bluuebunny/crossref_metadata_2025 huggingface dataset:
Persistent Photoluminescence and Mechanoluminescence of a Highly Sensitive Pressure and Temperature Gauge in Combination with a 3D‐Printable Optical Coding Platform
Authors: Zheng Teng , Luo Jiangcheng , Peng Dengfeng , Peng Liang , Woźny Przemysław , Barzowska Justyna , Kamiński Mikołaj , Mahlik Sebastian , Moszczyński Jan , Soler‐Carracedo Kevin , Rivera‐López Fernando , Hemmerich Hanoch , Runowski Marcin
Published: October 2024

Distinct types of luminescence that are activated by various stimuli in a single material offer exciting developmental opportunities for functional materials. A versatile sensing platform that exhibits photoluminescence (PL), persistent luminescence (PersL), and mechanoluminescence (ML) is introduced, which enables the sensitive detection of temperature, pressure, and force/stress. The developed Sr2MgSi2O7:Eu2+/Dy3+ material exhibits a linear relationship between ML intensity and force and can be used as an ML stress sensor. Additionally, the bandwidth of the PL emission band and the PL lifetime of this material are remarkably sensitive to temperature, with values of ≈0.05 nm K−1 and 1.29%/K, respectively. This study demonstrates PersL pressure sensing for the first time, using long‐lasting (seconds) lifetime as a manometric parameter. The developed material functions as an exceptionally sensitive triple‐mode visual pressure sensor; specifically, it exhibits: i) a sensitivity of ≈−297.4 cm GPa−1 (8.11 nm GPa−1) in bandshift mode, ii) a sensitivity of ≈272.7 cm−1/GPa (14.8 nm GPa−1) in bandwidth mode, and iii) a sensitivity of 42%GPa−1 in PL‐lifetime mode, which is the highest value reported to date. Notably, anti‐counterfeiting, night‐vision safety‐sign, 8‐bit optical‐coding, and QR‐code applications that exhibit intense PersL are demonstrated by 3D‐printing the studied material in combination with a polymer.
Cognition in (pre)symptomatic Dutch‐type hereditary and sporadic cerebral amyloid angiopathy
Authors: van Dort Rosemarie , Kaushik Kanishk , Rasing Ingeborg , van der Zwet Reinier G. J. , Schipper Manon R. , van der Grond Jeroen , van Rooden Sanneke , van Zwet Erik W. , Terwindt Gisela M. , Middelkoop Huub A. M. , Hart Ellen P. , van Osch Matthias J. P. , van Walderveen Marianne A. A. , Wermer Marieke J. H.
Published: October 2024

INTRODUCTION

Cerebral amyloid angiopathy (CAA) is a main cause of cognitive dysfunction in the elderly. We investigated specific cognitive profiles, cognitive function in the stage before intracerebral hemorrhage (ICH), and the association between magnetic resonance imaging (MRI) based cerebral small vessel disease (cSVD) burden in CAA because data on these topics are limited.

METHODS

We included Dutch‐type hereditary CAA (D‐CAA) mutation carriers with and without ICH, patients with sporadic CAA (sCAA), and age‐matched controls. Cognition was measured with a standardized test battery. Linear regression was performed to assess the association between MRI‐cSVD burden and cognition.

RESULTS

D‐CAA ICH− mutation carriers exhibited poorer global cognition and executive function compared to age‐matched controls. Patients with sCAA performed worse across all cognitive domains compared to D‐CAA ICH+ mutation carriers and age‐matched controls. MRI‐cSVD burden is associated with decreased processing speed.

DISCUSSION

CAA is associated with dysfunction in multiple cognitive domains, even before ICH, with increased MRI‐cSVD burden being associated with slower processing speed.

Highlights

Cognitive dysfunction is present in early disease stages of cerebral amyloid angiopathy (CAA) before the occurrence of symptomatic intracerebral hemorrhage (sICH).

Presymptomatic Dutch‐type CAA (D‐CAA) mutation carriers show worse cognition than age‐matched controls.

More early awareness of cognitive dysfunction in CAA before first sICH is needed.

Increased cerebral small vessel disease CAA‐burden on magnetic resonance imaging is linked to a decrease in processing speed.
Comparison of brief olfactory and cognitive assessments to neuroimaging biomarkers in the prediction of cognitive decline and dementia in the MCSA cohort
Authors: Devanand Davangere P. , Lee Seonjoo , Luchsinger José A. , Knopman David , Vassilaki Maria , Motter Jeffrey N.
Published: October 2024

INTRODUCTION

We evaluated impaired odor identification and global cognition as simple, cost‐effective alternatives to neuroimaging biomarkers to predict cognitive decline and dementia in the Mayo Clinic Study of Aging.

METHODS

Six hundred forty‐seven participants (mean 8.1, standard deviation 3.4 years’ follow‐up) had the following baseline procedures: modified Blessed Information Memory Concentration Test (BIMCT), 12‐item Brief Smell Identification Test (BSIT), structural brain magnetic resonance imaging (MRI), and positron emission tomography (PET) imaging with 11C‐Pittsburgh compound B (11C‐PiB) and fluorodeoxyglucose (FDG; subset).

RESULTS

Cognitive decline developed in 102 participants and dementia in 34 participants. In survival analyses, PiB PET showed robust prediction for cognitive decline. Impaired BSIT, impaired BIMCT, MRI, and FDG measures were also significant predictors. The combination of demographics + BSIT + BIMCT showed strong predictive utility (C‐index 0.81), similar to demographics + PiB PET (C‐index 0.80). Similar but stronger results were obtained for prediction of dementia.

DISCUSSION

Impairment in both odor identification test and global cognition was comparable to PiB PET for predicting cognitive decline and dementia.

Highlights

In 647 participants in the population‐based Mayo Clinic Study of Aging, several clinical markers and biomarkers each predicted cognitive decline or dementia during an average 8 years of follow‐up.

The combination of the demographic variables of age, sex, and education with a brief odor identification test (BSIT) and a global cognitive test (Blessed Information Memory Concentration Test) showed strong predictive utility (C‐index 0.81) for cognitive decline that was similar to the demographic variables combined with Pittsburgh Compound B amyloid imaging (C‐index 0.80).

Combining a brief odor identification test with a brief cognitive test needs consideration as a simple, cost‐effective option in the clinical assessment of individuals at risk of cognitive decline and dementia, as well as a potential tool to identify individuals who may benefit from disease‐modifying treatments and to screen participants for prevention trials.
n‐ZrS3/p‐ZrOS Photoanodes with NiOOH/FeOOH Oxygen Evolution Catalysts for Photoelectrochemical Water Oxidation
Authors: Tian Zhangliu , Wang Meng , Chen Ganwen , Chen Jie , Da Yumin , Zhang Hanqian , Jiang Rui , Xiao Yukun , Cui Baihua , Jiang Chonglai , Ding Yishui , Yang Jinlin , Sun Zejun , Han Cheng , Chen Wei
Published: October 2024

Photoelectrochemical water splitting offers a promising approach for carbon neutrality, but its commercial prospects are still hampered by a lack of efficient and stable photoelectrodes with earth‐abundant materials. Here, we report a strategy to construct an efficient photoanode with a coaxial nanobelt structure, comprising a buried‐ZrS3/ZrOS n−p junction, for photoelectrochemical water splitting. The p‐type ZrOS layer, formed on the surface of the n‐type ZrS3 nanobelt through a pulsed‐ozone‐treatment method, acts as a hole collection layer for hole extraction and a protective layer to shield the photoanode from photocorrosion. The resulting ZrS3/ZrOS photoanode exhibits light harvesting with good photo‐to‐current efficiencies across the whole visible region to over 650 nm. By further employing NiOOH/FeOOH as the oxygen evolution reaction cocatalyst, the ZrS3/ZrOS/NiOOH/FeOOH photoanode yields a photocurrent density of ~9.3 mA cm−2 at 1.23 V versus the reversible hydrogen electrode with an applied bias photon‐to‐current efficiency of ~3.2 % under simulated sunlight irradiation in an alkaline solution (pH=13.6). The conformal ZrOS layer enables ZrS3/ZrOS/NiOOH/FeOOH photoanode operation over 1000 hours in an alkaline solution without obvious performance degradation. This study, offering a promising approach to fabricate efficient and durable photoelectrodes with earth‐abundant materials, advances the frontiers of photoelectrochemical water splitting.
Modulating Pore Wall Chemistry Empowers Sonodynamic Activity of Two‐Dimensional Covalent Organic Framework Heterojunctions for Pro‐Oxidative Nanotherapy
Authors: Wu Ruohui , Hua Mengying , Lu Yanjia , Chen Liang , Chen Yu , Hu Zhongqian
Published: October 2024

Covalent organic frameworks (COFs) have garnered growing interest in the field of biomedicine; however, their application in sonodynamic therapy remains underexplored due to limited understanding of their intrinsic activity and structure–property relationships. Here, we present a pore wall chemistry modulation strategy for empowering sonodynamic activity to two‐dimensional (2D) COF heterojunctions through in situ growth of COFs on bismuth oxycarbonate nanosheets (B NSs). Compared to the negligible sonodynamic effects observed in the pristine B NSs, the 2D heterojunction with vinyl‐decorated COF pore walls demonstrates a 3.6‐fold enhancement in sonocatalytic singlet oxygen generation. This performance also significantly outperforms that of isoreticular COFs functionalized with methoxy or non‐substituted groups. Mechanistic studies reveal that the vinyl groups in the B@COF (BC) heterojunction facilitate the separation and transfer of charge carriers while also enhancing the adsorption of oxygen molecules. Furthermore, peroxymonosulfate (PMS) loading into the porous COFs boosts the therapeutic efficacy of antitumor nanotherapy via sonocatalytic dual oxidative species generation. These findings underscore the critical role of pore wall chemistry in modulating the sonocatalytic properties of COFs, and advance the development of COF‐based sonosensitizers for pro‐oxidative applications.
Ferroelectric Dipoles Tailoring Solid‐Electrolyte‐Interphase Chemistry to Enable Reversible Lithium Metal Batteries
Authors: Xu Baolei , Zhang Chunxiao , Wang Wenran , Zhu Hai , Ma Li , Wang Meiyu , Liang Chaoping , Zhou Liangjun , Wang Li , Chen Libao , Ivey Douglas G. , Wei Weifeng
Published: October 2024

Solid‐electrolyte interphase (SEI) plays a decisive role in building reliable Li metal batteries. However, the scarcity of anions in Helmholtz layer (HL) caused by electrostatic repulsion usually leads to the inferior SEI derived from solvents, resulting in dendrites and ‘dead’ Li. Therefore, regulating the distribution of anions in electric double layer (EDL) and continuously introducing more anions into HL to tailor anions‐derived SEI is crucial for achieving stable Li plating/stripping. Herein, by jointly utilizing the controlled defects of reduced graphene oxide (rGO) and the oriented dipoles of ferroelectric BaTiO3 (BTO), the rGO‐BTO composite layer sustainedly brings more TFSI− and NO3− into anion‐defecient HL, promoting favorable decomposition of anions and guiding the generation of robust and fast‐Li+‐transport SEI containing more inorganics LiF and Li3N species. Thus, the resulting Li deposit shows smooth and dense morphologies without dendrites, leading to high average Coulombic efficiency. The Li//Cu@rGO‐BTO (10 mAh cm−2 plated Li) cell exhibits an enhanced Li plating/stripping stability (2700 h) and a higher rate capability. The LiFePO4 full cell (N/P≈6.3) using rGO‐BTO displays an enhanced capacity retention (82.0 % @ 430 cycles). This work provides a new insight on the construction of robust SEI by regulating the distribution of anions within EDL.
Photo‐Triggered Fluorescence Polyelectrolyte Nanoassemblies: Manipulate and Boost Singlet Oxygen in Photodynamic Therapy
Authors: Yao Yongkang , Chen Shangjun , Yan Chenxu , Wang Junyou , Liu Jianjun , Zhu Wei‐Hong , Fan Chunhai , Guo Zhiqian
Published: October 2024

Photodynamic therapy (PDT) is a clinically approved therapeutic modality that has shown great potential for cancer treatment. However, there exist two major problems hindering PDT applications: the nonspecific phototoxicity requiring patients to stay in dark post‐PDT, and the limited photodynamic efficiency. Herein, we report a photo‐triggered porphyrin polyelectrolyte nanoassembling (photo‐triggered PPN) strategy, in which porphyrin photosensitizer and photoswitchable energy accepter are assembled into polyelectrolyte micelles by a combined force of charge interaction and metal‐ligand coordination. The polyelectrolyte‐based PPN exhibits good biocompatibility, and bestows a unique “confining isolated” inner microenvironment for fully overcoming the π–π stacking of porphyrins with significant photodynamic efficiency (123‐fold enhancement). Due to the high Förster resonance energy transfer (FRET) (91.5 %) between porphyrin and photoswitch in closed‐form, we could use light as a specific trigger to modulate photoswitch between closed‐ and open‐form, and manipulate the 1O2 generation in three stages: pre‐PDT (quenching 1O2 generation), during PDT (activating 1O2 generation), and post‐PDT (silencing 1O2 generation). This de novo strategy has for the first time realized remotely manipulating and boosting 1O2 generation in PDT, well resolving the critical and general challenges of limited photodynamic efficiency and side effects from nonspecific phototoxicity.
Resolving Structures of Paramagnetic Systems in Chemistry and Materials Science by Solid‐State NMR: The Revolving Power of Ultra‐Fast MAS
Authors: Koppe Jonas , Sanders Kevin J. , Robinson Thomas C. , Lejeune Arthur L. , Proriol David , Wegner Sebastian , Purea Armin , Engelke Frank , Clément Raphaële J. , Grey Clare P. , Pell Andrew J. , Pintacuda Guido
Published: October 2024

Ultra‐fast magic‐angle spinning (100+kHz) has revolutionized solid‐state NMR of biomolecular systems but has so far failed to gain ground for the analysis of paramagnetic organic and inorganic powders, despite the potential rewards from substantially improved spectral resolution. The principal blockages are that the smaller fast‐spinning rotors present significant barriers for sample preparation, particularly for air/moisture‐sensitive systems, and are associated with low sensitivity from the reduced sample volumes. Here, we demonstrate that the sensitivity penalty is less severe than expected for highly paramagnetic solids and is more than offset by the associated improved resolution. While previous approaches employing slower MAS are often unsuccessful in providing sufficient resolution, we show that ultra‐fast 100+kHz MAS allows site‐specific assignments of all resonances from complex paramagnetic solids. Combined with more reliable rotor materials and handling methods, this opens the way to the routine characterization of geometry and electronic structures of functional paramagnetic systems in chemistry, including catalysts and battery materials. We benchmark this approach on a hygroscopic luminescent Tb3+ complex, an air‐sensitive homogeneous high‐spin Fe2+ catalyst, and a series of mixed Fe2+/Mn2+/Mg2+ olivine‐type cathode materials.
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

Using 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

Heterogeneous 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

Photocatalytic 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

A 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

The 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

Ferric 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

There 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

Evaluating 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

This 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

A 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

Background

We 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.

Methods

We 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.

Results

The 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).

Conclusions

PFS/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

Background

Venous 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.

Aim

Validating 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 Methods

We 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.

Results

Among 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.

Conclusions

Our 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

Transformations 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

Aromatic 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.
Prevalence of carotid ultrasound screening in survivors of childhood cancer: A report from the Childhood Cancer Survivor Study
Authors: Bryce Yolanda , Whitton Jillian A. , Stratton Kayla L. , Leisenring Wendy M. , Chow Eric J. , Armstrong Gregory , Weil Brent , Dieffenbach Bryan , Howell Rebecca M. , Oeffinger Kevin C. , Nathan Paul C. , Tonorezos Emily S.
Published: October 2024

Introduction

Many childhood cancer survivors are at risk for cardiovascular disease and stroke. The North American Children's Oncology Group long‐term follow‐up guidelines recommend carotid ultrasound in cancer survivors 10 years after neck radiation therapy (RT) ≥40 Gy. The use of carotid ultrasound in this population has not been described.

Methods

Survivors of childhood cancer diagnosed 1970‐1999 (N = 8693) and siblings (N = 1989) enrolled in the Childhood Cancer Survivor Study were asked if they had ever had a carotid ultrasound. Prevalence of carotid ultrasound was evaluated. Prevalence ratios (PR) and 95% confidence intervals (CIs) were evaluated in multivariate Poisson regression models.

Results

Among participants with no reported cardiovascular condition, prevalence of carotid ultrasound among survivors with RT ≥40 Gy to the neck (N = 172) was 29.7% (95% CI, 22.5–36.8), significantly higher than those with <40 Gy (prevalence 10.7%; 95% CI, 9.9%–11.4%). Siblings without a cardiovascular condition (N = 1621) had the lowest prevalence of carotid ultrasound (4.7%; 95% CI, 3.6%–5.7%). In a multivariable models among survivors with no reported cardiovascular condition and RT ≥40 Gy to the neck, those who were over age 50 (vs. 18–49) at follow‐up (PR = 1.82; 95% CI, 1.09–3.05), with a history of seeing a cancer specialist in the last 2 years (PR = 2.58; 95% CI, 1.53–4.33), or having a colonoscopy (PR = 2.02; 95% CI, 1.17–3.48) or echocardiogram (PR = 6.42; 95% CI, 1.54–26.85) were more likely to have had a carotid ultrasound.

Conclusion

Many survivors do not undergo carotid ultrasound despite meeting existing guidelines. Health care delivery features such as having seen a cancer specialist or having other testing are relevant.
In Situ Preparation of Highly Active and Selective Fe‐MOF/V–C3N4 for Photocatalytic Hydroxylation of Benzene to Phenol
Authors: Jia Xu , Qiao Jiaolong , Xu Xuetong , Liu Cong , Zhang Liuxue , Liu Mengge , Zhang Huiqin , Li Wenzhuo , Jiao Shuyan , Wang Xiulian
Published: October 2024

The selective photocatalytic oxidation of benzene to phenol under mild conditions is of great significance for the next‐generation phenol industry. In order to improve the efficiency of the phenol production process, a heterojunction catalyst based on Fe‐MOF/V–C3N4 was synthesized by solvothermal method. Compared with Fe‐MOF and C3N4, the photogenerated charge separation rate of this composite catalyst was significantly enhanced, and the photogenerated electron‐hole complexation was significantly weakened.Under the optimal conditions, the yield and selectivity of phenol were 18.75 % and 96 % respectively, and the photocatalytic activity remained high after four reaction cycles. The improved strategy for this catalyst will provide some new insights for the development of more efficient photocatalysts for the direct hydroxylation of benzene to phenol.
On the Pólya conjecture for the Neumann problem in planar convex domains
Authors: Filonov N.
Published: October 2024

Denote by the counting function of the spectrum of the Neumann problem in the domain on the plane. G. Pólya conjectured that . We prove that for convex domains . Here is the first zero of the Bessel function .
Safety, Tolerability, Pharmacodynamics, and Pharmacokinetics of Recombinant Neorudin, a New Anticoagulant Drug in Patients With Acute Coronary Syndrome
Authors: Liu Yu‐bin , Liang Yan , Liu Hui‐chen , Feng Guang‐xun , Zhou Xing‐chen , Zhang Lin , Zhang Xiao‐long , Li Qiang , Ren Bo‐yuan , Xia Xia , Zhu Jun , Wu Chu‐tse , Jin Ji‐de
Published: October 2024

This study evaluated the safety, tolerability, pharmacodynamics, and pharmacokinetics of recombinant neorudin (EPR‐hirudin [EH]) in patients with acute coronary syndrome (ACS), providing a basis for further therapeutic research. This open‐label, single‐center, nonrandomized, nonblinded, and noncontrolled trial categorized 24 patients with nonprogressive ACS who met the screening criteria into 3 groups. They received an intravenous injection of neorudin (0.4 mg/kg), followed by an intravenous drip at doses of 0.15, 0.30, and 0.45 mg/kg/h for 3 days in the low‐, medium‐, and high‐dose groups, respectively. The safety, tolerability, pharmacodynamics, and pharmacokinetics of EH were assessed after treatment, indicating that neorudin was safe and well tolerated in nonprogressive ACS. No serious adverse events or clinical composite end points were observed. The activated partial thromboplastin time and thrombin time increased significantly and dose dependently following EH administration across all groups compared to pretreatment values. Conversely, thrombin activity significantly decreased after drug administration but returned to baseline levels shortly after drug withdrawal. Within the administered dose range, neorudin exposure increased with the dose, and its half‐life was approximately 2 hours. Neorudin was found to be safe and tolerable for treating patients with nonprogressive ACS, demonstrating therapeutic efficacy at doses up to 0.45 mg/kg/h over a 3‐day period.
Conformational and Solvent Effects on the Photoinduced Electron Transfer Dynamics of a Zinc Phthalocyanine–Benzoperylenetriimide Conjugate: A Nonadiabatic Dynamics Simulation
Authors: Liu Sha‐Sha , Wei Xin , Zheng Yan , Liu Shuai , Xu Dong‐Hui , Li Laicai , Cui Ganglong , Liu Xiang‐Yang
Published: October 2024

Herein, we employed a combination of static electronic structure calculations and nonadiabatic dynamics simulations at linear‐response time dependent density functional theory (LR‐TDDFT) level with the optimally tuned range‐separated hybrid (OT‐RSH) functional to explore the ultrafast photoinduced dynamics of a zinc phthalocyanine‐benzoperylenetriimide (ZnPc‐BPTI) conjugate. Due to the flexibility of the linker, we identified two major conformations: the stacked conformation (ZnPc‐BPTI‐1) and the extended conformation (ZnPc‐BPTI‐2). Since the charge transfer states are much lower than the lowest local excitation in ZnPc‐BPTI‐1, which is contrary to ZnPc‐BPTI‐2, the ultrafast electron transfer (~3.6 ps) is only observed in the nonadiabatic simulations of ZnPc‐BPTI‐1 upon local excitation around the absorption maximum of ZnPc. However, when considering the solvent effects in benzonitrile: the lowest S1 states are both charge transfer states from ZnPc to BPTI for different conformers. Subsequent nonadiabatic dynamics simulations indicate that both conformers experience ultrafast electron transfer in benzonitrile with two time constants of 90 [100] fs and 1.40 [1.43] ps. Our present work not only agrees well with previous experimental study, but also points out the important role of conformational changes and solvent effects in regulating the photodynamics of organic donor‐acceptor conjugates.
Stoichiometric‐Ratio‐Controlled Fe and Ni Non‐Noble Metal Catalysts Supported on γ‐Al2O3 for Turquoise Hydrogen and Carbon Nanotubes Production
Authors: Rajpoot Aakash , Ahmad Khan Afaq , Mohan Indra , Sengupta Siddhartha , Ahmad Ejaz
Published: October 2024

Herein, we synthesized a series of catalysts comprising iron (Fe), and nickel (Ni) supported on γ‐Al2O3 nano‐powder (Fe−Ni/γ‐Al2O3) by controlling the stoichiometric ratio of the metals through the facile co‐precipitation method. The ratio of Fe and Ni on the γ‐Al2O3 support varied from 0 to 70 weight percent (wt %). The freshly prepared catalysts phase, structure, and crystallinity exhibited variability as the Fe and Ni stoichiometric ratios were altered. The catalyst demonstrated effective performance in methane cracking, producing turquoise hydrogen and carbon nanotubes (CNTs) using a temperature‐programmed reactor coupled with mass spectrometry. It was observed that the Fe3Ni4 catalyst, comprising 30 % Fe and 40 % Ni, exhibited a maximum methane conversion rate of 85 % and a hydrogen yield of 72.55 %. Moreover, the values of turnover frequency (2.38 min−1) indicated that the Fe3Ni4 had a better production rate and was consistent with the conversion process throughout the reaction. The structural attributes of the spent catalysts were examined, revealing variations in the lateral length, uniformity, and diameters (~33 to 56 nm) of the produced Carbon Nanotubes (CNTs) when transitioning from catalyst Fe0Ni7 to Fe7Ni0. The investigation underscored the significance of metal stoichiometrically controlled catalysts and their catalytic efficacy in methane cracking applications.
Orbital‐Driven Insights into Enantioselective Hydrofunctionalization of Alkenes Catalyzed by Co‐Salen Complexes: Study on Singlet and Triplet States
Authors: Gupta Shivangi , Rawal Parveen , Gupta Puneet
Published: October 2024

The Co(salen) ([LCo(II)]) mediated hydrofunctionalization of alkenes is a highly significant method for forming enantioselective products. In this work, we conducted comprehensive computational investigations to gain insights of the reaction mechanism. The orbital analysis and intrinsic bond orbital analysis (IBO) were utilized to unravel the flow of electrons during the progress of the reaction. We explored various spin state surfaces to understand the possible pathways for the reaction. Initially, [LCo(II)] reacts with an oxidant tertbutyl peroxybenzoate, yielding [LCo(III)OC(O)Ph] and [LCo(III)OtBu]. Subsequently, [LCo(III)OC(O)Ph] reacts with silane to form cobalt hydride ([LCo(III)H]), with the triplet spin state surface being the preferred pathway, featuring an energy barrier of 14.2 kcal mol−1. IBO analysis across this step revealed that it involves the transfer of hydrogen as a hydride. Subsequently, the [LCo(III)H] complex in a triplet spin state undergoes a minimum energy crossing point (MECP) to transition into the singlet spin state, representing its most stable configuration. The [LCo(III)H] complex further reacts with styrene via hydrogen atom transfer on the singlet spin state surface, followed by oxidation and subsequent reaction with indole on the doublet spin surface to yield the hydrofunctionalized product. This work also explores potential enantioselective steps in the reaction.