytic systems have been established, leading to two different types of α‐carbonyl cations and, eventually, two different types of products, i.e. the α,β‐ and β,γ‐unsaturated carbonyl compounds. Broad spectrum of alkynes including aryl alkyne, ynamide, alkynyl ether, and alkynyl sulfide could be utilized and the migration priorities of different groups in the Wagner–Meerwein rearrangement step was elucidated. Density functional theory calculations further supported the intermediacy of α‐carbonyl cations via the N−O bond cleavage in both the two catalytic systems. Another key feature of this methodology was the fragmentation of synthetically inert tert‐butyl groups into readily transformable olefin functionalities. The synthetic potential was highlighted by the scale‐up reactions and the downstream diversifications including the formal synthesis of nicotlactone B and galbacin.
Low‐Temperature Hydrogenation of CO2 to Methanol in Water on ZnO‐Supported CuAu Nanoalloys
Authors: Mosrati Jawaher , Ishida Tamao , Mac Hung , Al‐Yusufi Mohammed , Honma Tetsuo , Parliniska‐Wojtan Magdalena , Kobayashi Yasuhiro , Klyushin Alexander , Murayama Toru , Abdel‐Mageed Ali M.
Published: October 2023

Optimizing processes and materials for the valorization of CO2 to hydrogen carriers or platform chemicals is a key step for mitigating global warming and for the sustainable use of renewables. We report here on the hydrogenation of CO2 in water on ZnO‐supported CuAu nanoalloys, based on ≤7 mol % Au. CuxAuy/ZnO catalysts were characterized using 197Au Mössbauer, in situ X‐ray absorption (Au LIII‐ and Cu K‐edges), and ambient pressure X‐ray photoelectron (APXP) spectroscopic methods together with X‐ray diffraction and high‐resolution electron microscopy. At 200 °C, the conversion of CO2 showed a significant increase by 34 times (from 0.1 to 3.4 %) upon increasing Cu93Au7 loading from 1 to 10 wt %, while maintaining methanol selectivity at 100 %. Limited CO selectivity (4–6 %) was observed upon increasing temperature up to 240 °C but associated with a ≈3‐fold increase in CO2 conversion. Based on APXPS during CO2 hydrogenation in an H2O‐rich mixture, Cu segregates preferentially to the surface in a mainly metallic state, while slightly charged Au submerges deeper into the subsurface region. These results and detailed structural analyses are topics of the present contribution.
Metal‐Free Photocatalytic CO2 Reduction to CH4 and H2O2 under Non‐sacrificial Ambient Conditions
Authors: Zou Weixin , Cheng Yingyi , Ye Yu‐Xin , Wei Xiaoqian , Tong Qing , Dong Lin , Ouyang Gangfeng
Published: October 2023

Photocatalytic CO2 reduction to CH4 requires photosensitizers and sacrificial agents to provide sufficient electrons and protons through metal‐based photocatalysts, and the separation of CH4 from by‐product O2 has poor applications. Herein, we successfully synthesize a metal‐free photocatalyst of a novel electron‐acceptor 4,5,9,10‐pyrenetetrone (PT), to our best knowledge, this is the first time that metal‐free catalyst achieves non‐sacrificial photocatalytic CO2 to CH4 and easily separable H2O2. This photocatalyst offers CH4 product of 10.6 μmol ⋅ g−1 ⋅ h−1 under non‐sacrificial ambient conditions (room temperature, and only water), which is two orders of magnitude higher than that of the reported metal‐free photocatalysts. Comprehensive in situ characterizations and calculations reveal a multi‐step reaction mechanism, in which the long‐lived oxygen‐centered radical in the excited PT provides as a site for CO2 activation, resulting in a stabilized cyclic carbonate intermediate with a lower formation energy. This key intermediate is thermodynamically crucial for the subsequent reduction to CH4 product with the electronic selectivity of up to 90 %. The work provides fresh insights on the economic viability of photocatalytic CO2 reduction to easily separable CH4 in non‐sacrificial and metal‐free conditions.
Understanding the chemistry of graphene oxide on redox flow lithium‐ion batteries with a view to enhancing the battery's high‐density storage
Authors: Onoh Edwin U. , Nwanya Asumpta C. , Shinde Nanasaheb M. , Nwulu Nnamdi , Ezema Fabian I.
Published: October 2023

The use of graphene oxide (GO) has shown potential in improving the performance of redox flow lithium‐ion batteries (RFLIBs). These types of batteries use a liquid electrolyte containing redox‐active species to store and release energy. Despite being scalable, RFLIBs face limitations, namely, low energy density of the electrolyte and reduced cycling stability of the electrodes. However, GO's unique properties, such as its high conductivity as well as large surface area, create an attractive option for enhancing the electrochemical properties of both the electrolyte and electrodes in RFLIBs. When used as an electrode, GO improves the kinetic reversibility reactions, leading to increased electrochemical activity towards redox couples. Charge transfer resistances of positive and negative reactions are reduced, leading to increased voltage energy and efficiency of lithium batteries in terms of energy usage. As redox flow batteries made of lithium ions are an established subsystem and a growing research and development field, there is potential to enhance their performance and reduce costs through the use of GO. The objective of this review is to provide an overview of the chemistry of GO as it pertains to RFLIBs use, covering topics such as its surface chemistry, functionalization, and interactions with redox‐active species, as well as its potential for enhancing high‐density storage of electricity in batteries. Specifically, it will discuss the impact of GO on redox reactions in the electrolyte, including its ability to raise the redox‐active species concentration as well as enhance their stability. The review will also examine how GO impacts the electrodes, including its potential to increase their surface area and conductivity and promote cycling stability. Additionally, the review will address the importance of optimizing the quantity and distribution of GO in both the electrolyte and electrodes of RFLIBs.
In vitro antiviral activity of favipiravir and its 6‐ and 3‐O‐substituted derivatives against coronavirus: Acetylation leads to improvement of antiviral activity
Authors: Elizalde Valeria , Mirazo Santiago , Romero Angel H. , Alvarez Guzman
Published: October 2023

Favipiravir is currently approved for the treatment of the influenza virus and has shown encouraging results in terms of antiviral capacity in clinical studies against severe acute respiratory syndrome coronavirus 2. Favipiravir is a prodrug, where its favipiravir‐ribofuranosyl‐5B‐triphosphate metabolite is capable of blocking RNA replication of the virus. However, the antiviral efficiency of favipiravir is limited by two factors: (i) low accumulation in plasma and rapid excretion/elimination post‐administration and (ii) low conversion rate into the active metabolite. To tackle these problems, herein, we have designed new favipiravir analogues focusing on the replacement of the fluorine atom at the 6‐position by halogen or hydrogen atoms and 3‐O‐functionalization with labile groups. The first type of functionalization seeks to increase the antiviral activity because of the better ability of the keto‐tautomer as a function of the halogen, and it is hypothesized that the keto‐tautomer tends to promote the formation of the ribofuranosyl‐5B‐triphosphate (RTP) metabolite. Meanwhile, the second type of functionalization seeks to promote lipophilicity and increase accumulation in cells. From the in vitro antiviral activity against two coronavirus models (bovine and human 229E), it was identified that the replacement did not improve the antiviral activity against both the models, which seems to be attributable to the low water solubility of these new 6‐functionalized analogues. Meanwhile, with 3‐O‐functionalization, acetylation provided the most active compounds with higher half‐maximal inhibitory concentration and selectivity than favipiravir, whereas benzylation/methanosulfonation yielded the least active compounds. In summary, acetylation is found to be a convenient functionalization to enhance the antiviral profile of favipiravir.
EÜ Norderelbe – Zustandserfassung, Bewertung und Verstärkung ausgewählter Bauteile
Authors: Krontal Ludolf , Müller Lukas , Niebuhr Peter Lothar , Pitters Sarah , Finke Stefan , Lang Theodor
Published: October 2023

Der Zustand der etwa 100 Jahre alten Eisenbahnüberführung (EÜ) Norderelbe in Hamburg und die Trag‐ und Ermüdungssicherheit des Bauwerks wurden mithilfe verschiedener zerstörungsfreier Prüf‐ und Erfassungsmethoden, umfänglicher Bauwerksmessungen und messgestützter Bauwerksnachrechnungen erfasst und bewertet. Dabei wurden vereinzelte Defizite vorgefunden, die im Rahmen einer kurzfristig umgesetzten Verstärkungsmaßnahme behoben wurden. Von der Bestandsaufnahme über Bauwerksmessungen, Instandsetzung und weiterführendes Bauwerksmonitoring werden die einzelnen Schritte zur Sicherstellung des sicheren Betriebs bis zur Fertigstellung des Ersatzneubaus beschrieben. Es werden Erkenntnisse zum Systemverhalten der Stabbogenbrücke vorgestellt, die aus der umfangreichen messtechnischen Untersuchung gewonnen werden konnten.
Über die Widerstandspolarisation I. Ihre experimentelle Abtrennungsmöglichkeit von anderen Polarisationsarten
Authors: Falk Georg , Lange Erich
Published: October 2023

Die Widerstandspolarisation an einer mit AgJ bedeckten Ag‐Elektrode kann auf Grund der theoretisch abschätzbaren verschiedenen Einstellgeschwindigkeiten der einzelnen Polarisationsarten von den anderen Grundpolarisationsarten abgetrennt werden. Die mit einem Kathodenstrahloscillograph durchgeführten Gleichstrommessungen sowie die Untersuchung in der Wechselstrombrücke ergaben, daß an der betreffenden Elektrode unterhalb 1/100000 Sek. praktisch reine Widerstandspolarisation auftritt, während die sich anschließend langsamer ausbildende Polarisation zum Teil als Konzentrationspolarisation gedeutet werden kann.
Über die magnetische Suszeptibilität von Sauerstoff, der an Kohle, Kieselsäure und Platinmohr bei – 183°C sorbiert ist
Authors: Juza Robert , Grasenick Fritz
Published: October 2023

Es wird festgestellt, daß die magnetische Suszeptibilität von Sauerstoff, der bei – 183°C an Aktivkohle, aktiver Kieselsäure und Platinmohr sorbiert ist, von der Belegungsdichte abhängig ist. Dieser Suszeptibilitätswechsel wird mit einer Verschiebung des Gleichgewichtes 2 O2 ⇄ O4 in Zusammenhang gebracht.

An der Aktivkohle, für die nach der tensimetrischen Untersuchung im wesentlichen nur eine einmolekulare Belegung anzunehmen ist, wird der Sauerstoff zunächst mit der Suszeptibilität des O2‐Molekels gebunden, die partiellen Suszeptibilitäten sinken sodann über die des flüssigen Sauerstoffs zu noch niedrigeren Werten. Der integrale Suszeptibilitätswert nach Sättigung der Kohle stimmt mit der Suszeptibilität des flüssigen Sauerstoffs überein.

An Kieselsäure werden die ersten Sauerstoffmengen mit der Suszeptibilität des O2‐Sauerstoffs gebunden. Die Hauptmenge des Sauerstoffs, in dem Gebiet der mehrmolekularen Belegung, wird mit der Suszeptibilität des flüssigen Sauerstoffs gebunden. Diese beiden Sauerstoffsorten scheinen an der mit Sauerstoff gesättigten Kieselsäure unabhängig voneinander vorzuliegen.

An Platinmohr werden bei kleinen Konzentrationen in dem Gebiet der einmolekularen Sorption nach dem magnetischen Befund isolierte O2‐Moleküle gebunden. In der Nähe der Sättigungskonzentration ist das Präparat von großen Mengen flüssigen Sauerstoffs, dessen Tension etwas erniedrigt ist, umgeben. Die isolierte Lagerung der ersten O2‐Moleküle ist anscheinend verlorengegangen.
Kristallisation in synthetischen linearen Hochpolymeren 7. Mitteilung über Polyurethane
Authors: Brenschede W.
Published: October 2023

Synthetische lineare Hochpolymere lassen sich durch schnelles Abkühlen aus dem Schmelzfluß in einen glasartigen Zustand überführen, aus dem heraus durch Tempern fortschreitende Kristallisation erfolgen kann. Beobachtungen des Röntgendiagrammes, der Dichte und insbesondere der Doppelbrechung beim Tempern unterkühlen Polyurethans führen zu näheren Vorstellungen über die Zunahme kristalliner Ordnung in Hochpolymeren. Danach geht dieser Vorgang nicht so vor sich, daß starr verankerte Keime in eine amorphe Umgebung hineinwachsen, sondern es erfolgt gruppenweise ein spontaner Zusammenschluß benachbarter vorgeordneter Bereiche unter Hineindrehen in eine gemeinsame Richtung.
Über den Chemismus der organischen Katalysen
Authors: Langenbeck Wolfgang
Published: October 2023

Die Erscheinung der Katalyse ist sehr vielseitig. Stoffe aus fast allen Verbindungsklassen können als Katalysatoren wirken oder als Zwischenstoffe auftreten. Auf dem Gebiet der organischen Katalysatoren spielen die Kovalenzkatalysatoren und organische Schwermetallkomplexe die wichtigste Rolle. Kovalenzverbindungen sind als Zwischenstoffe thermodynamisch durchaus möglich, und es wird an einigen Beispielen gezeigt, wie man sie hat nachweisen und isolieren können. Die Wirkung organischer Eisenkomplexe beruht auf Wertigkeitswechsel des zentralen Eisenions, daneben spielen Kettenreaktionen eine Rolle. Aktive und aktivierende Gruppen. Übertragung der Aktivierung in aromatischen Systemen. Analoger Mechanismus bei den natürlichen Fermenten. Kofermente als Kovalenzkatalysatoren. Übertragung der Aktivierung in den Apoferment‐Molekeln.
Untersuchung der Assoziationsstruktur in schwerem Wasser und n‐Propanol mit Hilfe thermisch‐kalorischer Eigenschaften, insbesondere Messungen der spezifischen Wärmen
Authors: Eucken A. , Eigen M.
Published: October 2023

Es werden Entwicklung und Meßmethode eines adiabatisch arbeitenden Flüssigkeitskalorimeters beschrieben, mit dem zunächst Messungen der spezifischen Wärme Cp des flüssigen schweren Wassers im Temperaturgebiet zwischen 20 und 130° C durchgeführt wurden. Eine sorgfältige Fehlerabschätzung liefert einen Fehler von etwa 1,5 Promille in den Absolutwerten der spezifischen Wärme (Relativgenauigkeit gegenüber spezifischer Wärme des H2O 0,5 Promille).

Unter Zuhilfenahme weiterer experimenteller thermischer Daten des D2O1)2)3) werden der Ausdehnungskoeffizient, die isotherme Kompressibilität und die Molwärme Cv (Differenz Cp – Cv) berechnet. Die erhaltenen Ergebnisse werden einer eingehenden Diskussion – besonders hinsichtlich der Unterschiede zum leichten Wasser – unterworfen. Sie liefern eine quantitative Bestätigung der in früheren Arbeiten4)5)6)7) für die Konstitution des Wassers entwickelten Grundvorstellungen.

Anschließend werden die grundsätzlich verschiedenen Assoziationsverhältnisse in Alkoholen am Beispiel des n‐Propanols experimentell untersucht. Hierzu wurden Messungen der spezifischen Wärme Cp (zwischen 25 und 130°C) und der Schallgeschwindigkeit (zwischen 20 und 90° C) vorgenommen. Mit Hilfe dieser Daten und der aus Dichtemessungen8) berechneten Ausdehnungskoeffizienten wird die Molwärme Cv und daraus der Assoziationsanteil (CA) ermittelt, der sich in guter Übereinstimmung mit dem bereits auf theoretischem Wege erhaltenen Ergebnis befinde.
Spektroskopische Konstitutionsbestimmungen aus ultraroten Intensitätsmessungen an CH‐Schwingungsbanden
Authors: Lippert E. , Mecke R.
Published: October 2023

Zur Auswertung umfangreichen spektroskopischen Meßmaterials werden Übersichtsdiagramme vorgeschlagen, in denen jede Bande eines betrachteten Bandentyps nach Frequenzlage und Absorptionsstärke eingetragen wird. Solche Diagramme werden für den 2. und 3. Oberton der CH‐Valenz‐Schwingung nach eigenen und fremden Messungen aufgestellt. Aus den Diagrammen werden Gesetzmäßigkeiten über den Einfluß der Konstitution auf CH‐Banden gefolgert und Anwendungsmöglichkeiten für Konstitutionsbestimmungen aufgezeigt. Einige Spezialfälle von allgemeiner Bedeutung werden diskutiert.
Berücksichtigung des Eigenvolumens gelöster Ionen in der Ionenwolke in der Theorie der Verdünnungswärme von Elektrolytlösungen
Authors: Lange E. , Möhring K.
Published: October 2023

Herrn Professor Dr. Paul Günther, dem verdienstvollen Herausgeber der Zeitschrift für Elektrochemie, zu seinem 60. Geburtstag am 6. Dezember 1952 zugeeignet

Es wird untersucht, welche Auswirkungen die Mitberücksichtigung des Eigenvolumens gelöster Ionen nicht nur in Form einer gewissen Mindestentfernung, sondern auch einer Maximalzahl (Sättigung) im Raum um ein Zentralion auf die integrale Verdünnungswärme vollständig dissoziierter Elektrolyte hat. Es zeigt sich, daß für einen 1–1‐wertigen Elektrolyten erst in etwa oberhalb 0,1molaren Lösungen ein merklicher Effekt zu erwarten ist.
Zwischenmolekulare Kräfte und Ramaneffekt bei Mischungen des Acetons mit unpolaren Lösungsmitteln. I. Die Änderung der CO‐Valenzschwingung von Aceton mit wachsender Verdünnung
Authors: Wolff Hans
Published: October 2023

Die Untersuchungen von Goubeau und Heerdt über die Änderung der CO‐Valenzschwingung von Aceton bei wachsender Verdünnung mit unpolaren Lösungsmitteln werden durch Ermittlung reproduzierbarer Werte, Ausdehnung der Messungen zu niedrigeren Konzentrationen und Vermehrung der untersuchten Lösungsmittel ergänzt. Die Ansätze zur Deutung der experimentellen Befunde werden erweitert.