bluuebunny/crossref_metadata_2025 huggingface dataset:
Congenital spinal intramedullary epidermoid cyst
Authors: Sreekanth P. V. , Neeli Hemanth , Bhagat Abhinav Chander , Malik Rajesh , Meena Mukesh
Published: January 2025

Spinal epidermoid cysts are rare benign tumors, accounting for <1% of all spinal tumors, with intramedullary cases being particularly uncommon. We present a rare case of a congenital intramedullary epidermoid cyst in a 12-year-old male, who presented with progressive bilateral lower limb weakness and gait disturbance over five months. Magnetic resonance imaging revealed a well-defined intramedullary lesion at the D6-D8 level, exhibiting hypointensity on T1-weighted images, hyperintensity on T2-weighted images, diffusion restriction on diffusion-weighted images, and peripheral rim-like enhancement on post-contrast imaging, suggestive of an epidermoid cyst. Surgical resection was performed, and histopathological analysis confirmed the presence of lamellated keratinous material, consistent with an epidermoid cyst. This case is notable for the absence of associated spinal dysraphism, making it a rare presentation. Imaging features, including characteristic signal patterns and diffusion restriction, aided in the diagnosis, distinguishing it from other intramedullary lesions such as arachnoid cysts, dermoid tumors, and neoplasms.
Integrative GIS-AHP Techniques for Flood Susceptibility Analysis in Nashik, Maharashtra
Authors: Madhusudhan Reddy M. , Bhavani G. , Avinash Goud M. , Sushmanth J. , Sri Ramya N. , Praveen S.
Published: January 2025

This study delves into flood susceptibility analysis in Nashik, Maharashtra, employing Geographic Information Systems (GIS) and the Analytic Hierarchy Process (AHP). Nashik, a rapidly growing city along the Godavari River, faces significant flood risks due to its unique geographical and hydrological characteristics. With a population exceeding 6 million and covering an area of 15,582 square kilometers, Nashik's vulnerability to floods is compounded by factors such as rapid urbanization and diverse river networks including the Godavari, Vaitarna, Bhima, Girna, Kashyapi and Darna. The study integrates various thematic maps, encompassing aspect, distance to river, elevation, flow accumulation, flow direction, drainage density, contour, Landsat 8 imagery, normalized difference vegetation index, land use and land cover, annual rainfall, roughness, slope, stream network and topographic wetness index. These maps aid in accurately identifying flood-prone areas by considering surface features, flow characteristics and hydrological parameters. The findings highlight regions with high drainage density, low elevation and proximity to major rivers as particularly vulnerable to flooding.

Additional factors such as land cover, rainfall intensity and terrain roughness significantly influence flood susceptibility. Through the integrative GIS-AHP approach, policymakers, urban planners and emergency response agencies gain critical insights for implementing proactive measures to mitigate flood risks. The study underscores the importance of spatial analysis and multi-criteria decision-making techniques in effective flood risk management and urban planning in Nashik. It emphasizes the comprehensive nature of the flood susceptibility assessment, incorporating a total of 11 parameters used in the AHP technique. By integrating these parameters into a cohesive framework, this research contributes to a better understanding of flood dynamics in Nashik and aids in developing strategies for resilient urban development and disaster preparedness.
Ecofriendly Corrosion Inhibitor for Controlling Corrosion of CS Immersed in Hydrochloric Acid Solution
Authors: Sulochana S. , John Amalraj A. , Syed Abuthahir S.S. , Shek Dhavud S. , Sundararajan G.
Published: January 2025

The corrosion inhibitor's effect on carbon steel (CS) corrosion in 1N hydrochloric acid was investigated in this work. The inhibitor was derived from a water-based Trichosanthes cucumerina Linn plant extract (TCPL). The primary goal was to ascertain the efficacy and environmental safety of this technique. Our evaluation was based on the mass loss method. An inhibitory efficacy of 86.63% was achieved using this strategy. The mechanisms of corrosion inhibition have been investigated using electrochemical methods including PDP and EIS. Inhibition efficacy and corrosion rate are both affected by inhibitor concentration. There is equal regulation of the anodic and cathodic processes in the mixed-inhibitor inhibitor system. The findings of the PDP study corroborate this. The corrosion current and the resistance to linear polarisation may both be efficiently reduced by inhibitors.

When inhibitor systems are present on metal surfaces, electrochemical impedance investigations have shown that a protective covering, called the blanket effect, arises. A decrease in double layer capacitance and an increase in charge transfer resistance have been noted. The process of the protective layer's creation on the CS surface was explained by an FTIR investigation. Molecular bonds are formed between the metal and the active component, causing this process to occur. We used SEM and AFM to look at the protective layer's surface morphology. Comparing CS's surface element composition to those of blank, polished and inhibitor systems was done using EDAX technology. The results of the research could be useful for the acid-pickling industry.
Design, synthesis, spectral characterization and antibacterial studies of transition metal complexes of benzothiophene Schiff base
Authors: Madhukar V. , Jyothi S.
Published: January 2025

In the present work, a series of benzothiophene based Schiff base ligands 2-((E)-(1-methyl-3-nitro-1H-pyrazol-5-ylimino)methyl)benzo[b]thiophen-3-ol and their Cu(II), Co(II) and Ni(II) complexes were synthesized and characterized by physical, analytical and spectral data such as elemental analysis, FT-IR, 1H NMR, 13C NMR, ESI-Mass, UV-vis studies. Spectro-analytical experimental data confirms that all of these metal complexes have a square planar shape.

The synthesized Schiff base coordinates to the metal through imine nitrogen and phenolic oxygen atoms, making it a monobasic bi-dentate ligand. In addition, five different bacterial species were tested for metal complexes in the antibacterial tests.
Alleviating the Detrimental Effects of Salinity Stress by Application of Potassium: Growth, Yield and Photosynthetic Parameters of Mung bean (Vigna radiata) (L.) Wilczek
Authors: Ibrahimi Arifa , Kumar Yogesh , Jakhar Somveer
Published: January 2025

Among all the abiotic factors, salinity stress is one of the most harmful and it severely limits crop productivity. Potassium is considered as one of the exogenous protectants which may alleviate the harmful effects of salinity stress. To attain the stated goals, pot experiments were conducted with primary aims to estimate the negative impact of salinity stress in mung bean and to mitigate the effects of salinity stress using potassium. The response to the combination of salinity stress in mung bean (Vigna radiata L.) grown under net house conditions with three levels of application of potassium (0.24g, 0.40g and 0.48g) was studied.

Salinity stress decreased various growth parameters (plant height, shoot and root length, fresh and dry weight of root and shoot and leaf area), yield parameters (no. of pods/plant, no. of seeds/pod, weight of seeds and pods) and photosynthetic parameters (Chlorophyll content and carotenoid content). Potassium application alleviates the detrimental effects of salinity even in highest level of NaCl (100mM). Therefore, mung bean (Vigna radiata MH-1142) can be grown successfully at salt stress with application of 0.48 g of KNO3.
Phyto-fabrication of metal nanoparticles using Thar desert plants
Authors: Jangir B. , Mochi S. , Mishra A. , Jangid N.K. , Goel R. , Sharma A.
Published: January 2025

Nanoparticles possess characteristic properties that make them potential candidates for various applications in diversified fields. Developing novel strategies for the synthesis of nanoparticles is crucial to optimize their properties and expand their potential uses. The biological route of nanoparticle synthesis, also known as green method, has been portrayed as an efficient, cost effective and environmentally friendly technique. Biological materials like plants, bacteria, yeast, fungi and algae have indeed been reported to possess high bioreduction and stabilization abilities, enabling them to synthesize metallic nanoparticles of various sizes and shapes.

Among these biomaterials, this review mainly focuses on Thar desert plant-mediated biosynthesis of metallic nanoparticles. The phytochemicals in desert plants such as polyphenols, alkaloids, steroids, saponins and pregnane glycosides play a crucial role in reduction, capping and stabilization of metal nanoparticles. A systematic study of literature, based on effect of various desert plant materials and experimental conditions on properties of metal nanoparticles is also provided. This review also highlights the applications of nanoparticles stabilized by desert plants in various fields such as agriculture, food industry and medicine.
Removal of Synthetic Dyes from Textile Wastewater using Physical and Biological Methods: A Review
Authors: Saini Renu , Bansal Nidhi , Sharma Aruna
Published: January 2025

Dyes are a significant group of organic pollutants that are well-known for harming both humans and aquatic life in general. Dye-contaminated wastewater needs to undergo appropriate treatment before being released into main streams in order to minimize its detrimental impact on people and the environment. Adsorption, flocculation-coagulation, reverse osmosis and biological treatment are some current technologies that are frequently used to remove dye from wastewater.
Two-Level Study of Object-Oriented Programming by University Students
Authors: Dmitrieva T.A. , Prutzkow A.V. , Pylkin A.N.
Published: January 2025

The difficulties of learning the paradigm of object-oriented programming by university students are considered. Two approaches to learn object-oriented programming: Object-First (learning this paradigm at the start of programming learning) and Object-Later (prior learning of structured and procedural programming) are described. The expediency to use the second approach consisting of two levels is proved. The requirements to knowledge and skills being necessary for object-oriented programming are formulated. A review of programming languages used in both levels is presented. The conclusions are made; recommendations to study object-oriented programming are given.
Frequency of occurrence of modifiable risk factors for osteoporosis in young people
Authors:   Kemerovo State Medical University of the Ministry of Health of Russia, Kemerovo, Russia, Letaeva M.V. , Koroleva M.V. ,   Kemerovo State Medical University of the Ministry of Health of Russia, Kemerovo, Russia, Averkieva Yu.V. ,   Kemerovo State Medical University of the Ministry of Health of Russia, Kemerovo, Russia, Malyshenko O.S. ,   Kemerovo State Medical University of the Ministry of Health of Russia, Kemerovo, Russia, Bogulko K.A. ,   Kemerovo State Medical University of the Ministry of Health of Russia, Kemerovo, Russia, Golobokova E.A. ,   Kemerovo State Medical University of the Ministry of Health of Russia, Kemerovo, Russia
Published: January 2025

The prevalence of modifiable risk factors for osteoporosis has been studied in young people. The study included 396 (75.1%) women and 131 (24.9%) men, for a total of 527 people. A questionnaire was developed that included questions on physical activity, nutrition, lifestyle, and the presence of bad habits. The following frequency of occurrence of risk factors was established: 233 (44.2%) people had one risk factors 166 (31.5%) - two, 92 (17.5%) - three, 36 (6.8%) people had four. The majority of respondents (425 (80.6%) people) had insufficient dietary calcium intake (56.2% of the age norm). The results of the study demonstrate a high prevalence of modifiable risk factors in young people, which undoubtedly indicates the need for preventive measures to prevent the development of osteoporosis and its complications in the future.
Keywords: osteoporosis, young age, risk factors, vitamin D, calcium, physical activity.
Determining trends in the epidemiological process and quality of medical care for breast cancer
Authors:   Associate Professor of the Department of General Hygiene, Irkutsk State Medical University of the Ministry of Health of Russia, Candidate of Medical Sciences, Zaykova Z.A. , Bayanova T.A. ,   Ph.D. in Medicine, Associate Professor of the Department of Epidemiology, Irkutsk State Medical University, Zubrinsky K.G. ,   physician-statistician, Irkutsk Oncology Center
Published: January 2025

The analysis of primary breast cancer incidence among women in the Irkutsk region for 2011–2023 and mortality from it was conducted based on general indicators and by age groups for women under 50 and over 50 years old to clarify the epidemiological situation and trends of ongoing processes. The primary breast cancer incidence continues to grow in the region: «rough» indicators – by 1.4 and standardized indicators – by 1.2 times. The increase in breast cancer incidence is also demonstrated in two large age groups with a greater increase in women under 50 – 1.8 versus 1.3 times in women over 50. The mortality rate of women from breast cancer in these age groups has a multidirectional trend: up to 50 years of age, an increase of 9% was registered; over 50 years of age – an insignificant decrease of 8.3%. In contrast to the all-Russian trend towards a decrease in mortality in 2011–2023, in the Irkutsk region the overall mortality rate from breast cancer did not change in relative terms and decreased insignificantly by 17.0% in standardized terms. In contrast to the all-Russian trend towards a decrease in mortality in 2011–2023, in the Irkutsk region the overall mortality rate from breast cancer did not change according to «rough» indicators and decreased insignificantly by 17.0% according to standardized ones. In women in the region, cancer is most often diagnosed in the upper quadrants, the central part of the breast, as well as cancer that extends beyond one or more localizations C50.0–C50.6 according to ICD-10. All indicators of the quality of oncological care for women with breast cancer improved in the Irkutsk region during the study period. Moreover, in 2023, two quality indicators were higher than the all-Russian values: 48.6% of patients with breast cancer were actively identified (44.0% in the Russian Federation) and in almost 100% of cases, diagnoses were confirmed morphologically (99.8% versus 99.2% in the Russian Federation). Achieving the all-Russian level for all indicators of the quality of oncological care will make it possible to reverse the situation with regard to mortality and achieve optimal results in improving the quality of life of women with breast cancer.
Key words: breast cancer, trends, primary morbidity, mortality, neglect, one-year mortality, quality of medical care.
Comparative analysis of risk factors for death in patients of different age groups with severe COVID-19-associated pneumonia
Authors:   Medical Institute FSAO HE M.K. Ammosov North-Eastern Federal University, Yakutsk, Chulakova N.A. , Potapov A.F. ,   Medical Institute FSAO HE M.K. Ammosov North-Eastern Federal University, Yakutsk, Ivanova A.A. ,   Medical Institute FSAO HE M.K. Ammosov North-Eastern Federal University, Yakutsk, Chulakov K.V. ,   Head of the Department of Civil Defence of RS (Y) Yakut Republican Clinical Hospital, Yakutsk
Published: January 2025

The study examines the risk factors for mortality in patients across various age groups through a retrospective analysis of 591 medical records of patients with severe COVID-19-associated pneumonia treated in the intensive care unit (ICU). Univariate and multivariate analyses were conducted to identify risk factors for mortality in two distinct groups: patients under the age of 60 (group 1) and those aged 60 years and older (group 2), and comparative analysis between these two groups was performed. Mortality in group 1 was observed to be 46.9%, whereas in group 2 it was 73.3%. Patients in group 2 exhibited a comparatively lower weight and body mass index (BMI), a higher number of concomitant diseases, and more severe assessments according to the APACHE II and SOFA scales. The clinical presentation on day 1 did not differ between the groups based on the following criteria: hypercoagulation (93.1% in group 1 and 93.3% in group 2, p=0.950), septic shock (11.9% in group 1 and 18.1% in group 2, p=0.080), acute kidney injury (AKI) (12.5% in group 1 and 16.7% in group 2, p=0.206), and multiple organ failure syndrome (MODS) (55% in group 1 and 52.2% in group 2, p=0.236). In group 1, a higher prevalence of acute liver failure was observed (25% vs. 5.1%, p<0.001), whereas group 2 exhibited a greater incidence of acute cerebral failure (ACF) (13.8% vs. 34.8%, p=0.001). Group 1 also demonstrated significantly elevated leukocytosis (p<0.001) and alanine aminotransferase (ALT) levels (p<0.001). Conversely, group 2 showed lower levels of lymphopenia (p<0.001), hypoalbuminemia (p<0.001), and platelet count (p<0.001), in addition to higher levels of blood urea nitrogen (p<0.001), creatinine (p<0.001), and brain natriuretic hormone (NTproBNP) (p=0.003). In patients under 60 years old with severe COVID-19-associated pneumonia, the independent risk factor for death was the development of MODS on the first day of admission in the ICU. For patients over 60 years old, independent risk factors for death were age, the presence of chronic kidney disease (CKD), the severity of hypoxia as determined by the PaO2/FiO2 ratio upon admission to the ICU, the development of MODS, septic shock, and acute cerebral disorder.
Keywords: coronavirus disease 2019, COVID-19, predictors, age, risk factors
Features of placental damage in patients with perinatal losses during premature birth and acute COVID-19
Authors:   – PhD in Medical Sciences, Associate Professor of the Department of obstetrics and gynecology of South Ural State Medical University of the Ministry of Health of the Russian Federation, obstetrician-gynecologist Regional Clinical Hospital No. 2, Ishchenko L.S. , Voropaeva E.E. ,   Grand PhD in Medical Sciences, Professor of the Department of pathological anatomy and forensic medicine of Professor V.L. Kovalenko of South Ural State Medical University of the Ministry of Health of the Russian Federation, Deputy Chief Physician for Obstetrics and Gynecology, Regional Clinical Hospital No. 2, Kazachkov E.L. ,   Grand PhD in Medical Sciences, Professor, Head of the Department of Pathological Anatomy and Forensic Medicine of Professor V.L. Kovalenko of South Ural State Medical University of the Ministry of Health of the Russian Federation, Kazachkova E.A. ,   Grand PhD in Medical Sciences, Professor, Professor of the Department of Obstetrics and Gynecology of the South Ural State Medical University of the Ministry of Health of the Russian Federation, Kholopova A.Yu. ,   postgraduate student of the Department Department of pathological anatomy and forensic medicine of Professor V.L. Kovalenko of South Ural State Medical University of the Ministry of Health of the Russian Federation, Khaidukova Yu.V. ,   Head of the 2nd Obstetric Department of the Regional Clinical Hospital No. 2, Shamaeva T.N. ,   PhD in Pedagogical Sciences, Associate Professor, Associate Professor of the Department of Mathematics, Medical Informatics, Computer Science and Statistics, Physics of South Ural State Medical University of the Ministry of Health of the Russian Federation
Published: January 2025

A morphological study of the placenta in patients with perinatal losses in preterm labor and acute COVID-19 of varying severity, manifested in the II and III trimesters of gestation, was performed. It was found that the features of placental damage in patients with perinatal losses are statistically significant predominance of thrombosis, inflammatory changes and manifestations of placentitis SARS-CoV-2 in comparison with placentas of patients without perinatal losses.
Keywords: pregnancy, novel coronavirus infection, COVID-19, preterm labor, perinatal mortality, placental damage
Unsupervised machine learning-based image recognition of raw IR spectra: Toward chemist-like chemical structural classification and beyond numerical data
Authors: Fuku Kentarou , Yoshida Takefumi
Published: January 2025

Recent advances in artificial intelligence have significantly improved spectral data analysis. In this study, we used unsupervised machine learning to classify chemical compounds based on infrared (IR) spectral images, without relying on prior chemical knowledge. The potential of machine learning for chemical classification was demonstrated by extracting IR spectral images from the Spectral Database for Organic Compounds and converting them into 208620-dimensional vector data. Hierarchical clustering of 230 compounds revealed distinct main clusters (A–G), each with specific subclusters exhibiting higher intracluster similarities. Despite the challenges, including sensitivity to spectral deviations and difficulty of distinguishing delicate chemical structures in spectra with low transparency in the fingerprint area, the proposed image recognition approach exhibits good potential. Both principal component analysis (PCA) and k-means clustering produced similar results. Furthermore, the method demonstrated high robustness to noise. The Tanimoto coefficient was used to evaluate the molecular similarity, providing valuable insights. However, some results deviated from chemists’ intuitions. The study also highlighted that the scaling composition formulas and molecular weights did not affect the classification results because high-dimensional features dominated the process. A comparison of the clustering results obtained from molecular fingerprints, using the adjusted Rand index as a metric, indicated that the image data provided better classification performance than numerical data of the same resolution. Overall, this study demonstrates the feasibility of using machine learning with IR spectral image data for chemical classification and offers a novel perspective that complements traditional methods, although the classifications may not always align with chemists’ intuitions. This approach has broader implications for fields such as drug discovery, materials science, and automated spectral analysis, where handling large, raw spectral datasets is essential.
Bicyclic Sulfonium Pincer Ligand with a Thiatriptycenium Backbone - Synthesis and Applications in π-Acid Catalysis
Authors: Zafar Mohammad , Shamali Donia , Barel Nitsan , Danovich David , Tulchinsky Yuri
Published: January 2025

A bicyclic PSP-pincer ligand featuring a sulfonium cation at the bridgehead position of its rigid triptycene-like scaffold was synthesized and metallated with a bis-cationic Pt(II) center. The resulting tris-cationic Pt(II) complex exhibits excellent photostability and improved catalytic performance compared to its analogue with the previously reported sulfonium pincer ligand.
Evolving Cyclopropenium Derivatives into High-Performance Bifunctional Organocatalysts towards Ring-Opening Alternating Copolymerization
Authors: Wu Cunluo , Song Xinyuan , Han Qingqing , Zhong Ronglin , Wang Xiaowu , Li Zhibo , Liu Yiliu
Published: January 2025

Bifunctional catalysts, known for their superior activity and selectivity compared to binary systems, hold great promise for ring-opening copolymerization (ROCOP). Here, we present our recent advancements in developing high-performance bifunctional organocatalysts by integrating borane with triamino-cyclopropenium (TAC) derivatives. Specifically, we developed a bifunctional catalyst by conjugating 9-borabicyclo[3.3.1]nonane (9-BBN) with TAC-Cl through an optimized alkyl linker (TB-3). This catalyst exhibited outstanding performance in the controlled ROCOP of epoxides and anhydrides, demonstrating high activity, selectivity, and thermal stability, and outperforming both binary catalytic systems and quaternary ammonium-borane analogues. Notably, further transformation of the TAC moiety into its cyclopropenimine (CPI) derivative led to the creation of a cyclopropenimine-borane bifunctional organocatalyst (CPI-B). The strong yet dissociative intramolecular N-B coordination between the CPI and BBN units imparts remarkable air stability to CPI-B. Additionally, the N/B Lewis pair in CPI-B effectively activates protic initiators, enabling precise control over end-group functionality and polymer topology in ROCOP. These advancements significantly broaden the practical utility of CPI-B in polymer synthesis.
Synthesis of Protoberberine Alkaloids by C–H Functionalization and Anionic Aza-6π-Electrocyclization: Dual Activity as AMPK Activators and Inhibitors
Authors: Cao Yujie , Perry Justin , Zhang Eryun , Trinh Andy , Kacker Arnav , Cruz Shayne , Ceballos Hannah , Pan Aaron , Huang Wendong , Kou Kevin
Published: January 2025

5’-Adenosine monophosphate-activated protein kinase (AMPK) plays a critical role in maintaining cellular energy homeostasis, and its activation has garnered attention for treating chronic metabolic diseases. Inhibitors of AMPK are underdeveloped but bear implications in treating cancers, controlling autophagy, and elderly wasting. Protoberberine alkaloids are typically regarded as AMPK activators. Herein, we report a modular synthesis strategy to access a collection of oxyberberine alkaloids, including the first synthesis of stepharotudine. In vitro assays reveal how subtle structural modifi-cations can negate AMPK activation while conferring unprecedented inhibitory properties within the same class of com-pounds, which was previously unknown. Key steps in the synthesis include an oxidative Rh(III)-catalyzed C–H function-alization using electron-rich alkenes, NaH-mediated reductive N–O bond cleavage, and the first example of an anionic aza-6π-electrocyclization. Additionally, we provide mechanistic support for nucleophilic hydride transfer reactivity with NaH in DMF.
HTA - An open-source software for assigning heads and tails to SMILES in polymerization reactions
Authors: Ferrari Brenda de Souza , Giro Ronaldo , Steiner Mathias
Published: January 2025

Artificial Intelligence (AI) techniques are transforming the computational discovery and design of polymers. The key enablers for polymer informatics are machine-readable molecular string representations of the building blocks of a polymer, i.e., the monomers. In monomer strings, such as SMILES, symbols at the head and tail atoms indicate the locations of bond formation during polymerization. Since the linking of monomers determines a polymer’s properties, the performance of AI prediction models will, ultimately, be limited by the accuracy of the head and tail assignments in the monomer SMILES. Considering the large number of polymer precursors available in chemical data bases, reliable methods for the automated assignment of head and tail atoms are needed. Here, we report a method for assigning head and tail atoms in monomer SMILES by analyzing the reactivity of their functional groups. In a reference data set containing 206 polymer precursors, the HeadTailAssign (HTA) algorithm has correctly predicted the polymer class of 204 monomer SMILES, representing an accuracy of 99%. The head and tail atoms were correctly assigned to 187 monomer SMILES, representing an accuracy of 91%. The HTA code is available for validation and reuse at https://github.com/IBM/HeadTailAssign
Emergent Magnetic Ordering in Iron(II)-based Metal-Organic Framework Glasses
Authors: Das Chinmoy , Salamon Soma , Landers Joachim , Weiß Jan-Benedikt , Xue Wen-Long , Kolodzeiski Pascal , Pallach Roman , Wende Heiko , Henke Sebastian
Published: January 2025

Metal-organic framework (MOF) glasses combine the structural tunability of crystalline MOFs with the processability of amorphous materials, offering exciting opportunities for functional hybrid materials. We report a one-pot, solvent-free synthesis of two Fe²⁺-based MOF glasses, gFe-bipy (Fe2(im)3(bim)(bipy)) and gFe-tBubipy (Fe2(im)3(bim)(tBubipy)0.25; im– = imidazolate, bim– = benzimidazolate, bipy = 2,2’-bipyridine, tBubipy = 4,4’-di-tert-butyl-2,2’-bipyridine). These glasses feature a continuous random network structure composed of four-connected tetrahedral and octahedral Fe²⁺ nodes. Despite their amorphous nature, both glasses exhibit a high degree of local structural order, enabling strong magnetic exchange interactions between Fe²⁺ centers. Remarkably, these materials are the first MOF glasses to exhibit long-range magnetic ordering, with gFe-tBubipy undergoing an antiferromagnetic ordering transition at 14 K. The magnetic ordering transition of gFe-tBubipy is attributed to its high spin density and specific local structure, distinguishing this antiferromagnetic MOF glass from other amorphous antiferromagnetic materials. The combination of long-range magnetic ordering with exceptionally low glass transition temperatures (Tg = 85–87 °C) positions these materials as highly promising candidates for applications in spintronics, quantum computing and other technologies that benefit from facile processing and shaping. This discovery underscores the transformative potential of MOF glasses as hybrid materials, bridging modular design, processability, and advanced magnetic functionality.
The smart way of simultaneous scaling up and optimizing the synthesis of PGS for further rapid thermal cross-linking with the use of response surface methodology
Authors: Wrzecionek Michał , Kryszak Bartłomiej , Gadomska-Gajadhur Agnieszka
Published: January 2025

Due to its very good biocompatibility, poly(glycerol sebacate) – PGS – is probably one of the most interesting synthetic biomaterials. This material passes several in vitro and in vivo tests with the use of quite a wide range of cells and animals. Nowadays, PGS is known as a good material for tissue engineering, drug delivery systems, surgical sealants, and other biomedical uses. Unfortunately, prepolymer synthesis and its subsequent cross-linking are usually time-consuming processes carried out at high temperatures, which is not beneficial from an economic and ecological point of view. This work describes a study of PGS prepolymer synthesis with the use of an acid catalyst in the Fischer mechanism. Mathematical methods were used to optimize and develop a fast and stable synthesis method, which allowed the obtaining of prepolymer in a short time without risk of gelation in the reactor. The proposed method could be easily used in industry.
A tale of two mechanisms: The p53 modulator COTI-2 is a Zn metallochaperone
Authors: Şimşek İrem , Shahbazi-Raz Farsheed , Krause Michael J. , Mohammadzadeh Azam , Kosar Maryam , Xu Peihan , Khan Samra , Tykhoniuk Olena , DaDalt Ashley , Almasri Deya'a , Watanabe Lara K. , Breault Kaitlyn , Hayward John J. , Pick Fraser S. , Ho Richard L. , Rawson Jeremy M. , Trant John F.
Published: January 2025

Mutations in, or misregulation of, Tp53 are found in approximately 50% of all cancers. p53 functions by ensuring that cells with irretrievably damaged DNA undergo apoptosis. When p53 is non-functional in cells that may also be undergoing uncontrolled cell growth (due to other mutations), cancer readily emerges. Consequently, restoring the function of misregulated and mutated Tp53 is an incredibly important goal in therapeutic oncology. Tp53 mutations often induce conformational changes that inhibit the protein’s ability to engage its DNA response element. Small molecule chaperones could theoretically restore the proper shape and activity, but this is a far more challenging design problem than the typical paradigm of designing inhibitors of protein function. Consequently, it is unsurprising that there are no approved p53-targeting drugs. COTI-2, a thiosemicarbazone with orphan-drug status for ovarian cancer, has proven an effective cytotoxic agent against various cancer cell lines in vitro, exhibited efficacy in vivo, and has demonstrated a good safety profile in Phase 1b human clinical trials. The proposed mechanism, direct engagement and refolding of mutant p53, has been supported by a combination of cell-based assays and transcriptomics data. We propose that this is an unlikely mechanism of action, and that instead COTI-2 is acting as a selective, well-tolerated, zinc chaperone to replace zinc ions lost to p53 mutants’ deficient zinc-binding. We discuss that COTI-2 likely also works through other mechanisms but demonstrate that zinc-binding is necessary for the exceptional bioactivity. The promising therapeutic potential of this molecule and additional evidence for its zinc chaperone activity is discussed. This would make it the first well-tolerated zinc chaperone with pharmacological implications not only for cancer but for other zinc deficiency-related diseases.
Proton-driven lithium separation using alkali-templated coordination cages
Authors: Sun Xiang , Wu Kai , Teeuwen Paula , Pracht Philipp , Wales David , Nitschke Jonathan
Published: January 2025

The extraction of lithium from natural deposits is energy intensive because Li+ is found together with physiochemically similar alkali (Na+, K+) and alkaline earth (Mg2+, Ca2+) metals. Methods for the direct and specific extraction of lithium from salt mixtures are thus essential to ensure an adequate supply of this metal for the batteries needed to decarbonize the world economy. Here we present the preparation of alkali-metal-templated coordination cages and their application to lithium extraction. Within the cage framework, protons amplify the different binding properties between Li+ and similar metal ions: protons associate exclusively with Li+ in close proximity at the cage vertices, repelling other cations as a result of increased electrostatic repulsion and reduced availability of coordinating nitrogen atoms. We developed this proton-driven lithium recognition within coordination cages into a separation cycle capable of extracting Li+ from a mixture of salts that includes Na+, K+, Mg2+ and Ca2+.
Enantioselective domino carbopalladation/Csp3-Pd capture using carbenes generated from N-tosylhydrazones: Access to chiral 3,3-disubstituted oxindoles bearing chiral quaternary carbon center
Authors: Venugopalan Nair Vysakh , Karthikraja Esackraj , Subramanian Venkatesan , Govindasamy Sekar
Published: January 2025

N-tosylhydrazones have become convenient synthons in organic synthesis ever since their inception as diazo precursors. Yet, enantioselective processes involving N-tosylhydrazones are quite rare and challenging. In our continuing efforts in maneuvering Pd carbenes to synthesize complex heterocycles, we have developed a domino process for intercepting the enantioenriched alkyl-Pd species in a Mizoroki-Heck cascade. In this enantioselective domino process, N-alkyl acrylamides undergo a regiospecific 5-exo-trig cyclization to form an alkyl palladium species at a chiral quaternary carbon center that lacks a facile β-hydrogen. The alkyl palladium species formed is then trapped via carbene generated from bench-stable N-tosylhydrazones. The method constructs a chiral quaternary carbon center and provides direct access to chiral 3,3-disubstituted oxindoles with yields up to 91% and enantioselectivity >99% with tolerance for diverse functional groups. Mechanistic investigations revealed that a cationic Heck cascade is involved. The structure of the active catalytic species has been studied by HRMS analysis and linear relationship plot between the % ee of the catalyst and % ee of the product. Based on these experimental insights, computational studies of the catalytic cycle have been done to study the energetics of the steps involved. Further, the stereochemical outcome of the reaction has been justified by comparing the free energies of the diastereomeric transition states involved in the enantio-determining step. The constructed alkene handle next to the chiral center enhances the utility of this methodology. Apart from ease of functionalization, the proximity of the chiral center to the alkene, facilitates efficient transfer of chirality during transformations. This highlights the utility of the synthesized 3,3-disubstituted oxindoles as valuable chiral synthons. This has been demonstrated via a handful of synthetic transformations of the model oxindole and formal synthesis of five natural products, namely (+)-esermethole, (+)-physostigmine, (+)-deoxyseroline, (+)-phenserine and (+)-physovenine, which are a couple of steps apart in synthesis according to reported procedures.
Implementation of an ellipsoidal-cavity field correction for computed molecular oscillator strengths in solution: A(nother) benchmark study
Authors: Garcia-Alvarez Jorge C. , Gozem Samer
Published: January 2025

We recently compared oscillator strengths (OS) obtained from electronic structure calculations f_comp to OSs derived from experimental spectra f_exp multiplied by the refractive index n of the solution in which the spectra were measured. The choice of nf_exp instead of f_exp as reference accounts for the macroscopic flux of energy in a dielectric (the experimental solvent). Here, we apply a correction to f_comp values that accounts for the local electromagnetic field driving the absorption transition (which is generally different from the macroscopic field). We refer to these modified OSs as f_comp,S. The correction is obtained by assuming that each molecule occupies an ellipsoidal cavity, fitted to its van der Waals surface, surrounded by a continuum dielectric model representing the solvent. Sets ranging from 33 - 85 experimental transitions are used for the benchmarking. For LR-CCSD and EOM-CCSD, we find that f_comp,S generally gives a better agreement with experimental strengths than f_comp. For LR-CCSD in the length gauge, for instance, there is a 1 to 1 scaling of the (nf_exp, f_comp,S) pairs. Instead, the results for TD-DFT depend on the amount of HF exchange used in the functional: pure functionals typically also have a 1 to 1 scaling of the (nf_exp, f_comp,S) pairs, while for hybrid functionals f_comp,S overestimates nf_exp to a degree that appears proportional to the amount of HF exchange present in the functional.
Improved C5-amide bioisosteres for human neuraminidase 1 inhibitors based on 2-deoxy-2,3-didehydro-N-acetyl neuraminic acid (DANA)
Authors: Radwan Mostafa , Carvajal Elisa Garcia , Cairo Christopher
Published: January 2025

Neuraminidase enzymes (NEU) play a crucial role in many physiological and pathological conditions. Humans have four isoenzymes of NEU and their specific roles continue to be investigated. Isoenzyme-selective inhibitors are needed as research tools and may lead to future therapeutics. We tested a series of new candidate inhibitors by replacing the C5-amide of 2-deoxy-2,3-dididehydro-N-acetyl neuraminic acid (DANA) with amide bioisosteres. Design of candidate inhibitors was accomplished using substituents that were components of previously identified NEU inhibitors combined with alternative amide bioisosteres. Compounds were tested for inhibition of the four human NEU, and inhibitory activities were compared to reference amide compounds. We observed that 1,4-disubstituted-1,2,3-triazole was the best bioisostere for inhibitors of NEU1. Inhibitor 542 showed high potency for NEU1 (K¬i = 0.4 ± 0.1 μM) and gave significant improvement in selectivity compared to the reference amide compound 502. Additionally, compound 542 had improved lipophilic characteristics which could provide improved pharmacokinetic properties. Screening of these inhibitors also identified a selective NEU2 inhibitor 543 (Ki = 2.6 ± 0.6 μM), illustrating that amide bioisostere replacement can identify improved inhibitors for multiple NEU isoenzymes.
Multiscale Vehicle Traffic Air Pollutant Exposure and Equity Analysis in the United States using a Novel Emissions Exposure Surrogate
Authors: Antonczak Brittany , Thompson Tammy , DePaola Mindi , Rowangould Gregory
Published: January 2025

This study develops a refined surrogate, “emission density,” to access exposure to hazardous air pollutants from on-road vehicle traffic in communities across the U.S. that balances spatial precision and computational burden. Our results show that people of color and lower-income people are disproportionately exposed to higher levels of traffic emissions almost everywhere in the U.S. Specifically, 89% of U.S. counties exhibit significant associations between increased exposure to NOX and PM2.5 emissions and higher proportions of people of color and lower household incomes. On average, people of color experience twice as the exposure of White individuals, while low-income households are exposed to more than three times the exposure. Additionally, medium- and heavy-duty vehicles contribute disproportionately to emissions relative to traffic volume. Despite declines in vehicle emission rates, the growth in near-roadway populations, rising traffic volumes, and persistent inequities present ongoing public health and environmental justice concerns. This analysis offers critical insights for identifying the most impacted communities and evaluating the effectiveness of potential policies at local, state, and national levels to reduce exposure.
Heteronuclear Spin Decoupling under Cryogenic Magic-Angle-Spinning Dynamic Nuclear Polarization Conditions
Authors: Jabbour Ribal , Qadri Zeba , Madhu P K , Equbal Asif
Published: January 2025

Heteronuclear decoupling is an essential element in the solid-state magic-angle spinning (MAS) Dynamic nuclear polarization (DNP) experiments involving low gamma (γ) nuclei like 13C and 15N coupled to protons. Under the constraints of limited (< 100 kHz) maximum radio frequency (RF) amplitude and intermediate (30-45 kHz) spinning frequencies, imposed by the cryogenic DNP setup, the typically utilized heteronuclear decoupling schemes like TPPM and SPINAL-64 suffer from near rotary-resonance recoupling (R3). Here, we demonstrate the effectiveness of the refocused continuous-wave (rCW) decoupling sequence for heteronuclear 1H decoupling near the R3 regime under DNP conditions. We compare the performance of rCWApA decoupling with the widely used SPINAL-64 scheme and show a significant improvement in the heteronuclear decoupling efficiency, confirmed through T2' evaluations. The superior decoupling efficiency of rCWApA stems from its half-wave symmetry in the RF interaction frame, which enables effective decoupling of first and second-order effective heteronuclear coupling Hamiltonian, even at low RF amplitude levels and hence minimizing R3 effects better than any other decoupling scheme.
AMUSET-TICA: A Tensor-Based Approach for Identifying Slow Collective Variables in Biomolecular Dynamics
Authors: Cao Siqin , Nüske Feliks , Liu Bojun , Soley Micheline , Huang Xuhui
Published: January 2025

Elucidating Collective Variables (CVs) for biomolecular dynamics is crucial for understanding numerous biological processes. By leveraging the tensor-train data structure, a multilinear version of the AMUSE (Algorithm for Multiple Unknown Signals) algorithm for Koopman approximation (AMUSEt) was recently developed to identify CVs for biomolecular dynamics. To find slow CVs, AMUSEt transforms input features (e.g., pairwise atomic distances) into nonlinear basis functions (e.g., Gaussian functions) and encodes nonlinear basis functions within a tensor-train structure via the time-lagged correlation functions. Due to the need to fit these tensor-train data structures into computer memory, AMUSEt can handle only a limited number of input features. Consequently, AMUSEt relies on manually selecting and ranking features based on physical intuition to fully capture the slow dynamics. However, when applied to complex biological systems with numerous features, this selection and ranking process becomes increasingly challenging. To address this challenge, here we present AMUSET-TICA (AMUSEt-based Time-lagged Independent Component Analysis), a CV-identification method using time-structure-independent components (tICs) as the input features for AMUSEt. The key insight of AMUSET-TICA lies in its highly effective embedding of high-dimensional atomistic protein conformations, achieved by expanding orthogonal tICs into overlapping Gaussian basis functions through a tensor-product data structure. This eliminates the need for manually selecting and ranking input features for a wide range of biomolecular systems. We demonstrate that AMUSET-TICA consistently and significantly outperforms AMUSEt and tICA in identifying slow CVs for three different biomolecular systems: alanine dipeptide, the N-terminal domain of L9 (NTL9), and the FIP35 WW domain. For all these systems, the CVs generated by AMUSET-TICA accurately describe the slowest dynamical modes underlying these biological conformational changes. Furthermore, we show that AMUSET-TICA achieves performance comparable to deep-learning approaches like VAMPnets in identifying the slowest dynamical modes, while being significantly more computationally efficient in terms of CPU time. In addition, the CVs yielded by AMUSET-TICA provide insights into the folding mechanisms of NTL9 and the FIP35 WW domain, including CV3 and CV4 of the WW domain, which capture its two parallel folding pathways. We expect AMUSET-TICA can be widely applied to facilitate the investigation of biomolecular dynamics.
Индуцированное со-растворителем гомохиральное распознавание карбоновых кислот на основе 3,5-биарил-2,3-дигидро-5H-тиазоло[3,2-a]пиримидинов в кристаллах комплексов Mg+2 и Ca+2
Authors: Агарков А.С. , Кожихов А.А. , Маилян М. , Французова Л.В. , Лодочникова О.А. , Соловьева С.Е. , Антипин И.С.
Published: January 2025

Получены комплексы на основе двух структурно родственных карбоновых кислот на основе 3,5-биарил-2,3-дигидро-5H-тиазоло[3,2-a]пиримидинов и исследована их кристаллическая структура. Не являясь изоструктурными, комплексы сформированы принципиально одинаковым образом. Катион металла (магния или кальция) координирован по шести положениям молекулами растворителей, причём большее количество положений занято молекулами основного растворителя, а минорное(ые) – молекулой со-растворителя (вода в комплексе магния и этиленгликоль в комплексе кальция). Молекулы растворителей формируют собой первую координационную сферу катиона магния, составляя вместе с ним «катионное ядро». Наличие в первой координационной сфере металла «дефектных» позиций, занятых молекулами со-растворителя, является фактором, асимметризующим дальнейший рост комплекса. А именно, формирование второй координационной сферы анионами карбоновых кислот посредством первичных водородных связей O–H‧‧‧O типа происходит с участием двух лигандов одинаковой конфигурации со стороны, противоположной молекуле со-растворителя.
Analisis kemampuan literasi numerasi dalam memecahkan masalah pada materi perbandingan ditinjau dari gaya belajar
Authors: Pebrianti Chindy , Ambarawati Mika
Published: January 2025

Penelitian ini mengkaji kemampuan literasi numerasi berdasarkan gaya belajar pada siswa kelas VII di MTs Daarul Ulum Ampelgading. Jenis penelitian ini kualitatif deskriptif, dengan subjek awal penelitian sebanyak 31 siswa hingga subjek akhir yang terpilih sebanyak 6 siswa. Kemampuan numerasi siswa dapat diketahui dengan mengumpulkan data melalui lembar angket gaya belajar, tes kemampuan literasi, dan wawancara. Kemampuan numerasi dan numerasi dapat terlihat dari proses pengerjaan soal literasi dan numerasi yang telah disiapkan.  Reduksi data, penyajian data dan penarikan kesimpulan dilakukan dalam analisis data. Hasil penelitian mengungkapkan bahwa siswa yang memiliki gaya belajar visual yakni: kemampuan literasi 50 %, numerasi 0 % dan literasi numerasi 0 %. Siswa dengan gaya belajar visual mampu memahami soal tetapi tidak dengan penyelesaiannya. Sedangkan siswa yang memiliki gaya belajar auditorial yakni: kemampuan literasi 50 %, numerasi 50 % dan literasi numerasi 50 %.  Siswa dengan gaya belajar tersebut mampu memahami soal beserta dengan penyelesaiannya. Sedangkan siswa yang memiliki gaya belajar kinestetik dapat memahami soal namun tidak beserta penyelesaiannya. Siswa dengan gaya belajar kinestetik yakni: Kemampuan literasi 50 %, numerasi 50 % dan literasi numerasi 0 %.