bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fast Collective Hydrogen‐Bond Dynamics in Hexafluoroisopropanol Related to its Chemical Activity
Authors: Caporaletti Federico , Gunkel Lucas , Fernández‐Ibáñez M. Ángeles , Hunger Johannes , Woutersen Sander 
Published: October 2024

AbstractUsing fluorinated mono‐alcohols, in particular hexafluoro‐isopropanol (HFIP), as a solvent can enhance chemical reaction rates in a spectacular manner. Previous work has shown evidence that this enhancement is related to the hydrogen‐bond structure of these liquids. Here, we investigate the hydrogen‐bond dynamics of HFIP and compare it to that of its non‐fluorinated analog, isopropanol. Ultrafast infrared spectroscopy experiments show that the dynamics of individual hydrogen‐bonds is about twice as slow in HFIP as in isopropanol. Surprisingly, from dielectric spectroscopy we find the opposite behavior for the dynamics of hydrogen‐bonded clusters: collective rearrangements are 3 times faster in HFIP than in isopropanol. This difference indicates that the hydrogen‐bonded clusters in HFIP are smaller than in isopropanol. The differences in cluster size can be traced to changes in the hydrogen‐bond donor and acceptor strengths upon fluorination. The smaller cluster size can boost reaction rates in HFIP by increasing the concentration of reactive, terminal OH‐groups of the clusters, whereas the fast collective dynamics can increase the rate of formation of hydrogen‐bonds with the reactants. The longer lifetime of the individual hydrogen‐bonds in HFIP can enhance the stability of the hydrogen‐bonded clusters, and so increase the probability of reactant‐solvent hydrogen‐bonding.
Stabilization of High‐Valent Molecular Cobalt Sites through Oxidized Phosphorus in Reduced Graphene Oxide for Enhanced Oxygen Evolution Catalysis
Authors: Yang Jiahui , Dai Guoliang , Song Wenjuan , Win Poe Ei Phyu , Wang Jiong , Wang Xin 
Published: October 2024

AbstractHeterogeneous molecular cobalt (Co) sites represent one type of classical catalytic sites for electrochemical oxygen evolution reaction (OER) in alkaline solutions. There are dynamic equilibriums between Co2+, Co3+ and Co4+ states coupling with OH−/H+ interaction before and during the OER event. Since the emergence of Co2+ sites is detrimental to the OER cycle, the stabilization of high‐valent Co sites to shift away from the equilibrium becomes critical and is proposed as a new strategy to enhance OER. Herein, phosphorus (P) atoms were doped into reduced graphene oxide to link molecular Co2+ acetylacetonate toward synthesizing a novel heterogeneous molecular catalyst. By increasing the oxidation states of P heteroatoms, the linked Co sites were spontaneously oxidized from 2+ to 3+ states in a KOH solution through OH− ions coupling at an open circuit condition. With excluding the Co2+ sites, the as‐derived Co sites with 3+ initial states exhibited intrinsically high OER activity, validating the effectiveness of the strategy of stabilizing high valence Co sites.
Iron Oxide Clusters as Electron Donors Under Light Enhance Oxygen Reduction Kinetics at Atomically Dispersed Fe for Photocatalytic CH4 Partial Oxidation
Authors: Xu Yueyuan , Shen Xianfeng , Guo Shuai , Lv Yao , Wang Ke , Shi Yao , Li Yukun , Yan Mi , Zhang Peng , Dai Sheng , Lu Kuan , Xie Pengfei 
Published: October 2024

AbstractPhotocatalytic CH4 oxidation to CH3OH emerges as a promising strategy to sustainably utilize natural gas and mitigate the greenhouse effect. However, there remains a significant challenge for the synthesis of methanol by using O2 at low temperature. Inspired by the catalytic structure in soluble methane monooxygenase (MMO) and the corresponding reaction mechanism, we prepared a biomimetic photocatalyst with the decoration of Fe2O3 nanoclusters and satellite Fe single atoms immobilized on carbon nitride. The catalyst demonstrates an excellent CH3OH productivity of 5.02 mmol ⋅ gcat−1 ⋅ h−1 with CH3OH selectivity of 98.5 %. Mechanism studies reveal that the synergy between Fe2O3 nanoclusters and Fe single atoms establishes a dual‐Fe site as MMO for O2 activation and subsequent CH4 partial oxidation. Moreover, the light excitation of Fe2O3 nanoclusters with a relative narrow band gap could deliver the electrons and protons to atomic Fe that facilitating the oxygen reduction kinetics for the robust of CH3OH synthesis.
New Metal Complexes Incorporating Schiff Base Ligand Based on Pyridine Moiety: Synthesis, Spectral Characterization, DFT, Biological Evaluation, and Molecular Docking
Authors: Salah Nesma , Adly Omima M. I. , Ibrahim Magdy A. , Abdelaziz Maged , Abdelrhman Ebtesam M. 
Published: October 2024

ABSTRACTA new Schiff base ligand, HNMPC, was prepared and reacted with some metal ions, including Cu(II), Ni(II), Co(II), Mn(II), and VO(IV). The infrared, electronic, mass, electron spin resonance, nuclear magnetic resonance, thermal and elemental analysis, molar conductance, and magnetic susceptibility measurements were used to characterize the metal complexes. The HNMPC ligand acts as a monoanionic tridentate ONO donor in all complexes, and the coordinating sites are C=Opyridone, C=N, and the phenolate anion. All metal complexes exhibit octahedral configurations, and the results showed that the metal ion:ligand ratio was 1:2. The molecular structural parameters of the ligand and its metal complexes were determined based on the DFT level implemented in the Gaussian 09 program B3LYP/GENECP method at the 6‐311G(d,p) basis set for C, H, N, and O atoms and the SDD (Stuttgart/Dresden) basis set for the metal atoms. The theoretical data were correlated with the experimental results. Gram‐positive bacteria, Gram‐negative bacteria, yeast, and fungi were used to test the current compounds' antimicrobial activity. Investigating the antitumor activity of the ligand and its complexes against the HepG2 cell lines showed encouraging IC50 values that were on par with those of cisplatin. In order to determine the affinity and binding pattern for the synthesized compounds toward the VEGFR‐2 active site, molecular docking studies were conducted, and the results were correlated with antitumor data. Based on the obtained results, future work aimed to synthesize a new category of Schiff bases and their metal complexes derived from the current aminopyridine derivative with diverse aldehydes and ketones.
Triptycene based microporous hypercrosslinked polymer with amino functionality for selective CO2 capture
Authors: Ansari Mosim , Helal Aasif , Abdelnaby Mahmoud Mohamed , Hakeem Abbas Saeed , Khan Mohd Yusuf 
Published: October 2024

AbstractThe increasing CO2 concentration in the atmosphere contributes significantly to global warming, necessitating effective capture techniques. Though amine‐based solvents are commonly used, they have drawbacks like high energy consumption and corrosion. Physical adsorption using microporous sorbents with polar groups emerges as a promising alternative, offering high efficiency and selectivity for CO2 capture. This work presents the design of a new microporous hypercrosslinked polymer with amino groups derived from the 3D molecular building block triptycene (TBMP‐NH2), for CO2 capture applications. The triptycene unit in the polymer backbone provides high surface area, thermal stability, and microporosity. TBMP‐NH2 demonstrates excellent thermal stability (Td > 350°C), considerable microporosity, and a high BET‐specific surface area of 866 m2/g, making it a promising microporous adsorbent. It exhibits a high CO2 adsorption capacity of 1.86 mmol/g at 273 K and 1.23 mmol/g at 298 K, with a Qst value of 33.95 kJ/mol, indicating a physisorption mechanism where the micropore volume (Vmic = 0.359 cm3/g) plays a crucial role. TBMP‐NH2 displays good CO2/N2 and CO2/CH4 selectivity, outperforming several reported porous polymers. Owing to its high physiochemical and thermal properties, and efficient and selective CO2 capture ability, TBMP‐NH2 can be considered a promising material for CO2 capture and environmental remediation application.
Photoluminescent and Electrochemiluminescent Detection of Fe3+ Using Cyclometalated Iridium Complexes via Fe3+‐Catalyzed Hydrolysis
Authors: Seung No Hyun , Sim Minhee , Shin Ik‐Soo , Kim Joohoon , Hong Jong‐In 
Published: October 2024

AbstractFerric ion (Fe3+) is a biologically abundant and important metal ion. We developed several cyclometalated iridium complex‐based molecular sensors (1, ppy‐1, 1‐phen, 1 a, and 1_OMe) for the detection of Fe3+ using an acetal moiety as the reaction site. The acetal moiety in iridium complexes undergoes Fe3+‐catalyzed hydrolysis and subsequent formation of a formyl group, resulting in turn‐off photoluminescent and electrochemiluminescent responses. Sensor 1 showed excellent selectivity toward Fe3+ over other biologically important metal ions. Furthermore, we compared the performance of the sensors based on the structural differences of the iridium complexes, and revealed a relationship between the structure and chemical properties through electrochemical experiments and computational calculations.
Institutional reverse mentoring: Bridging the student/leadership gap
Authors: O'Connor Rachael , Barraclough Lauren , Gleadall Steven , Walker Lucinda 
Published: October 2024

AbstractThere is growing interest in reverse mentoring from an equity, diversity and inclusion (EDI) perspective across the higher education (HE) sector. An interesting and under‐explored area is the extent to which reverse mentoring may be utilised to connect the student body with university leadership, a significant category of people making decisions that impact on student experiences but whom students may rarely (or in some cases never) interact with, often being associated with the idea of the faceless ‘university’. Consideration of the disconnect between students and university leaders and what, if anything, reverse mentoring conversations can bring to this space, has been limited. This paper shines a light on these relationships (and their importance) through its critical exploration of a reverse mentoring scheme via which students at a range of levels and from diverse disciplines and under‐represented backgrounds mentored senior leaders within a Russell Group university on EDI‐related topics. It is one of the first studies to collaboratively consider the perspectives of mentors (students from under‐represented backgrounds) and mentees (those in senior leadership positions), exploring the role and impact of reverse mentoring via novel applications of adapted indicators of leader–member exchange theory and facets of multicultural, ecological and relational mentoring. Key themes include understanding diverse identities, navigating hierarchies, influencing institutional change, creating compassionate, safe spaces and transforming practice through engagement with lived‐experience expertise. This paper seeks to further develop understanding of the intersections between student belonging and HE leadership through the vehicle of reverse mentoring.
Explainable Machine Learning Models to Predict Gibbs–Donnan Effect During Ultrafiltration and Diafiltration of High‐Concentration Monoclonal Antibody Formulations
Authors: Chen Chyi‐Shin , Ujiie Seiryu , Tanibata Reina , Kawase Takuo , Kobayashi Shohei 
Published: October 2024

ABSTRACTEvaluating the Gibbs–Donnan and volume exclusion effects during protein ultrafiltration and diafiltration (UF/DF) is crucial in biopharmaceutical process development to precisely control the concentration of the drug substance in the final formulation. Understanding the interactions between formulation excipients and proteins under these conditions requires a domain‐specific knowledge of molecular‐level phenomena. This study developed gradient boosted tree models to predict the Gibbs–Donnan and volume exclusion effects for amino acids and therapeutic monoclonal antibodies using simple molecular descriptors. The models’ predictions were interpreted by information gain and Shapley additive explanation (SHAP) values to understand the modes of action of the antibodies and excipients and to validate the models. The results translated feature effects in machine learning to real‐world molecular interactions, which were cross‐referenced with existing scientific literature for verification. The models were validated in pilot‐scale manufacturing runs of two antibody products requiring high levels of concentration. By only requiring a molecule's biophysicochemical descriptors and process conditions, the proposed models provide an in silico alternative to conventional UF/DF experiments to accelerate process development and boost process understanding of the underlying molecular mechanisms through rational interpretation of the models.
Identification and in vitro genotoxicity assessment of forced degradation products of glimepiride and glyburide using HEK cell‐based COMET assay
Authors: Jain Riya , Aishwarya Dande , Wankhade Shrutika , Anupriya  , Kumarasamy Murali , Peraman Ramalingam 
Published: October 2024

AbstractThis study focuses on characterizing the forced degradation products of antidiabetic drugs glimepiride (GMD) and glyburide (GBD), with previously unexplored genotoxicity. Drugs underwent stress induced by acid, base, and hydrogen peroxide. For GMD, impurities were profiled and isolated using Hypersil Gold C8 (250 × 10 mm, 5 μ) through semi‐preparative HPLC with a fraction collector. For GBD, impurity profiling was performed using semi‐preparative HPLC (Hypersil GOLD C18, 250 × 10 mm, 5 μ), and reverse‐phase flash chromatography (FP ECOFLEX C18 4 g column) for isolation. Although five GMD and three GBD impurities were detected, only three GMD and two GBD impurities were separated and assessed for purity using analytical RP‐HPLC with the purity percentages ranging from 96.6% to 99.9%. LC‐Orbitrap MS was used to identify these three GMD impurities (m/z: 408.122, 338.340, 381.160) and two GBD impurities (m/z: 369.065, 325.283). ProTox‐II in silico predictions classified all impurities as class 4 and 5, with no positive genotoxicity indications. In vitro comet assays, using HEK cells, indicated that for GMD, impurity 2 and impurity 5 were less genotoxic, whereas impurity 4 exhibited genotoxicity. For GBD, both impurities 1 and 3 were found to be genotoxic, with impurity 3 showing a higher level of genotoxicity than impurity 1.
Understanding voluntary pro‐environmental behavior among colleagues: Roles of green crafting, psychological empowerment, and green organizational climate
Authors: Zafar Hina , Tian Feng , Ho Jo Ann , Roh Taewoo , Latif Badar 
Published: October 2024

AbstractA concerning surge in pollution has drawn increased attention to sustainability efforts. The lack of environmentally conscious human behavior contributes significantly to environmental degradation. This research explores the impact of perceived colleague support towards the environment (PCSE) as a catalyst for promoting employees' green initiatives. Underpinned by the conservation of resources (COR) theory, the study reveals a sequential chain mediation model, wherein PCSE initiates a process leading to voluntary pro‐environmental behavior (VPEB) among employees, facilitated by green crafting (GC) and a supportive green organization climate (GOC). Additionally, the study examines the moderating role of psychological empowerment (PE) on the relationship between GC and GOC. Data were collected at two‐wav points with a 2‐week gap from the Pakistani textile sector. Results indicate that GC and GOC serially mediate the relationship between PCSE and VPEB of employees. Furthermore, the results support the mediation of GOC between PCSE and VPEB. However, the results did not support the moderating impact of PE. The study discusses important theoretical and practical implications for fostering green initiatives among employees.
Modeling Overall Survival in Patients With Pancreatic Cancer From a Pooled Analysis of Phase II Trials
Authors: Kabir Eva Rahman , Azam Faruque , Khan Tanisha Tabassum Sayka , Yasmin Hasina , Chowdhury Namara Mariam , Ahmed Syeda Maliha , Sagar Baejid Hossain , Tahrim Nasrin Ahmed 
Published: October 2024

ABSTRACTBackgroundWe evaluated the validity of surrogacy of progression‐free survival (PFS) or time‐to‐progression (TTP) and overall response rate (ORR) in phase II trials of pancreatic ductal adenocarcinoma (PDAC). In addition, we explored the impact of predictive variables on overall survival (OS) and developed an optimal OS model.MethodsWe analyzed 1867 clinical endpoint from 619 phase II PDAC trials with a systematic search from PubMed. Endpoint correlations were determined by Spearman's rank correlation. The assessed predictive factors included PFS/TTP, treatment size, therapy type, stage, and previous treatment. The relationship between predictors and OS was explored by a gamma generalized linear model (GLM) with a log‐link function and compared with linear models.ResultsThe Spearman rank correlation coefficient between PFS/TTP and OS was 0.88 (95% confidence interval [CI] 0.85–0.89; p < 0.0001; n = 610) and between ORR and OS was 0.58 (0.52–0.64; p < 0.0001; n = 514). Model comparison favored the GLM model over the linear model, offering more accurate predictions for higher OS values. Consequently, PFS/TTP was the strongest predictor (pseudo‐R2 = 0.75), with 1 added median PFS/TTP month associated with 13% (95% CI 13%–14%) increase in median OS. Subgroup analysis revealed that chemotherapy conferred significantly longer OS compared to targeted therapy in 1‐Agent and 2‐Agent trials, exhibiting a “very large” and “medium” effect size, respectively (rank biserial, rrb = 0.40 [95% CI 0.22–0.56] and rrb = 0.29 [0.16–0.41], both p < 0.0001), although inconsistent efficacy in 3‐Agent trials (rrb = 0.12 [−0.07–0.30], p = 0.21).ConclusionsPFS/TTP is a more reliable surrogate than ORR and a strong predictor of OS in phase II trials of pancreatic cancer. Moreover, gamma GLM (log‐link function) is a robust tool for modeling positively skewed survival data with non‐constant variance, thus can be applied to other cancers' OS data of such nature.
Simple, Effective and Validated. VTE CASE Risk Assessment Score for Venous Thromboembolism in Metastatic Germ Cell Tumour Patients Before First‐Line Chemotherapy
Authors: Michalski Wojciech , Macios Anna , Poniatowska Grażyna , Zastawna Inga , Demkow Tomasz , Wiechno Paweł 
Published: October 2024

ABSTRACTBackgroundVenous thromboembolism (VTE) may jeopardise excellent treatment results of germ cell tumours (GCT). We previously constructed a VTE risk score for GCT patients qualified for first‐line chemotherapy (CTH), including vein compression, clinical stage (CS) and haemoglobin concentration.AimValidating our score in a separate cohort and establishing the cut‐off point for the score. Re‐assessing the numerical score in the training cohort.Materials and MethodsWe retrospectively analysed a new cohort of GCT patients staged IS–IIIC. Area under the curve of receiver‐operating characteristic (AUC‐ROC) was calculated for the developed score, Khorana Risk Score (KRS) and Padua Prediction Score (PPS). AUC‐ROC of the integer score was calculated for the training cohort. Cut‐off point was established by Youden's and Liu's indices.ResultsAmong 336 eligible patients in the validation cohort, VTE occurred in 41 (12.2%). AUC‐ROC for our score, KRS and PPS were 0.818 (95% confidence interval (CI): 0.746–0.891), 0.608 (0.529–0.688) and 0.634 (0.547–0.720), respectively, p < 0.001. The optimal cut‐off point for a low/high risk was 6 (≤ 6 vs. ≥ 7). In the training cohort, 369 patients had complete data on vein compression. AUC‐ROC for our score, KRS and PPS were 0.819 (95% CI: 0.758–0.879), 0.710 (0.637–0.782) and 0.725 (0.651–0.800), p ≤ 0.001 and 0.015, respectively. Positive and negative predictive values were 30.8% and 96.5%, respectively.ConclusionsOur VTE risk score is a handy tool for GCT patients before first‐line CTH for metastatic disease. Outperforming KRS and PPS, it has a good discriminatory value, especially for identifying low‐risk patients.
Mechanochemical Transformations of Pharmaceutical Cocrystals: Polymorphs and Coformer Exchange
Authors: Trzeciak Katarzyna , Dudek Marta K. , Potrzebowski Marek J. 
Published: October 2024

AbstractTransformations of solid samples under solvent‐free or minimal solvent conditions set the future trend and define a modern strategy for the production of new materials. Of the various technologies tested in recent years, the mechanochemical approach seems to be the most promising for economic and ecological reasons. The aim of this review article is to present the current state of art in solid state research on binary systems, which have found numerous applications in the pharmaceutical and materials science industries. This article is divided into three sections. In the first part, we describe the new equipment improvements, which include the innovative application of thermo‐mechanochemistry, sono‐mechanochemistry, photo‐mechanochemistry, electro‐mechanochemistry, as well as resonant acoustic mixing (RAM), and transformation under high‐speed sample spinning (“SpeedMixing”). A brief description of techniques dedicated to ex‐situ and in‐situ studies of progress and the mechanism of solid matter transformation (PXRD, FTIR, Raman and NMR spectroscopy) is presented. In the second section, we discuss the problem of cocrystal polymorphism highlighting the issue related with correlation between mechanochemical parameters (time, temperature, energy, molar ratio, solvent used as a liquid assistant, surface energy, crystal size, crystal shape) and preference for the formation of requested polymorph. The last part is devoted to the description of the processes of coformer exchange in binary systems forced by mechanical and/or thermal stimuli. The influence of the thermodynamic factor on the selection of the best‐suited partner for the formation of a two‐component stable structure is presented.
Redox‐Induced Aromatic Substitution: A Study on Guanidino‐Functionalized Aromatics
Authors: Wild Ute , Engels Eliane , Hübner Olaf , Kaifer Elisabeth , Himmel Hans‐Jörg 
Published: October 2024

AbstractAromatic substitution of redox‐active aromatic compounds could be initiated by a preceding redox step. We report on the different reaction pathways of such redox‐induced substitution (RIAS) reactions between a redox‐active guanidino‐functionalized aromatic molecule (GFA) and an amine or guanidine. Oxidation of the GFA leads to an umpolung of the guanidine from a nucleophile to an electrophile and thereby enables addition of the amine or guanidine. Several examples are given, demonstrating the use of redox substitution in synthetic chemistry, e. g. for the convenient synthesis of novel N‐heteropolycyclic molecules and unsymmetrically‐substituted aromatics.