bluuebunny/crossref_metadata_2025 huggingface dataset:
In vitro antimicrobial and cytotoxic activity of Neem and Kirata herbal formulation mediated Silver nanoparticles
Authors:   Department of Orthodontics and Dentofacial Orthopaedics, Saveetha Dental College and Hospitals, Saveetha Institute of Medical and Technical sciences(SIMATS), Saveetha University, Chennai – 77, Rebekah R
Published: January 2023

Silver nanoparticles (AgNPs) gain great interest among noble metal nanoparticles due to their broad applications in medicine, dentistry, drug delivery, tissue and tumour imaging, biolabeling, and biosensing. The antibacterial, antifungal, antiviral, and antiparasitic activity of AgNPs is well documented in the literature. This study aimed to determine the antimicrobial and cytotoxic activity of Neem and Kirata herbal formulation-mediated silver nanoparticles against oral biofilm. The green synthesis of Neem and Kirata herbal formulation-mediated silver nanoparticles was done. The antimicrobial action against the strains of Candida albicans, Staphylococcus aureus, Enterococcus faecalis, and Streptococcus mutans were assessed. The results showed that the newly formulated nanoparticle had effective anti-microbial properties and decreased cytotoxic properties which make it advantageous for clinical applications and treatment modalities. It showed great potential for the nanoparticle in decreasing the bacterial effects and cytotoxic nature thereby providing future scope for clinical application in preventing oral biofilm formation and its deleterious effects.
Paradoxical cutaneous manifestations induced by TNF inhibitors in patients with inflammatory bowel disease
Authors:   Department of Hepato-Gastroenterology “Medicine C”, Ibn Sina University Hospital Center, Mohammed V University Rabat, Morocc, Alaou Rhita , Alami Sofia , Lagdali Nawal , Kadiri Maryeme , Berhili Camélia , Chabib Fatima-Zahra , Borahma Mohamed , Benelbarhdadi Imane , Ajana Fatima-Zahra ,   Department of Dermatology, Ibn Sina University Hospital Center, Mohammed V University Rabat, Morocco
Published: January 2023

Background: Anti-TNF drugs have revolutionized the management of numerous inflammatory diseases, yet they may produce paradoxical effects. Materials and Methods: A descriptive study was conducted on patients with chronic inflammatory bowel disease (IBD) on anti-TNF therapy who had developed paradoxical psoriasis. Results: Out of a total of 218 patients followed for IBD on TNF inhibitors, five presented with paradoxical psoriasis. In four patients, a specific treatment for psoriasis was associated with anti-TNF treatment. In one patient, a swap to ustekinumab was decided. Good progress was noted in four patients. In one, there was no improvement of the psoriasis on methotrexate, which was switched to another anti-TNF agent. Conclusion: In our experience, TNF inhibitor-induced psoriasis is relatively rare (prevalence of 2.3%). The choice of treatment is reached by assessing the benefit-risk balance. Key words: Paradoxical cutaneous manifestations; TNF inhibitors; Cutaneous manifestations; Inflammatory bowel disease
Carbamazepine-induced pellagra: Dermoscopic findings and response to oral nicotinamide
Authors:   Department of Dermatology, Venereology and Leprosy, Government Medical College, Srinagar, University of Kashmir, Jammu and Kashmir, India, Rather Shagufta , Reyaz Saika , Shah Aaqib Aslam , Nazim Malik
Published: January 2023

ABSTRACT Pellagra is a nutritional disorder characterized clinically by the four Ds: dermatitis, diarrhea, dementia, and severe systemic photosensitivity manifesting as death. The disorder results from a deficiency of niacin or its precursor tryptophan and is mainly associated with compromised dietary intake of niacin and tryptophan or excessive intake of leucine (a natural antagonist). Other causes include chronic alcohol intake, malabsorption, metabolic disorders, and the administration of certain medications. Herein, we report the clinical and dermoscopic findings in a twenty-year-old male with seizure disorder presenting with carbamazepine-induced pellagrous dermatitis that resolved after the administration of niacin. Key words: Pellagra; Photosensitivity; Carbamazepine; Dermoscopy; Niacin
Bardet–Biedl syndrome: Case report from a tertiary-care hospital in Srinagar, India
Authors:   Department of Dermatology, Venereology &, Reyaz Saika ,   amp,   amp,   amp,   Leprosy, Government Medical College Srinagar, Karan Nagar, Jammu and Kashmir, India, Rehman Fozia , Rather Shagufta , Sultan Sheikh Javeed
Published: January 2023

Bardet–Biedl syndrome (BBS) is a rare autosomal recessive ciliopathic disorder affecting multiple organ systems. The main clinical features are marked central obesity, retinal dystrophy, polydactyly, mental retardation, hypogonadism, and renal dysfunction. It affects both males and females. Herein, we report an interesting case of BBS with features of the BBS yet without cone-rod dystrophy, which is considered one of the hallmark features of this condition. To the best of our knowledge, this is the first report of Bardet–Biedl syndrome with the absence of cone-rod dystrophy and a normal fundus examination on the Indian subcontinent. Key words: Bardet–Biedl syndrome; Ciliopathic disorder; Polydactyly
Anterior cervical hypertrichosis: A rare location
Authors:   Department of Dermatology University hospital center of Tangier, Tetouan, Al Hoceima, Morroco, Chahoub Hanane , Al Faker Ibtissam , Marraha Farah , Rahmani Najlaa , Benyamna Younes , Gallouj Salim ,   Faculty of Medicine and Pharmacy Tangier, Abdelmalek Essaadi University, Tangier, Morocco
Published: January 2023

We report the case of a twelve-year-old male who presented with isolated anterior cervical hypertrichosis persistent since birth. No notion of trauma or local inflammation or the use of a topical treatment was noted. The patient had no other clinical symptoms and no similar family history. A clinical examination found a tuft of hair, approx. 6 × 3 cm in size, at the level of the mid-neck region, consisting of fine, brown hairs, 3 cm in length (Fig. 1a), with a dermoscopic appearance showing terminal hair and fluffy hair without other associated signs. (Fig. 1b). The rest of the somatic examination was unremarkable. A laser hair removal treatment was offered to the patient with a good response.
Pruritic papular eruption revealing HIV
Authors:   Department of Dermatology, University Hospital Hassan II, Fes, Morocco, 2Hassan Center of Pathology, Rabat, Morocco, Jroundi Chaymae , Baybay Hanane , El Bennaye Hajar , Couissi Imane , Douhi Zakia , Elloudi Sara , Mernissi Fatima Zahr , Rimani Mouna
Published: January 2023

Pruritic papular eruption (PPE) described in HIV is a skin disease often encountered in HIV-positive patients. It is most often a sign of severe immunodeficiency and is commonly reported in African, Southeast Asian, and Indian populations [1,2]. It affects both adult females and males and may also be seen in children. The elementary lesion is a discrete, firm, erythematous, urticarial, very itchy papule of the extremities, face, and trunk, sparing the palms and soles. Painful excoriations in the genital mucosa are sometimes described. The CD4+ lymphocyte count (CD4) is usually below 250 cells/mm3. Histopathology reveals a lymphohistiocytic, inflammatory, perivascular, and periannexal infiltrate with a variable number of eosinophils. According to the World Health Organization (WHO), it is recommended to all HIV patients with antiretroviral therapy (ART), regardless of the staging and the CD4 count [3]. However, an elective treatment for PPE has not yet been found. Regression has been noted in some cases after the initiation of antiretroviral therapy. UVB therapy seems to be the most successful method in cases not improving with antiretroviral therapy [4]. Herein, we report the case of a patient who presented with PPE revealing HIV.
A case of delayed diagnosis of Dowling Degos disease
Authors: Topal Servet , Topal İlteriş Oğuz , Bilgi Hülya
Published: January 2023

Dowling–Degos disease (DDD) is a rare genodermatosis characterized by acquired reticular hyperpigmentation of flexural sites, comedo-like lesions, and pitted facial scars. The classic disease is inherited by the autosomal dominant pattern. Herein, we present here the case of a fifty-year-old female diagnosed with Dowling–Degos disease.
Dermatological manifestations during HIV infection in children in Dakar, Senegal
Authors: Diatta Boubacar Ahy , Pie Nibirantije , Diop Khadim , Diatta Robert , Sarr Mamadou , Mendy Patrice , Diadie Saer , Ndiaye Maodo , Ndour Niar , Ndiaye Coumba , Diop Assane , Diallo Moussa , Niang Suzanne Oumou
Published: January 2023

Background: Dermatological manifestations are frequent and often constitute a circumstance of HIV discovery in 70% of cases [1]. They are observed in 83% of patients with AIDS and at an early stage in 75% [2,3,4,5]. The objective of this study was to describe the epidemiological, clinical, therapeutic, and evolutionary aspects of skin manifestations during HIV infection in children. Materials and Methods: We conducted a cross-sectional, multicentric, descriptive study over a period of ten years in two dermatology departments and one pediatric department in Dakar, Senegal. We included all HIV-seropositive children aged 0–15 years with mucosal cutaneous manifestations. A dermatologist and a specialist in the medical care of HIV performed the diagnosis of cutaneous manifestations. Data entry and analysis were performed with the SPSS software, version 9.05. Results: We collected 206 cases of cutaneous manifestations in 454 children followed for HIV infection. The hospital frequency was 45.3%. The children were male in 115 cases (55.83%) and female in 91 cases (44.17%), giving a sex ratio of 1.26. The mean age of the patients was sixty months, with extremes of one month to fourteen years. A mycotic dermatosis origin was noted in 47.37%, ringworm in 22.37%, dermatophytosis in 8.58%, oral candidiasis in 6.58%, seborrheic dermatitis in 6.58%, and perleche in 3.29%. Bacterial skin diseases were represented by furunculosis in 1.97%, and impetigo in 7.24%. Viral dermatoses included molluscum contagiosum in 10.53%, shingles in 9.21%, warts in 9.87%, and chickenpox in 3.95%. As for parasitic dermatoses, scabies was noted in 8.55, followed by larva migrans in 0.66% and cutaneous leishmaniosis in 0.66%. Immuno-allergic dermatoses accounted for 25% and included prurigo in 94.3%, atopic dermatitis in 1.90%, and fixed pigmented erythema in 1.90%. Conclusion: Cutaneous manifestations are a common discovery during HIV infection in children. They are marked by a predominance of infectious dermatoses in sub-Saharan Africa. Key words: skin diseases; HIV; children; Dakar
Director's Play as a Means of Mastering Dialogue by Older Preschoolers
Authors: Gusarenko Viktoriya Vladimirovna , Zonova Anastasiya Aleksandrovna , Krol' Elizaveta Robertovna , Gurova Nina Nikolaevna , Zimnitskaya Natal'ya Slavovna , Dogadaev Oleg Nikolaevich
Published: January 2023

The subject of the study is the use of the possibilities of the director's game for the development of dialogic speech in older preschool children. The study was conducted on the basis of a preschool group at MBOU No. 12 in Minusinsk, Krasnoyarsk Krai (Russia). The study involved 40 preschoolers. The age of preschoolers is 5 – 6 years. The relevance of the study is determined by the need of preschool pedagogy to use the possibilities of the game, including director's, as a means of mastering dialogue and dialogic speech of older preschool children. We conducted a study consisting of a ascertaining, formative and control experiment. The director's game "We are going to a birthday party" was developed. After analyzing the results of the study, its ascertaining stage, we came to the conclusion that children mainly have a low and average level of ability to maintain a dialogue. They found it difficult to answer questions, often thought about the teacher's questions, asked again, gave monosyllabic answers, did not know how to comment on their statements, could not defend their position in the dialogue. The children experienced embarrassment and tightness when making contact. The answers to the questions were monosyllabic, the replicas carried little information, important details were omitted. We suggested that the director's play can have an impact on the development of dialogue in children. She teaches children to conduct a dialogue correctly, develops the ability to maintain a dialogue, dialogical relations. During the control stage, the hypothesis of the study was confirmed. In the group of preschoolers where the director's game was used, the level of mastering dialogic speech became higher compared to the group where the director's game was not used.
Recombinant single-cycle influenza virus with exchangeable pseudotypes allows repeated immunization to augment anti-tumour immunity with immune checkpoint inhibitors
Authors: Kandasamy Matheswaran , Gileadi Uzi , Rijal Pramila , Tan Tiong Kit , Lee Lian N , Chen Jili , Prota Gennaro , Klenerman Paul , Townsend Alain , Cerundolo Vincenzo
Published: January 2023

Virus-based tumour vaccines offer many advantages compared to other antigen-delivering systems. They generate concerted innate and adaptive immune response, and robust CD8+ T cell responses. We engineered a non-replicating pseudotyped influenza virus (S-FLU) to deliver the well-known cancer testis antigen, NY-ESO-1 (NY-ESO-1 S-FLU). Intranasal or intramuscular immunization of NY-ESO-1 S-FLU virus in mice elicited a strong NY-ESO-1-specific CD8+ T cell response in lungs and spleen that resulted in the regression of NY-ESO-1-expressing lung tumour and subcutaneous tumour, respectively. Combined administration with anti-PD-1 antibody, NY-ESO-1 S-FLU virus augmented the tumour protection by reducing the tumour metastasis. We propose that the antigen delivery through S-FLU is highly efficient in inducing antigen-specific CD8+ T cell response and protection against tumour development in combination with PD-1 blockade.
Balancing selection on genomic deletion polymorphisms in humans
Authors: Aqil Alber , Speidel Leo , Pavlidis Pavlos , Gokcumen Omer
Published: January 2023

A key question in biology is why genomic variation persists in a population for extended periods. Recent studies have identified examples of genomic deletions that have remained polymorphic in the human lineage for hundreds of millennia, ostensibly owing to balancing selection. Nevertheless, genome-wide investigation of ancient and possibly adaptive deletions remains an imperative exercise. Here, we demonstrate an excess of polymorphisms in present-day humans that predate the modern human-Neanderthal split (ancient polymorphisms), which cannot be explained solely by selectively neutral scenarios. We analyze the adaptive mechanisms that underlie this excess in deletion polymorphisms. Using a previously published measure of balancing selection, we show that this excess of ancient deletions is largely owing to balancing selection. Based on the absence of signatures of overdominance, we conclude that it is a rare mode of balancing selection among ancient deletions. Instead, more complex scenarios involving spatially and temporally variable selective pressures are likely more common mechanisms. Our results suggest that balancing selection resulted in ancient deletions harboring disproportionately more exonic variants with GWAS (genome-wide association studies) associations. We further found that ancient deletions are significantly enriched for traits related to metabolism and immunity. As a by-product of our analysis, we show that deletions are, on average, more deleterious than single nucleotide variants. We can now argue that not only is a vast majority of common variants shared among human populations, but a considerable portion of biologically relevant variants has been segregating among our ancestors for hundreds of thousands, if not millions, of years.
Adaptation to glucose starvation is associated with molecular reorganization of the circadian clock in Neurospora crassa
Authors: Szőke Anita , Sárkány Orsolya , Schermann Géza , Kapuy Orsolya , Diernfellner Axel CR , Brunner Michael , Gyöngyösi Norbert , Káldi Krisztina
Published: January 2023

The circadian clock governs rhythmic cellular functions by driving the expression of a substantial fraction of the genome and thereby significantly contributes to the adaptation to changing environmental conditions. Using the circadian model organism Neurospora crassa, we show that molecular timekeeping is robust even under severe limitation of carbon sources, however, stoichiometry, phosphorylation and subcellular distribution of the key clock components display drastic alterations. Protein kinase A, protein phosphatase 2 A and glycogen synthase kinase are involved in the molecular reorganization of the clock. RNA-seq analysis reveals that the transcriptomic response of metabolism to starvation is highly dependent on the positive clock component WC-1. Moreover, our molecular and phenotypic data indicate that a functional clock facilitates recovery from starvation. We suggest that the molecular clock is a flexible network that allows the organism to maintain rhythmic physiology and preserve fitness even under long-term nutritional stress.
Hierarchical sequence-affinity landscapes shape the evolution of breadth in an anti-influenza receptor binding site antibody
Authors: Phillips Angela M , Maurer Daniel P , Brooks Caelan , Dupic Thomas , Schmidt Aaron G , Desai Michael M
Published: January 2023

Broadly neutralizing antibodies (bnAbs) that neutralize diverse variants of a particular virus are of considerable therapeutic interest. Recent advances have enabled us to isolate and engineer these antibodies as therapeutics, but eliciting them through vaccination remains challenging, in part due to our limited understanding of how antibodies evolve breadth. Here, we analyze the landscape by which an anti-influenza receptor binding site (RBS) bnAb, CH65, evolved broad affinity to diverse H1 influenza strains. We do this by generating an antibody library of all possible evolutionary intermediates between the unmutated common ancestor (UCA) and the affinity-matured CH65 antibody and measure the affinity of each intermediate to three distinct H1 antigens. We find that affinity to each antigen requires a specific set of mutations – distributed across the variable light and heavy chains – that interact non-additively (i.e., epistatically). These sets of mutations form a hierarchical pattern across the antigens, with increasingly divergent antigens requiring additional epistatic mutations beyond those required to bind less divergent antigens. We investigate the underlying biochemical and structural basis for these hierarchical sets of epistatic mutations and find that epistasis between heavy chain mutations and a mutation in the light chain at the VH-VL interface is essential for binding a divergent H1. Collectively, this is the first work to comprehensively characterize epistasis between heavy and light chain mutations and shows that such interactions are both strong and widespread. Together with our previous study analyzing a different class of anti-influenza antibodies, our results implicate epistasis as a general feature of antibody sequence-affinity landscapes that can potentiate and constrain the evolution of breadth.
A data integration framework for spatial interpolation of temperature observations using climate model data
Authors: Economou Theo , Lazoglou Georgia , Tzyrkalli Anna , Constantinidou Katiana , Lelieveld Jos
Published: January 2023

Meteorological station measurements are an important source of information for understanding the weather and its association with risk, and are vital in quantifying climate change. However, such data tend to lack spatial coverage and are often plagued with flaws such as erroneous outliers and missing values. Alternative meteorological data exist in the form of climate model output that have better spatial coverage, at the expense of bias. We propose a probabilistic framework to integrate temperature measurements with climate model (reanalysis) data, in a way that allows for biases and erroneous outliers, while enabling prediction at any spatial resolution. The approach is Bayesian which facilitates uncertainty quantification and simulation based inference, as illustrated by application to two countries from the Middle East and North Africa region, an important climate change hotspot. We demonstrate the use of the model in: identifying outliers, imputing missing values, non-linear bias correction, downscaling and aggregation to any given spatial configuration.
Comprehensive analysis of fatty acid metabolism-related gene signatures for predicting prognosis in patients with prostate cancer
Authors: Wang Hongbo , Liu Zhendong , Wang Yubo , Han Dali , Du Yuelin , Zhang Bin , He Yang , Liu Junyao , Xiong Wei , Zhang Xingxing , Gao Yanzheng , Shang Panfeng
Published: January 2023

Fatty acid metabolism (FAM) is an important factor in tumorigenesis and development. However, whether fatty acid metabolism (FAM)-related genes are associated with prostate cancer (PCa) prognosis is not known. Therefore, we established a novel prognostic model based on FAM-related genes to predict biochemical recurrence in PCa patients. First, PCa sequencing data were acquired from TCGA as the training cohort and GSE21032 as the validation cohort. Second, a prostate cancer prognostic model containing 10 FAM-related genes was constructed using univariate Cox and LASSO. Principal component analysis and t-distributed stochastic neighbour embedding analysis showed that the model was highly effective. Third, PCa patients were divided into high- and low-risk groups according to the model risk score. Survival analysis, ROC curve analysis, and independent prognostic analysis showed that the high-risk group had short recurrence-free survival (RFS), and the risk score was an independent diagnostic factor with diagnostic value in PCa patients. External validation using GSE21032 also showed that the prognostic model had high reliability. A nomogram based on a prognostic model was constructed for clinical use. Fourth, tumor immune correlation analyses, such as the ESTIMATE, CIBERSORT algorithm, and ssGSEA, showed that the high-risk group had higher immune cell infiltration, lower tumour purity, and worse RFS. Various immune checkpoints were expressed at higher levels in high-risk patients. In summary, this prognostic model is a promising prognostic biomarker for PCa that should improve the prognosis of PCa patients. These data provide new ideas for antitumour immunotherapy and have good potential value for the development of targeted drugs.
Growth and Yield of Stevia (Stevia rebaudiana Bertoni) as Influenced by Plant Density and Pinching
Authors: Junaidath P. , Sindhu P. V. , Prameela P. , Beena C. , Menon Syama S.
Published: January 2023

A field experiment was carried out to standardize spacing and pinching time to enhance the yield and quality of stevia (Stevia rebaudiana Bertoni) at the Department of Agronomy, College of Agriculture, Thrissur, Kerala, from September 2021 to May 2022. The design of the experiment was factorial RBD and replicated thrice. The experiment comprised three levels of spacing (15 cm × 10 cm, 20 cm × 10 cm, and 15 cm × 15 cm) and four pinching intervals (pinching at 20 days after planting (DAP), pinching at 30 DAP, pinching at flower bud initiation and no pinching) in all possible combinations. The plants grown with closer spacing (15 cm × 10 cm) were the tallest at all growth stages. The pinching of the apical bud caused a reduction in plant height and increased the number of branches. Pinched plants recorded higher fresh and dry leaf weights than plants left non-pinched. More leaves were registered under the wider (15 cm × 15 cm) spacing than narrower spacings. Pinching favored the formation of more lateral buds, producing a more significant number of branches and, finally, more leaves per plant. High-density planting of stevia yielded the highest aboveground fresh mass (10925 kg ha-1), whereas lower plant densities yielded the lowest aboveground fresh mass (7330 kg ha-1). The stevia planted at a spacing of 15 cm × 10 cm and pinched at flower bud initiation (11980 kg ha-1) produced higher herbage.
Comparative Study of Cement Replacement with Waste Plastic in Interlocking Paving Stone for Highway Construction in Nigeria
Authors: Dawodu Praise Onimisi , Apata A. C. , Imoh U. U. , Akintunde Femi
Published: January 2023

Portland cement remains the major binder used in the construction of concrete pavements, interlocking stones, and many other aspects of construction, and this implies a high dependence on the commodity thus making it scares and expensive and hence the need to explore other alternatives. This research compares the use of waste plastics and Portland cement for the production of paving stones. In this study, three cases were considered, each case having a study sample and a control sample. Case 1, case 2, and case 3 had mix ratios of (in order of, binder to sand to granite) 1:1:1, 1:1:1.5, and 1:1.5:2.5 respectively, of which the controls were made using Portland cement as the binder and the samples were made with waste plastic as the binder. The comparison was done using compressive strength and water absorption resistance values of the controls and the sample. The results showed that paving stones made from Portland cement have better compressive strength in all cases compared to the samples, the highest compressive strength obtained from the controls was 45N/mm2 while that of the sample was 25N/mm2, however, the study sample showed the highest water absorption resistance percentage of 5%, when compared to the control samples which had as low as 0.8%. This infers that paving stones made from melted waste plastics may not be as strong as those made from Portland cement can be used for roads expected to carry lighter traffic, and are also very suitable for areas of high water table or areas prone to flooding. The samples in this research were made locally and were limited to the three mix ratios mentioned. Further research can be done using a mechanized method to produce the samples, also partial replacement of cement with waste plastic may hence the strength of the paving stone.
Non‐Destructive Low‐Temperature Contacts to MoS2 Nanoribbon and Nanotube Quantum Dots
Authors: Schock Robin T. K. , Neuwald Jonathan , Möckel Wolfgang , Kronseder Matthias , Pirker Luka , Remškar Maja , Hüttel Andreas K.
Published: January 2023

Molybdenum disulfide nanoribbons and nanotubes are quasi‐1D semiconductors with strong spin–orbit interaction, a nanomaterial highly promising for quantum electronic applications. Here, it is demonstrated that a bismuth semimetal layer between the contact metal and this nanomaterial strongly improves the properties of the contacts. Two‐point resistances on the order of 100 kΩ are observed at room temperature. At cryogenic temperature, Coulomb blockade is visible. The resulting stability diagrams indicate a marked absence of trap states at the contacts and the corresponding disorder, compared to previous devices that use low‐work‐function metals as contacts. Single‐level quantum transport is observed at temperatures below 100 mK.
Revealing Atomic‐Level Surface Passivation of PbI2‐Reconditioned Red Perovskite Quantum Dots
Authors: Yang Liuli , Huang Jianhua , Xu Zheyuan , Li Yang , Hou Shijin , Tan Yike , Du Juan , Wang Xiao , Li Ziwei , Pan Anlian
Published: January 2023

CsPbI3 perovskite quantum dots (QDs) are promising materials for high‐efficiency and low‐cost red fluorophores in advanced display and light‐sensing applications. However, structural and spectral stabilities of CsPbI3 QDs by traditional preparation are seriously broken in water or light environment. Here, a compositional engineering strategy with an additional PbI2‐recondition process to synthesize highly‐stable CsPbBr1.2I1.8 @ SiO2 QDs is demonstrated. Time‐ and temperature‐dependent photoluminescence and Raman measurements prove that spectral stability and exciton binding energy of QDs are greatly improved within this strategy. Notably, high‐resolution structure characterizations, point‐to‐point diffraction patterns and line‐scanning of element distributions provide strong and direct evidence at atomic‐level to reveal that PbI2‐recondition can repair defects well, which helps to construct perfect lattices and homogeneous SiO2 passivation layers to prevent the surface bonding of molecules. Moreover, our red perovskite QDs are further designed to prepare various anti‐counterfeiting labels as multi‐scale complex patterns to store and protect information. The proposed recondition strategy explores a new avenue to prepare stable and high‐quality red perovskite QDs for new‐generation lighting and light‐sensing devices.
Synthesis of Acyl Fluorides from Carboxylic Acids with KI/AgSCF3 for Efficient Amide and Peptide Synthesis
Authors: Nagano Shuji , Maruoka Keiji
Published: January 2023

A facile synthesis of acyl fluorides from carboxylic acids in a practical and byproduct‐free manner was effected with commercially available KI/AgSCF3 reagents under conditions of high functional group tolerance, and the acyl fluoride intermediates were easily transformed to the corresponding esters, amides, and several carbon‐carbon bond‐forming products. This approach can be successfully applied to straightforward peptide synthesis from amino acids including sterically hindered amino acids.

magnified image
Thermodynamic efficiency of membrane‐assisted distillation processes
Authors: Kruber Bettina , Droste Karen , Skiborowski Mirko
Published: January 2023

Membrane processes are considered as comparably mild separation processes offering the potential for significant energy savings compared with azeotropic distillation processes. Despite higher investment and material costs, they are of particular interest for improving the energy efficiency in the chemical industry. However, energy savings of more than 20%–30% are rarely reported and even a general superiority can be disputed. To further elucidate this controversial, the current study pursues a quantitative assessment of the thermodynamic efficiency of pervaporation and vapor permeation processes with stand‐alone distillation and hybrid membrane‐assisted distillation processes for the separation of azeotropic mixtures. The results confirm the case‐dependent potential of distillation processes to outperform membrane‐assisted separations in terms of energy efficiency, considering proper heat integration. Although energy efficiency is becoming significantly important, it should be considered in the context of economic performance to determine an optimal trade‐off and to select the best process alternative during conceptual process design.
ConvPred: A deep learning‐based framework for predictions of potential organic reactions
Authors: Wang Wenlong , Liu Qilei , Dong Yachao , Du Jian , Meng Qingwei , Zhang Lei
Published: January 2023

The traditional theory‐based technologies on reaction prediction are not efficient due to their heavy dependence on human expertise and experience. To this end, this article proposes a framework for predictions of potential organic reactions based on reaction templates and two‐dimensional convolutional neural network (2D CNN) model. The quantum mechanics‐based σ‐profiles and the sub‐molecular structure‐based ECFP4 are used individually to encode chemical reactions. Using 605,753 patented reactions extracted from the USPTO 1976‐2016 database and their generated counterparts, the 2D CNN models are trained to evaluate the likelihood of molecular transformations by learning the feature differences between reactants and products. The classification accuracies of the σ‐profiles‐based model and the ECFP4‐based model for the non‐trained reactions are 97.881 and 99.593%. Challenging reactions from literature involving identification of chemo‐, stereo‐, and regio‐selectivity are correctly predicted. Furthermore, a σ‐profiles‐based visual reaction fingerprint is introduced to provide novel insights into the model interpretability.
Synergetic thermodynamic/kinetic separation of C3H8/CH3F on carbon adsorbents for ultrapure fluoromethane electronic gas
Authors: Huang Jiawu , Peng Junjie , Wei Xuan , Du Shengjun , Yang Cuiting , Xiao Jing
Published: January 2023

Atomic layer etching (ALE) using the environmentally friendly electronic gas fluoromethane (CH3F) is guided for fabricating nanoscale electronic components. The adsorptive purification of CH3F provide a viable direction to remove trace amounts of impurities to produce highly pure CH3F (>99.9999%) for the ALE process. Herein, to remove trace propane (~100 ppm) in CH3F, we report synergetic thermodynamic and kinetic separation of C3H8/CH3F over glucose‐derived carbon molecular sieve CMS‐T, (T as pyrolysis temperature). With pore size slightly larger than the kinetic diameter of C3H8, CMS‐600 allows both strong confined adsorption of C3H8 and a higher diffusion rate of C3H8 over CH3F, resulting in a remarkable separation factor of 51.1. Breakthrough experiment demonstrates a high dynamic production capacity of 457 L kg−1 of 7 N CH3F (<100 ppb of C3H8) over CMS‐600 with excellent cycling stability. Adsorption purification over carbon provides a feasible approach for industrial hyperpurification of electronic gas.
Fludarabine versus cyclophospamide in combination with myeloablative total body irradiation as conditioning for patients with acute myeloid leukemia treated with allogeneic hematopoietic cell transplantation. A study from the Acute Leukemia Working Party of the European Society for Blood and Marrow Transplantation
Authors: Giebel Sebastian , Labopin Myriam , Schroeder Thomas , Swoboda Ryszard , Maertens Johan , Bourhis Jean Henri , Grillo Giovanni , Salmenniemi Urpu , Hilgendorf Inken , Kröger Nicolaus , Poiré Xavier , Cornelissen Jan J. , Arat Mutlu , Savani Bipin , Spyridonidis Alexandros , Nagler Arnon , Mohty Mohamad
Published: January 2023

Total body irradiation (TBI) at a dose of 12 Gy combined with cyclophosphamide (CyTBI12Gy) is one of the standard myeloablative regimens for patients with acute myeloid leukemia (AML) treated with allogeneic hematopoietic cell transplantation (allo‐HCT). In clinical practice, cyclophosphamide may be substituted with fludarabine (FluTBI12Gy) to reduce toxicity. We retrospectively compared outcomes of CyTBI12Gy with FluTBI12Gy for patients with AML treated in complete remission (CR) with allo‐HCT from either a matched sibling or unrelated donor. Of 1684 adults who met inclusion criteria, 109 patients in each group were included in a matched‐pair analysis. The cumulative incidence of relapse at 2 years was 25% in the FluTBI12Gy compared to 28% in the CyTBI12Gy group (p = .44) while non‐relapse mortality (NRM) was 17% versus 19%, (p = .89) respectively. The rates of leukemia‐free survival and overall survival were 65% versus 54% (p = .28) and 70% versus 60.5% (p = .17). Cumulative incidence of grade 2–4 acute graft‐versus‐host disease (GVHD) was significantly lower for FluTBI12Gy than CyTBI12Gy (16% vs. 34%, p = .005), while the incidences of grade 3–4 acute GVHD and chronic GVHD did not differ significantly. The probability of GVHD and relapse‐free survival was 49% in the FluTBI12Gy and 41% in the CyTBI12Gy group (p = .17). We conclude that for patients with AML treated with allo‐HCT in CR, cyclophosphamide may be substituted with fludarabine in a regimen based on TBI at a dose of 12 Gy without negative impact on the efficacy. FluTBI12Gy is associated with reduced risk of grade 2–4 acute GVHD and encouraging survival rates.
A phase II study of combination daunorubicin, cytarabine (Ara‐c), and nilotinib (TAsigna) (DATA) in patients newly diagnosed with acute myeloid leukemia with KIT expression
Authors: Al‐Kali Aref , Tibes Raoul , Atherton Pamela , Palmer Jeanne , Alkhateeb Hassan B. , Patnaik Mrinal , Begna Kebede , Gangat Naseema , Hashmi Shahrukh , He Rong , Litzow Mark
Published: January 2023

Acute myeloid leukemia (AML) is a challenging cancer in terms of achieving and maintaining long‐duration remissions. Many novel therapies have been added to the standard regimen (combining cytarabine and anthracycline “7 + 3”) to achieve such goals. Nilotinib is an oral multikinase inhibitor that is active against KIT tyrosine kinase, an important stem cell target. In this trial, we combined nilotinib with 7 + 3 induction (daunorubicin 60 mg/m2), high‐dose cytarabine consolidation, and subsequently, if the patient was a candidate, for 2 years' maintenance therapy in patients with AML and KIT (CD117) expression. Patients were allowed to proceed to allogeneic hematopoietic cell transplantation (HCT) if deemed necessary. Our primary goal was increased complete remission rate with this combination. Thirty‐four patients (with a median age 58.5 years) were enrolled on a single‐arm phase II bi‐institutional study; 21 (62%) patients achieved remission. The complete remission rate was 78% in evaluable patients. Thirteen of 34 (38%) patients had allogeneic HCT, all thirteen of which are still alive (100%). Common (>20%) grade 3 non‐hematological toxicities included febrile neutropenia, hypophosphatemia, elevated liver enzymes, and hypertension. Only one patient (3%) died in induction due to liver failure, which was thought secondary to daunorubicin. Our current study reveals good outcomes in patients who received HCT and may warrant a larger study to confirm our findings in that specific population.
Unterscheidung zwischen sauren und basischen Oberflächenhydroxylgruppen auf Metalloxiden durch Fluoridsubstitution: Eine Fallstudie am Beispiel von defektreichem, blauem TiO2 aus der laserbasierten Defekterzeugung
Authors: Lau Kinran , Niemann Felix , Abdiaziz Kaltum , Heidelmann Markus , Yang Yuke , Tong Yujin , Fechtelkord Michael , Schmidt Torsten C. , Schnegg Alexander , Campen R. Kramer , Peng Baoxiang , Muhler Martin , Reichenberger Sven , Barcikowski Stephan
Published: January 2023

Sowohl oberflächennahe Sauerstofffehlstellen als auch Hydroxylgruppen an der Oberfläche spielen eine entscheidende Rolle in der Katalyse. Dennoch bleiben die genauen Zusammenhänge durch die limitierte analytische Zugänglichkeit dieser Struktureigenschaften oft wenig verstanden. Zur selektiven Quantifizierung der sauren und basischen Oberflächenhydroxide wurde in dieser Studie deshalb eine Fluoridsubstitution am Beispiel zweier Serien von TiO2 (Rutil und P25) untersucht, welche eine zunehmende Dichte an Ti3+‐Sauerstofffehlstellen aufwiesen. Die Materialien sind durch gepulster Laserdefekt‐Engineering in Flüssigkeit (PUDEL) hergestellt worden. Aus EPR‐ und EEL‐Spektroskopie geht hervor, dass sich die lasergenerierten Ti3+ beim Rutil potentiell in der Nähe der Partikeloberfläche befinden, während diese beim P25 tiefer in den Partikeln vorzuliegen scheinen. Anhand der pH‐abhängigen Fluoridsubstitution zeigt sich, dass sich auf dem laserbehandelten Rutil zunehmend saure (verbrückende) Hydroxylgruppen gebildet haben, welche potentiell auf die Hydrierung der lasergenerierten, oberflächennahen Ti3+‐Zentren zurückgeht. Beim P25 blieb die Dichte an Hydroxylgruppen trotz nachweislicher Bildung von Ti3+‐Zentren bei der Laserbehandlung unverändert. Wir gehen davon aus, dass die hier eingesetzte pH‐abhängige Substitutionsmethode von Hydroxiden durch Fluoride zukünftig eine einfache und robuste Charakterisierung von Oberflächen‐OH und deren Korrelation mit Defekten in Metalloxiden zulassen wird.
A “Pre‐Division Metal Clusters” Strategy to Mediate Efficient Dual‐Active Sites ORR Catalyst for Ultralong Rechargeable Zn‐Air Battery
Authors: Zhao Yun‐Xiu , Wen Jing‐Hong , Li Ping , Zhang Peng‐Fang , Wang Su‐Na , Li Da‐Cheng , Dou Jian‐Min , Li Yun‐Wu , Ma Hui‐Yan , Xu Liqiang
Published: January 2023

To conquer the bottleneck of sluggish kinetics in cathodic oxygen reduction reaction (ORR) of metal‐air batteries, catalysts with dual‐active centers have stood out. Here, a “pre‐division metal clusters” strategy is firstly conceived to fabricate a N,S‐dual doped honeycomb‐like carbon matrix inlaid with CoN4 sites and wrapped Co2P nanoclusters as dual‐active centers (Co2P/CoN4@NSC‐500). A crystalline {CoII2} coordination cluster divided by periphery second organic layers is well‐designed to realize delocalized dispersion before calcination. The optimal Co2P/CoN4@NSC‐500 executes excellent 4e− ORR activity surpassing the benchmark Pt/C. Theoretical calculation results reveal that the CoN4 sites and Co2P nanoclusters can synergistically quicken the formation of *OOH on Co sites. The rechargeable Zn‐air battery (ZAB) assembled by Co2P/CoN4@NSC‐500 delivers ultralong cycling stability over 1742 hours (3484 cycles) under 5 mA cm−2 and can light up a 2.4 V LED bulb for ≈264 hours, evidencing the promising practical application potentials in portable devices.
Evaluierung und Verbesserung der Stabilität von Poly(ethylenoxid)‐basierten Festkörperbatterien mit Hochvoltkathoden
Authors: Yusim Yuriy , Trevisanello Enrico , Ruess Raffael , Richter Felix H. , Mayer Alexander , Bresser Dominic , Passerini Stefano , Janek Jürgen , Henss Anja
Published: January 2023

Festkörperbatterien (Solid‐State‐Batteries, SSBs) mit Poly(ethylenoxid) (PEO) und Hochvoltkathodenaktivmaterialien (CAMs) wie LiNi1−‐x−yCoxMnyO2 (NCM) zeigen beim Zyklisieren oftmals “Spannungsrauschen”, was mit einem Zellversagen verbunden ist. Darüber hinaus finden sich in der Literatur ganz unterschiedliche Aussagen zur Langzeit‐Zyklenperformance von PEO in Kontakt mit Hochvolt‐CAMs. In der vorliegenden Arbeit wird experimentell nachgewiesen, dass das Spannungsrauschen tatsächlich durch Lithiumdendriten, die den festen Polymerelektrolyten (SPE) penetrieren, verursacht wird. Eine Lösung für dieses Problem kann die Verwendung von PEO mit einem höheren Molekulargewicht sein, was zu einer verbesserten Zyklenstabilität führt. Zusätzlich kann mittels Röntgenphotoelektronenspektroskopie (XPS) gezeigt werden, dass es an der Kathodenseite zur Bildung von oxidativen Degradationsprodukten nach dem Zyklisieren mit NCM als CAM kommt, was mittels der üblichen Fourier‐Transformations‐Infrarot‐Spektroskopie (FTIR) aufgrund ihrer begrenzten Oberflächensensitivität nicht nachgewiesen werden kann. Damit tragen unsere Ergebnisse dazu bei, nicht nur die Stabilität von PEO‐basierten SSBs besser bewerten zu können, sondern zeigen auch, dass durch die Wahl eines höhermolekularem PEOs die Stabilität gegenüber Hochvolt‐CAM signifikant gesteigert werden kann.
Fundamental Understanding of Electronic Structure in FeN4 Site on Electrocatalytic Activity via dz2‐Orbital‐Driven Charge Tuning for Acidic Oxygen Reduction
Authors: Li Xueli , Chen Tengge , Yang Bolong , Xiang Zhonghua
Published: January 2023

The structural diversity of active sites resulting from traditional pyrolysis hinder our understanding of the local coordination environment (LCE) around the active site, and its effects on performance in the oxygen reduction reaction (ORR). We created a series of FeN4 active‐site configurations via a pyrolysis‐free approach where LCEs are defined by covalent organic polymers (COPs). Our results suggest a more positive charge on iron atoms in the vicinity of an electron‐withdrawing side‐chain; that is, a high‐valence configuration (FeH+N4) that is achieved with a COPBTC@Cl‐CNTs catalyst subject to
‐orbital tuning. A new descriptor ξ, defined as the band center of iron atoms projected on the
‐orbital, was introduced to quantitively explain a volcano‐like regulation mechanism. When ξ is distributed between −1.887 and −1.862 eV, the catalytic performance of the COPBTC@Cl‐CNTs electrocatalyst is optimized.
Evaluation and Improvement of the Stability of Poly(ethylene oxide)‐based Solid‐state Batteries with High‐Voltage Cathodes
Authors: Yusim Yuriy , Trevisanello Enrico , Ruess Raffael , Richter Felix H. , Mayer Alexander , Bresser Dominic , Passerini Stefano , Janek Jürgen , Henss Anja
Published: January 2023

Solid‐state batteries (SSBs) with high‐voltage cathode active materials (CAMs) such as LiNi1−x−yCoxMnyO2 (NCM) and poly(ethylene oxide) (PEO) suffer from “noisy voltage” related cell failure. Moreover, reports on their long‐term cycling performance with high‐voltage CAMs are not consistent. In this work, we verified that the penetration of lithium dendrites through the solid polymer electrolyte (SPE) indeed causes such “noisy voltage cell failure”. This problem can be overcome by a simple modification of the SPE using higher molecular weight PEO, resulting in an improved cycling stability compared to lower molecular weight PEO. Furthermore, X‐ray photoelectron spectroscopy analysis confirms the formation of oxidative degradation products after cycling with NCM, for what Fourier transform infrared spectroscopy is not suitable as an analytical technique due to its limited surface sensitivity. Overall, our results help to critically evaluate and improve the stability of PEO‐based SSBs.
Rapid gelation of dual physical network hydrogel with ultra‐stretchable, antifreezing, moisturing for stable and sensitive response
Authors: Zhang Yuxia , Li Qinglin , Chen Jiawen , Zheng Yanyan , Lu Xiaoyu , Chen Qinhui
Published: January 2023

Dual physical network hydrogel possesses robust energy dissipation mechanism. However, the demanding conditions of the second monomer radical polymerization aren't benefit for the dispersion of conductive filler. Moreover, the stable and sensitive response under extreme environment puts forward the requirements for mechanical, antifreezing and moisture retention properties. Herein, a dual physical networks hydrogel (polyacrylic acid‐chitosan‐graphene/glycerol, noted as PAA‐CS‐G/Gly) was prepared rapidly (<0.5 h) without chemical cross‐linking agents at room temperature. The rapid gelation, ionic coordination of Ag+ together with certain viscosity chitosan promoted the dispersion of graphene. PAA‐CS‐G/Gly showed ultra‐stretchable properties (~2500%), good toughness (3.11 MJ/m3), breaking strength (0.27 MPa) and fatigue resistance. PAA‐CS‐G/Gly had good adhesion properties, outstanding tolerance for freezing (−80°C) and moisture retention. More importantly, PAA‐CS‐G/Gly strain sensor had excellent sensitivity (GF, up to 9.449) at 300% ~ 900% strain. It could sensitively detect human joint movements and even subtle activities such as talking and swallowing. PAA‐CS‐G/Gly hydrogel is expected to adhere directly to the human body for flexible monitoring of human size movement under extreme environmental conditions.
High‐performance nano‐TiO2@polyvinylidene fluoride composite separators prepared by electrospinning for safe lithium‐ion battery
Authors: Li Datuan , Gao Xingxu , Cao Min , Sheng Lei , Yang Ling , Xie Xin , Gong Yun , Hu Qingyang , Xie Qiangqiang , Wang Tao , He Jianping , Huang Xianli
Published: January 2023

Traditional polyolefin separators cannot guarantee safety for lithium‐ion batteries at high temperature due to their low melting point, especially for high power discharge. Therefore, it is imperative to develop separators with excellent thermal stability. In this paper, we have prepared TiO2 modified PVDF composite separators by electrospinning. When compared with commercial PE separators, this kind of composite separators show superior thermal stability at 160°C. In addition, it is found that the 0.5‐TiO2@PVDF separator exhibits excellent flame retardant and optimal tension strength. Meanwhile, the 0.5‐TiO2@PVDF separator exhibits ideal liquid electrolyte storage capacity, which improves the ionic conductivity (0.68 mS cm−1). As a result, the LiCoO2||Li cells with 0.5‐TiO2@PVDF separator have high discharge capacity retention rate at a current density of 1 C (300 cycles) and excellent rate performance (1.75 mAh at 5 C). In short, nano‐TiO2 modified PVDF separator has a great application prospect in high‐performance and high‐safety lithium‐ion batteries.