bluuebunny/crossref_metadata_2025 huggingface dataset:
Prenatal exposure to pesticide mixture in Argentina: A pilot study in puerperal women from Santa Fe province
Authors: Colussi Carlina Leila , Martinez Guillaume , Bellenger Jean‐Philippe , Poletta Gisela Laura , Simoniello María Fernanda
Published: February 2024

Introduction

The epidemiological investigation of congenital anomalies (CA) represents a challenge due to the multiplicity of associated risk factors, notably environmental ones. The monitoring of genotoxic effects in different populations is a useful tool in human biomonitoring and has great biological importance in estimating the exposure risks to complex mixtures of chemical substances.

Objective

This study aimed to determine the presence of environmental xenobiotics and evaluate their genotoxic effect, in mothers of newborns with and without CA, and the possible association/correlation between those biomarkers and CA.

Materials and methods

A descriptive case and control cross‐sectional study was developed on 290 postpartum women from Santa Fe, Argentina.

Results

Significant differences were observed between both groups, for places of residence and gynecological variables. Metabolites of organochlorine (OC), organophosphate (OP), and pyrethroid (PYR) pesticides were detected. The most frequently detected compounds were atrazine (ATZ) (57.14%), carbendazim (CBZ) (46.42%), and methylparaben (46.42%), among others. A positive correlation was found between the number of pesticides in blood and genotoxic variables. On the other hand, mothers of children with genitourinary anomalies were the ones with the highest concentrations of ATZ and OP.

Discussion and conclusion

These results showed a deep background in the health reality of Santa Fe, which could greatly impact the health of future adults, who have been born preterm. On the other hand, the mixture of pesticides detected confirms the environmental living conditions of women and the transplacental exposure to these compounds in each pregnancy. The potential effects on long‐term descendent health are unknown and unpredictable.
Virtual schools for care‐experienced learners in Scotland: Reflections on an emerging concept in a new context
Authors: McIver Leanne , Bettencourt Michael
Published: February 2024

The ‘virtual school’ is an approach to supporting care‐experienced children and young people in education. The Virtual School Head (VSH) has been a statutory role within the education landscape in England since 2014. In Scotland, where the education, social care and legal systems are distinct from those in England, there has been a recent increase in the number of local authorities utilising this concept. This research aimed to explore the role and remit of Virtual School Head Teachers (VSHTs) in Scotland, and to identify similarities and differences with those of VSHs in England, to uncover learning about the emergence of this concept and role in a new context. We conducted semi‐structured interviews with relevant post‐holders in Scotland, using key concepts from the published literature on virtual schools in England, and analysed these qualitatively to identify themes. We discuss some of the similarities and differences we identified, noting that while the purpose of the role, and the means by which it functions, were largely common to both countries, there were also nuanced differences. Key similarities included the importance of positioning within the local authority, and the development of relationships with social work. Differences were largely underpinned by the educational and legal contexts in which the post‐holders operated, and included control of budgets and specificity of remit. This research contributes to our understanding of the role of the VSHT in Scotland, and identifies some emerging features as the virtual school concept is translated to a new context.
Einfluss einer Wärmebehandlung auf das Verbundkriechen von hochfestem Beton
Authors: Schwarz Yannik , Sanio David , Mark Peter
Published: February 2024

Die Verbundwirkung von Beton und Betonstahl ermöglicht es, Kräfte zwischen den beiden Baustoffen zu übertragen. An der mechanischen Verzahnung der Rippen mit dem umliegenden Beton entstehen dabei hohe Druckspannungen auf die Betonkonsolen. Dies führt bei Dauerlast zu Kriechverformungen (Verbundkriechen). Die Relativverschiebung (Schlupf) zwischen Bewehrungsstab und Beton nimmt dabei stetig zu, was sich nachteilig auf Rissbreiten und Dauerhaftigkeit auswirken kann. Im Beitrag wird die Reduktion des Verbundkriechens durch eine initiale rapide Wärmebehandlung bei 80 °C mit 60 % relativer Luftfeuchte und Dauern von 4, 16 oder 24 h experimentell untersucht. Hierfür werden Probekörper aus hochfestem Beton – im Anschluss an die entsprechende Wärmebehandlung – im Auszugsversuch für 300 d mit einer konstanten Dauerlast beaufschlagt und der kontinuierliche Anstieg der Relativverschiebungen aufgezeichnet. Als Referenz dienen nicht temperierte Proben. Die Kriechverformungen werden anhand von unbelasteten Proben von den Schwindeffekten separiert. Zudem werden unerwünschte Biegeeffekte aus der unvermeidlichen Vorkrümmung der Betonstähle identifiziert und rechnerisch eliminiert. Die Ergebnisse zeigen, dass durch die Wärmebehandlung das Verbundkriechen um etwa 40 % geringer ausfällt.
Crocus sativus tepals extract suppresses subcutaneous adipose tissue hypertrophy and improves systemic insulin sensitivity in mice on high‐fat diet
Authors: Bursać Biljana , Bellachioma Luisa , Gligorovska Ljupka , Jovanović Mirna , Teofilović Ana , Vratarić Miloš , Vojnović Milutinović Danijela , Albacete Alfonso , Martínez‐Melgarejo Purificación A. , Morresi Camilla , Damiani Elisabetta , Bacchetti Tiziana , Djordjevic Ana
Published: February 2024

Obesity is a pressing problem worldwide for which standard therapeutic strategies have limited effectiveness. The use of natural products seems to be a promising approach to alleviate obesity and its associated complications. The tepals of Crocus sativus (Cr) plant, usually wasted in saffron production, are an unexplored source of bioactive compounds. Our aim was to elucidate the mechanisms of Cr tepals extract in obesity by investigating its effects on adipocyte differentiation, visceral adipose tissue (VAT) and subcutaneous adipose tissue (SAT) hypertrophy, and lipid metabolism in an animal model of diet‐induced obesity. To this end, mouse 3T3‐F442A preadipocytes were treated with Cr tepals extract and the expression of adipocyte differentiation genes was determined. Caloric intake, body mass, triglycerides, systemic insulin sensitivity, histology, insulin signaling, and lipid metabolism in VAT and SAT were analyzed in mice fed a 60% fat diet for 14 weeks and treated orally with Cr tepals extract during the last 5 weeks of the diet. We demonstrated for the first time that Cr tepals extract inhibits adipocyte differentiation in vitro. The animal model confirmed that oral treatment with Cr tepals extract results in weight loss, improved systemic insulin sensitivity, lower triglycerides, and improved lipid peroxidation. The suppressive effect of Cr tepals extract on adipocyte hypertrophy and inflammation was observed only in SAT, which, together with preserved SAT insulin signaling, most likely contributed to improved systemic insulin sensitivity. Our results suggest the functionality of SAT as a possible target for the treatment of obesity and its complications.
Digitalisation and environmental management activities: The effects of family ownership`
Authors: Issah Wunnam Basit , Ferdous Lutfa Tilat , Bhuiyan Faruk , Sharif Taimur
Published: February 2024

While digitalisation has significant implications for environmental management activities, this nexus has received minimal attention in research. Given this backdrop, this study uses a unique survey dataset of 386 micro and small enterprises (MSEs) and conducts an OLS regression analysis to examine the impact of digitalisation on environmental management activities. The study also investigates how family ownership moderates this relationship. The study finds that digitalisation supports environmental management activities as an important strategic mechanism, and that family ownership has a negative moderating effect on the relationship between digitalisation and environmental management activities. This study contributes to ‘institutional theory’ by highlighting its applicability to the new context of MSEs in emerging markets. Further, the study provides managerial insights into how to ensure environmental management practices in the digital age.
Finite element analysis megatrends: A road less traveled
Authors: Patil Arun Y. , Kundu Tanmay , Kumar Raman
Published: February 2024

In today's environment, finite element analysis is crucial for Mechanical Engineers. In today's highly competitive industries, graduates need to be productive from Day one as they enter the industry. To meet the vast range of industrial requirements or even for higher education, education institutes must adhere to an industry enabled curriculum as defined in collaboration with industry employees. As students reach their prefinal year of mechanical engineering studies, they will encounter courses like finite element analysis, design of machine elements, and failure analysis in design, which will serve as foundation steps for their future careers. As students need to compete in the real world, it becomes imperative to have a thorough understanding of both theoretical and practical issues. The focus of current work is to provide them a platform to think as a real‐time problem‐solving engineer to address the society‐based problems and how he/she approaches the problem in an optimized way and finally, convert the entire work to tangible documents in the form of research articles. Since 2018, a new vertical called as “advanced computer aided engineering (CAE)” has emerged to link and prepare people for the business. In the realm of finite element method (FEM) theoretical and allied laboratory work, the current study discusses sustainability while selecting the problem statement. The entire emphasis is on eco‐environment with nature's sustainability along with the go‐green concept in terms of materials, design, optimization, cost, quality, and so on. The present work includes several new features that were not present in the previous curriculum, such as transforming the work to high‐quality journals, student feedback, subscription‐based journal selection for the manuscript, and embedding experimental and analytical work alongside simulation studies. This time, 40 teams participated, with around 36 project works being qualified for publication in prestigious journals and 8–10 works being filed for Indian patents. In terms of quality and quantity of work completed, this is the best output attained in contrast to previous iterations. Because of the increasing growth rate of higher education, our students have been able to get into Top 100 QS ranked universities. The figures show that because of faculty involvement in the FEM lab, Advanced CAE I, and Advanced CAE II, over the previous 4–5 years, students were able to publish more than 50 publications in prestigious peer‐reviewed International/National Journals and Conference papers.
Comparison of IL‐2‐antibody to IL‐2‐Fc with or without stereotactic radiation therapy in CEA immunocompetent mice with CEA positive tumors
Authors: Williams Lindsay , Li Lin , Yazaki Paul J. , Wong Patty , Hong Teresa , Poku Erasmus K. , Hui Susanta , Ghimire Hemendra , Shively John E. , Kujawski Maciej
Published: February 2024

Background

The potent immune effects of interleukin‐2 (IL‐2) for cancer therapy can be increased by genetic fusion of IL‐2 to the Fc domain of an antibody (IL‐2‐Fc) or tumor targeted by genetic fusion to a whole antibody known as an immunocytokine (ICK).

Methods

An anti‐CEA ICK (M5A‐IL‐2) was compared to an IL‐2‐Fc fusion protein using tumor therapy and PET imaging in CEA transgenic immunocompetent mice bearing CEA positive colon or breast tumors. Combination with stereotactic radiation therapy (SRT) was performed with either ICK or IL‐2‐Fc.

Results

ICK and IL‐2‐Fc had comparable antitumor effects in both tumor models, although ICK had higher tumor uptake and slower blood clearance than an IL‐2‐Fc. Analysis of IFNγ+/CD8+ and FoxP3+/CD4+ T cells revealed higher levels of IFNγ‐producing CD8+ T cells in ICK treated mice versus more efficient Treg elimination in IL‐2‐Fc treated mice. No significant or lasting toxicity was detected for either agent. Combination therapies with SRT revealed comparable efficacy and induction of immune memory for both ICK and IL‐2‐Fc when mice were rechallenged post‐therapy.

Conclusions

IL‐2‐Fc had comparable antitumor efficacy to CEA‐targeted M5A‐IL‐2 ICK, while both fusion proteins induced immune memory when combined with SRT. Differences in the therapeutic mechanisms of both agents were observed.
Experiences of caregivers of children with cancer in Malawi: A qualitative study
Authors: Phiri Lophina , Li William Ho Cheung , Phiri Patrick G. M. C. , Cheung Ankie Tan , Wanda‐Kalizang'oma Watipaso , Kamwendo Anizia , Lemon Sellina
Published: February 2024

Background

Studies have shown that caregivers of children with cancer experience challenges when caring for their children. To date, no studies have examined the experience of caregivers of children with cancer in Malawi, a low‐income country in sub‐Saharan Africa. Hence, this study aimed to explore the experiences of caregivers of Malawian children receiving cancer treatment.

Methods

This explorative qualitative study used semi‐structured interviews to collect data from 22 caregivers of children receiving cancer treatment. The data were analysed using qualitative content analysis.

Results

Five themes emerged from the QCA. The caregivers perceived their children's cancer as a burden, a form of psychological torture and a disruptor of family routines and social lifestyles. They also reported self‐isolation due to the stigma that they faced in the course of caring for their children and a need for informational, psychosocial, spiritual and financial support.

Conclusion

Caregivers of Malawian children with cancer experience physical and psychosocial challenges as they are caring for their children with cancer. Developing appropriate interventions would enable nurses to offer optimal support to these caregivers in dealing with these challenges and meeting their needs effectively.
Novel Bis(2‐cyanoacrylamide) Linked to Sulphamethoxazole: Synthesis, DNA Interaction, Anticancer, ADMET, Molecular Docking, and DFT Studies
Authors: Ragheb Mohamed A. , Mohamed Fatma G. , Diab Hadeer M. , Ragab Mona S. , Emara Marwan , Elwahy Ahmed H. M. , Abdelhamid Ismail A. , Soliman Marwa H.
Published: February 2024

In the light of advancement and potential extensive use of medication design and therapy, new bis(cyanoacrylamides) incorporating sulphamethoxazole derivatives (7 a–7 f) were synthesized and confirmed by different spectral tools. In vitro anticancer activity towards different human cancer cells (HCT116, MDA‐MB‐231 and A549) was assessed using MTT assay. Among all derivatives, 4C‐ and 6C‐spacer derivatives (7 e and 7 f) had the most potent growth inhibitory activities against HCT116 cells with IC50 values of 39.7 and 28.5 μM, respectively. 7 e and 7 f induced apoptosis and suppressed migration of HCT116 cells. These compounds also induced a significant increase in caspase‐3 and CDH1 activities, and a downregulation of Bcl2 using ELISA. pBR322 DNA cleavage activities of cyanoacrylamides were determined using agarose gel electrophoresis. Furthermore, 7 e and 7 f showed good DNA and BSA binding affinities using different spectroscopic techniques. Furthermore, molecular docking for 7 e and 7 f was performed to anticipate their binding capabilities toward various proteins (Bcl2, CDH1 and BSA). The docking results were well correlated with those of experimental results. Additionally, density functional theory and ADMET study were performed to evaluate the molecular and pharmacokinetic features of 7 e and 7 f, respectively. Thus, this work reveals promising antitumor lead compounds that merit future research and activity enhancement.
Discovery of α‐Obscurine Derivatives as Novel Cav3.1 Calcium Channel Blockers
Authors: Wang Lei , Li Wen‐Yan , Yuan Zai‐Feng , Zhao Qin‐Shi
Published: February 2024

Voltage‐gated calcium channels (VGCCs), particularly T‐type calcium channels (TTCCs), are crucial for various physiological processes and have been implicated in pain, epilepsy, and cancer. Despite the clinical trials of TTCC blockers like Z944 and MK8998, none are currently available on the market. This study investigates the efficacy of Lycopodium alkaloids, particularly as natural product‐based TTCC blockers. We synthesized eighteen derivatives from α‐obscurine, a lycodine‐type alkaloid, and identified five derivatives with significant Cav3.1 blockade activity. The most potent derivative, compound 7, exhibited an IC50 value of 0.19±0.03 μM and was further analyzed through molecular docking, revealing key interactions with Cav3.1. These findings provide a foundation for the structural optimization of Cav3.1 calcium channel blockers and present compound 7 as a promising lead compound for drug development and a tool for chemical biology research.
Prognostic impact of peripheral artery disease in patients with and without high bleeding risk undergoing percutaneous coronary intervention
Authors: Spirito Alessandro , Cohen Rebecca , Sartori Samantha , Vogel Birgit , Baber Usman , Pileggi Brunna , Smith Kenneth , Nicosia Danielle , Kamaleldin Karim , Farhan Serdar , Kini Annapoorna , Sharma Samin K. , Dangas George , Mehran Roxana
Published: February 2024

Background

Peripheral artery disease (PAD) is associated with worse outcomes after percutaneous coronary intervention (PCI). The aim of this study was to assess the prognostic impact of PAD according to high bleeding risk (HBR) status.

Methods

Consecutive patients undergoing PCI with drug‐eluting stent implantation at a tertiary‐care center (Mount Sinai Hospital) between 2012 and 2019 were stratified according to HBR and PAD status. The primary outcome was major adverse cardiac events (MACE), a composite of all‐cause death, myocardial infarction (MI), and stroke 1 year after PCI. Secondary outcomes included major bleeding.

Results

Out of 16,750 patients, 43% were HBR and 57% were no‐HBR. Within the two groups, PAD patients were 14% and 6%, respectively, and were more likely to have comorbidities and to undergo complex PCI than no‐PAD patients. Within the HBR group, PAD was associated with an increased risk of MACE (11.4% vs. 7.3%, hazard ratio [HR]: 1.59, 95% confidence interval [CI]: 1.27–1.99, p < 0.001) and a numerical nonsignificant increase of major bleeding (8.5% vs. 6.9%, HR: 1.25, 95% CI: 0.98–1.59, p = 0.066) as compared with no‐PAD. Among no‐HBR patients, rates of MACE and major bleeding were numerically but not significantly higher in the PAD group. After multivariable adjustment, PAD was no longer a predictor of adverse outcomes, irrespective of HBR status.

Conclusions

At 1‐year after PCI, PAD was associated with increased 1‐year risks of MACE in HBR patients. After adjustment for cardiovascular risk factors and comorbidities, the effect of PAD on adverse events was largely attenuated.
Delayed replantation of avulsed permanent maxillary central incisor: Case report with 6‐year follow‐up
Authors: Rai Amita , Koirala Bandana , Dali Mamta , Shrestha Sneha
Published: February 2024

Key Clinical Message

Replantation should be attempted in any case of avulsion, be it immediate or delayed. Retention of the replanted tooth helps in preservation of adjacent alveolar bone. Despite the occurrence of replacement resorption, the tooth can stay healthy and functional in the arch for a longer duration.
Application of Intermetallic Compounds as Catalysts for the Selective Hydrogenation of CO2 to Methanol
Authors: Quilis Carlos , Mota Noelia , Millán Elena , Pawelec Barbara , Navarro Yerga Rufino M.
Published: February 2024

Direct catalytic conversion of CO2 to methanol via renewable hydrogen has emerged as a promising technology among the various CO2 conversion techniques. However, efficient hydrogenation of CO2 using conventional Cu‐ZnO‐based catalysts, which are currently used for industrial methanol production from synthesis gas, remains a challenge due to inefficient energy conversion, poor stability and sluggish CO2 conversion kinetics. As the catalytic activity, stability and methanol selectivity of conventional Cu/ZnO catalysts are still insufficient for industrial applications, novel catalyst formulations using transition metals/metal oxides and supported noble metal nanostructures have emerged. Among them, intermetallic compounds are being explored for their unique electronic and crystalline structures, which can be tailored by controlled, precise, and seamless tuning of interatomic distances, specific arrangements and electronic structure to enhance their stability and activity for the selective hydrogenation of CO2 to methanol. In this context, intermetallic catalysts containing Pd, Cu and Ni combined with metal oxide nanoparticles (ZnO, Ga2O3, In2O3, etc.) have been shown to be more effective than the classical Cu‐ZnO‐Al2O3. This review analyses the progress made in the study of these intermetallic catalysts by analysing different aspects of their preparation, characterization, effects of promoters, support interactions, etc. Future research perspectives are discussed in the context of potential industrial applications of intermetallics for direct methanol production via CO2 hydrogenation.
Synergistic Photoredox and Electrochemical Catalysis in Organic Synthesis and Late‐Stage Functionalizations
Authors: Sun Ci‐Yang , Lin Ting‐Jun , Chen Yu‐Yu , Li Hung‐Li , Chiang Chien‐Wei
Published: February 2024

This review delves into the innovative field of interfacial photoelectrochemical (iPEC) and photoelectrochemical (PEC) catalysis, the dynamic synthesis methodologies that seamlessly integrates electrochemical and photoredox catalysis for efficient and environmentally friendly reactions. Utilizing minute quantities of photocatalysts, visible light becomes a powerful tool, generating transient excited states to catalyze a spectrum of reactions through single‐electron oxidation or reduction events. The review categorizes recent advancements, highlighting applications in organic synthesis, late‐stage modifications, and the distinctive features of photoelectrochemical methodology. Despite being in its early stages, this synergistic approach holds great promise for propelling organic synthesis forward, with potential applications in large‐scale synthesis and diverse late‐stage functionalizations, including asymmetric catalysis and bioconjugation strategies for biomolecule modifications.
Nitrogen‐Based Imperfections in Graphitic Carbon Nitride – New Trend for Enhancing Photocatalytic Activity?
Authors: Eroglu Zafer , Ozer Melek Sermin , Metin Önder
Published: February 2024

This review comprehensively explores the engineering of nitrogen vacancies (N‐vacancies) in polymeric carbon nitride (CN) and uncovering their profound impact on the photocatalytic applications of CN. The intentional creation of N‐vacancies in CN obtained by removing the targeted N atoms emerges as a crucial strategy for fine‐tuning its photo(catalytic)physical properties. Defect‐centric investigations illuminate enlarged surface areas, increased substrate interactions and spotlight the correlation between N‐vacancy and photoredox transformations. Key N‐vacancies (NHx, N2C, N3C) play exceptional roles in elevating the photocatalytic activity of CN. Besides comprehensively navigating the competitive literature of CN research, this review highlights the controlled manipulation of N‐vacancies in CN as an instrumental avenue for customized property tailoring. Additionally, it provides a perspective on the generation of N‐vacancies considering temperature, time, and reaction atmosphere by inspecting available synthesis strategies, particularly thermal treatments, along with advanced characterization techniques shedding light on the profound influence of N‐vacancies on the structural and electronic properties of CN. Moreover, this review underlines the impact of defects in CN on its photocatalytic performance, tuning bandgaps, midgap state formation, and creating active sites within the lattice. The versatile strategy employed in vacancy engineering within CN shows great potential for designing new‐generation photocatalysts with tailored functionalities.
Titanium MXenes as Heterogeneous Catalysts for the Styrene‐to‐Benzaldehyde Oxidation: Influence of the Etching Conditions
Authors: Rapeyko A. , Barjola A. , Seva M. D. , Sahuquillo O. , Navalón S. , Giménez E. , Llabrés i Xamena F. X.
Published: February 2024

Ti3C2Tz MXenes are prepared under different etching conditions and tested as heterogeneous catalysts for the selective oxidation of styrene to benzaldehyde. A clear dependence is observed between the etching conditions (hydrofluoric acid concentration and etching time) and the surface chemistry, morphology and catalytic performance of the resulting MXenes. Under appropriate conditions, etching of the Ti3AlC2 MAX phase precursor with concentrated HF produces Ti3C2Tz MXenes with highly accessible accordion‐like structures and accessible Ti−O surface terminations that can act as active species for the catalytic process, keeping up with the best catalysts reported so far for this reaction. The present study represents one of the few existing reports on catalytic properties of MXenes under mild liquid‐phase conditions, paving the way for future developments of this new family of 2D materials for fine chemical applications.
Visible Light‐Induced Enantioselective Radical Reactions Catalyzed by Redox‐Active Chiral Lewis Acids
Authors: Cao Shi , Hong Sungwoo
Published: February 2024

This Concept outlines cutting‐edge progress in catalytic and enantioselective radical reactions facilitated by redox‐active chiral Lewis acids upon visible light excitation. These catalytic systems exploit the high reactivity of radical species to enable efficient stereocontrolled radical recombination. We delve into the design, underlying mechanisms, and practical applications of these catalysts, aiming for precise stereocontrolled bond formation. The synergistic blend of chirality and reactivity has brought a new level of precision to enantioselective radical additions, reshaping the approach to asymmetric synthesis. This Concept focuses on the recent progress and effective application of redox‐active chiral Lewis acids, including Rh, Ir, Ga and Ni, in catalyzing enantioselective radical reactions, which offers a comprehensive perspective on modern methods and projecting future directions in enantioselective radical chemistry.
Poly(iminoborane)s with Aromatic Side Groups: Insights into the Microstructure from Monodisperse Model Oligomers
Authors: Maier Matthias , Friedrich Alexandra , Schneider Johannes S. , Sprenger Jan A. P. , Klopf Jonas , Fritze Lars , Finze Maik , Helten Holger
Published: February 2024

While certain inorganic main‐group polymers such as silicones (polysiloxanes) are ubiquitous in our everyday life, poly(iminoborane)s have been elusive for a long time. Incorporation of heterocyclic building blocks into their backbone has recently enabled access to the first derivatives of this inorganic‐polymer class, as this approach effectively prevents undesired side‐reactions to borazines. Information about the microstructure of these cyclolinear macromolecules, however, has been scarce. Herein, we present the synthesis of a series of monodisperse oligomers with up to 7 boron and 8 nitrogen atoms, representing the longest well‐defined molecular [>B=N<]x chain to date. We accomplished to characterize six of them structurally in the solid state by single‐crystal X‐ray diffraction, thus providing valuable insight into the microstructure of poly(iminoborane)s. In addition, we report on the synthesis of new poly(iminoborane) derivatives featuring aryl side groups, with an increased content of unsubstituted phenyl groups. The p‐(n‐butyl)phenyl‐substituted species 13 represents the highest‐molecular‐weight sample of this class of inorganic polymers to date.
Near‐IR‐Absorbing Bis‐Donor Functionalized Aza‐BODIPY Derivatives: Synthesis and Photophysical Study by Using Transient Optical Spectroscopy
Authors: Pinjari Dilip , Imran Muhammad , Dad Pratiksha , Misra Rajneesh , Zhao Jianzhang
Published: February 2024

A series of near‐IR absorbing 2,6‐diarylated BF2‐chelated aza‐boron‐dipyrromethenes (aza‐BDPs) derivatives bearing different electron donors (benzene, naphthalene, phenanthrene, phenothiazine and carbazole) were designed and synthesized. The effect of different electron donor substitutions on the photophysical properties was studied by steady‐state UV‐vis absorption and fluorescence spectra, electrochemical, time‐resolved nanosecond transient absorption (ns‐TA) spectroscopy and theoretical computations. The UV‐vis absorption spectra of AzaBDP‐PTZ and AzaBDP‐CAR (λabs=710 nm in toluene) showed a bathochromic absorption profile compared with the reference AzaBDP‐Ph (λabs=685 nm in toluene), indicating the non‐negligible electronic interaction at the ground state between donor and acceptor moieties. Moreover, the fluorescence is almost completely quenched for AzaBDP‐PTZ/AzaBDP‐CAR (fluorescence quantum yield, ΦF=0.2–0.7 % in toluene) as compared with the AzaBDP‐Ph (ΦF=27 % in toluene). However, the apparent intersystem crossing ability of these compounds is poor, based on the singlet oxygen quantum yield (ΦΔ=0.3–1.5 %). The ns‐TA spectral study showed typical Bodipy localized triplet state transient features, short‐lived excited triplet state for AzaBDP‐Ph (τT=53.2 μs) versus significantly long‐lived triplet state for AzaBDP‐CAR (τT=114 μs) was observed under deaerated experimental conditions. These triplet state lifetimes are much longer than that obtained with diiodoAzaBDP (intramolecular heavy atom effect, τT=1.5~7.2 μs). These information are useful for molecular structure design of triplet photosensitizers, for which longer triplet state lifetimes are usually desired. Theoretical computations displayed that the triplet state is mainly localized on the AzaBDP core, moreover, it was found that the HOMO/LUMO energy gap decreased after introducing donor moieties to the skeleton as compared with the reference.
Influence Mechanism of Interfacial Oxidation of Li3YCl6 Solid Electrolyte on Reduction Potential
Authors: Wang Xin , Yang Zhiqiang , Li Na , Wu Kang , Gao Kesheng , Zhao Enyue , Han Songbai , Guo Wenhan
Published: February 2024

Halide‐based solid electrolytes are promising candidates for all solid‐state lithium‐ion batteries (ASSLBs) due to their high ionic conductivity, wide electrochemical window, and excellent chemical stability with cathode materials. However, when tested in practice, their intrinsic electrochemical stability windows do not well match the conditions for stable operation of ASSBs. Existing literature reports halide‐based ASSBs that still operate well outside the electrochemical stability window, while ASSBs that do not operate within the window are not well studied or the studies are based on the cathode material interface. In this study, we aim to elucidate the mechanism behind all‐solid‐state battery failure by investigating how the reduction potential of Li3YCl6 solid‐state electrolyte itself changes under overcharging conditions. Our findings demonstrate that in Li‐In|Li3YCl6|Li3YCl6‐C half‐cells during the first state of charge, Cl ions participate in charge compensation, resulting in a depletion of ligands. This phenomenon significantly affects the reduction potential of Y3+, causing it to be reduced to Y2Cl3 and ultimately to Y0 at conditions far exceeding its actual reduction potential. Furthermore, we analyze the interfacial impedance induced by this process and propose a novel perspective on battery failure.
Highly Ordered Co‐Assembly of Bisurea Functionalized Molecular Switches at the Solid‐Liquid Interface
Authors: Stähler Cosima , Reynaerts Robby , Rinkovec Tamara , Verstraete Lander , Heideman G. Henrieke , Minoia Andrea , Harvey Jeremy N. , Mali Kunal S. , De Feyter Steven , Feringa Ben L.
Published: February 2024

Immobilization of stimulus‐responsive systems on solid surfaces is beneficial for controlled signal transmission and adaptive behavior while allowing the characterization of the functional interface with high sensitivity and high spatial resolution. Positioning of the stimuli‐responsive units with nanometer‐scale precision across the adaptive surface remains one of the bottlenecks in the extraction of cooperative function. Nanoscale organization, cooperativity, and amplification remain key challenges in bridging the molecular and the macroscopic worlds. Here we report on the design, synthesis, and scanning tunneling microscopy (STM) characterization of overcrowded alkene photoswitches merged in self‐assembled networks physisorbed at the solid‐liquid interface. A detailed anchoring strategy that ensures appropriate orientation of the switches with respect to the solid surface through the use of bis‐urea groups is presented. We implement a co‐assembly strategy that enables the merging of the photoswitches within physisorbed monolayers of structurally similar ‘spacer’ molecules. The self‐assembly of the individual components and the co‐assemblies was examined in detail using (sub)molecular resolution STM which confirms the robust immobilization and controlled orientation of the photoswitches within the spacer monolayers. The experimental STM data is supported by detailed molecular mechanics (MM) simulations. Different designs of the switches and the spacers were investigated which allowed us to formulate guidelines that enable the precise organization of the photoswitches in crystalline physisorbed self‐assembled molecular networks.
Molecular Dihydrogen Activation by (C5Me5)M/N (M=Rh, Ir) Transition Metal Frustrated Lewis Pairs: Reversible Proton Migration to, and Proton Abstraction from, the C5Me5 Ligand
Authors: Ferrer‐Bru Carlos , Ferrer Joaquina , Passarelli Vincenzo , Lahoz Fernando J. , García‐Orduña Pilar , Carmona Daniel
Published: February 2024

The masked transition‐metal frustrated Lewis pairs [Cp*M(κ3N,N’,N’’‐L)][SbF6] (Cp*=η5‐C5Me5; M=Ir, 1, Rh, 2; HL=pyridinyl‐amidine ligand) reversibly activate H2 under mild conditions rendering the hydrido derivatives [Cp*MH(κ2N,N’‐HL)][SbF6] observed as a mixture of the E and Z isomers at the amidine C=N bond (M=Ir, 3Z, 3E; M=Rh, 4Z, 4E). DFT calculations indicate that the formation of the E isomers follows a Grotthuss type mechanism in the presence of water. A mixture of Rh(I) isomers of formula [(Cp*H)Rh(κ2N,N’‐HL)][SbF6] (5 a–d) is obtained by reductive elimination of Cp*H from 4. The formation of 5 a–d was elucidated by means of DFT calculations. Finally, when 2 reacts with D2, the Cp* and Cp*H ligands of the resulting rhodium complexes 4 and 5, respectively, are deuterated as a result of a reversible hydrogen abstraction from the Cp* ligand and D2 activation at rhodium.
Sustainable process design for heat exchanger network considering inherent safety and process economics
Authors: Athar Muhammad , Shariff Azmi Mohd , Rashid Muhammad Imran , Aadil Mahboob Ahmed , Umer Asim , Irfan Muhammad
Published: February 2024

Process lifecycle has several stages, including process design covered in multiple stages. Process economics is a vital factor in finalizing the process design. Besides economics, inherent safety is an important concept contributing to sustainable process design generation. The inherent safety concept has been applied via equipment characteristics for individual equipment. Since a method considering inherent safety with equipment aspects and process economics has not been available, therefore, a new method has been proposed, namely sustainable process design for heat exchanger network (SPDHEN), to integrate inherent safety, equipment aspects, and process economics. SPDHEN uses indexing to identify the critical heat exchanger, which is then examined via hazard analysis for an explosion. For unacceptable hazards, inherent safety principles are engaged to generate design alternatives for which process economics is examined too. The final design would be inherently safer with the best profit margin. The proposed method has been studied for the ammonia synthesis loop. It is concluded that the explosion hazard has been reduced to a tolerable level by using inherent guide words with a marginal compromise on quantity of ammonia produced, that is, 0.32%. This method is straightforward and can be useful for process engineers to generate sustainable process designs for heat exchanger networks considering safety and process economics simultaneously.
Estimation of turbulent energy mixing factor in PWR sub‐channel by DNS
Authors: Singh R. K. , Mukhopadhyay Deb , Khakhar D. , Joshi J. B.
Published: February 2024

Turbulent mixing within sub‐channels plays a crucial role in understanding the thermal hydraulics of reactor channels. It serves as an empirical parameter in sub‐channel analysis and has long been a challenge in the nuclear industry. Conducting experiments in this context is challenging due to the stringent requirement of maintaining pressure balance among sub‐channels to prevent convection effects. Fortunately, direct numerical simulation (DNS) is emerging as an invaluable tool for addressing this persistent issue. DNS enables the direct computation of turbulent mixing by analyzing fluctuating lateral velocities, offering a more profound understanding of the underlying phenomena. In this study, DNS was conducted at six Reynolds numbers ranging from 17,640 to 1.5 × 105 in pressurized water reactor (PWR) geometry to investigate the lateral mixing driven by turbulence. By studying intricate mechanisms governing the turbulent mixing, the valuable insights into reactor thermal performance and safety are provided. Furthermore, a correlation for turbulent mixing of energy based on the DNS data has been derived, enhancing our ability to model and predict this critical aspect of reactor behaviour. Additionally, this paper explores temperature fluctuations occurring at the fuel rod surface due to turbulence. A probabilistic distribution for temperature fluctuation under specific reactor conditions is presented.
Regularly Tuning Quantum Interference in Single‐Molecule Junctions through Systematic Substitution of Side Groups with Varied Electron Effects†
Authors: Xie Xianjing , Zhang Yirong , Zhang Junrui , Cui Xingyuan , Liu Wei , Liu Xunshan
Published: February 2024

Comprehensive Summary

Investigating the quantum interference effect in single molecules is essential to comprehensively understand the underlying mechanism of single‐molecule charge transport. In this study, we employed the mother molecule m‐OPE and introduced a series of side groups with various electronic effects at the 2‐position of the central phenyl ring, creating four daughter m‐OPE derivatives. The single molecular conductivities of these molecule wires were measured using the scanning tunneling microscope breaking junction technique. Our findings demonstrate that the substitutions regularly modulate the destructive quantum interference occurring within the m‐OPE molecules. By combining optical and electrochemical investigations, along with density functional theory computations, we discover that the conductivity of the molecules corresponds to the electron‐donating/withdrawing ability of the substituents. Specifically, by adjusting the electron structures of the molecular backbone, we can systematically tailor the destructive quantum interference in the m‐OPE molecules.
Reduced Macrophage Uptake of Nanoparticles through Surface Modification of Polypeptides with Valine Residues†
Authors: Li Ning , Xiao Shanshan , Jin Xiaoxiong , Song Ziyuan
Published: February 2024

Comprehensive Summary

The structural and surface properties of nanomedicines play an important role in determining their biological fate. Surface chemistry of nanomedicines is one of the key parameters, where researchers used various strategies such as PEGylation to avoid the undesired clearance of nanoparticles (NPs) for enhanced targeting effect. Nevertheless, the fine‐tuning of surface chemistry through polymer functionalization remains largely unexplored. In this concise report, we find that the incorporation of only 10 mol% valine residues into the surface‐anchored poly(L‐glutamic acid) significantly lowered the macrophage uptake of NPs. The introduction of other hydrophobic amino acid residues, however, increased the NPs internalization instead. The chirality and the side‐chain structure of valine played an important role in the unexpected uptake behavior. We believe this work highlights the impact of slight changes of the surface‐anchored polymer structure on the behavior of NPs, drawing people's attention to the careful design of surface chemistry to optimize the nanomedicine design.
Post‐diagnostic multivitamin supplement use and colorectal cancer survival: A prospective cohort study
Authors: He Ming‐ming , Wang Kai , Lo Chun‐Han , Zhang Yiwen , Polychronidis Georgios , Knudsen Markus D. , Zhong Rong , Ma Yuan , Wu Kana , Chan Andrew T. , Giovannucci Edward L. , Ogino Shuji , Ng Kimmie , Meyerhardt Jeffrey A. , Song Mingyang
Published: February 2024

Background

Use of multivitamin supplements has been associated with lower incidence of colorectal cancer (CRC). However, its influence on CRC survival remains unknown.

Methods

Among 2424 patients with stage I–III CRC who provided detailed information about multivitamin supplements in the Nurses’ Health Study and Health Professionals Follow‐up Study, the authors calculated multivariable hazard ratios (HRs) of multivitamin supplements for all‐cause and CRC‐specific mortality according to post‐diagnostic use and dose of multivitamin supplements.

Results

During a median follow‐up of 11 years, the authors documented 1512 deaths, among which 343 were of CRC. Compared to non‐users, post‐diagnostic users of multivitamin supplements at a dose of 3–5 tablets/week had lower CRC‐specific mortality (HR, 0.55; 95% confidence interval [CI], 0.36–0.83, p = .005), and post‐diagnostic users at doses of 3–5 and 6–9 tablets/week had lower all‐cause mortality (HR, 0.81; 95% CI, 0.67–0.99, p = .04; HR, 0.79; 95% CI, 0.70–0.88), p < .001). The dose–response analysis showed a curvilinear relationship for both CRC‐specific (pnonlinearity < .001) and all‐cause mortality (pnonlinearity = .004), with the maximum risk reduction observed at 3–5 tablets/week and no further reduction at higher doses. Compared to non‐users in both pre‐ and post‐diagnosis periods, new post‐diagnostic users at dose of <10 tablets/week had a lower all‐cause mortality (HR, 0.81; 95% CI, 0.71–0.94, p = .005), whereas new users at a dose of ≥10 tablets/week (HR, 1.58; 95% CI, 1.07–2.33) and discontinued users (HR, 1.35; 95% CI, 1.14–1.59) had a higher risk of mortality.

Conclusions

Use of multivitamin supplements at a moderate dose after a diagnosis of nonmetastatic CRC is associated with lower CRC‐specific and overall mortality, whereas a high dose (≥10 tablets/week) use is associated with higher CRC‐specific mortality.
Phenotypic Models of Drug–Drug‐Gene Interactions Mediated by Cytochrome Drug‐Metabolizing Enzymes
Authors: Viviani Roberto , Berres Judith , Stingl Julia C.
Published: February 2024

Genetic polymorphisms in drug metabolizing enzymes and drug–drug interactions are major sources of inadequate drug exposure and ensuing adverse effects or insufficient responses. The current challenge in assessing drug–drug gene interactions (DDGIs) for the development of precise dose adjustment recommendation systems is to take into account both simultaneously. Here, we analyze the static models of DDGI from in vivo data and focus on the concept of phenoconversion to model inhibition and genetic polymorphisms jointly. These models are applicable to datasets where pharmacokinetic information is missing and are being used in clinical support systems and consensus dose adjustment guidelines. We show that all such models can be handled by the same formal framework, and that models that differ at first sight are all versions of the same linear phenoconversion model. This model includes the linear pharmacogenetic and inhibition models as special cases. We highlight present challenges in this endeavor and the open issues for future research in developing DDGI models for recommendation systems.
A Novel, Fully Automated, and Reagent‐Agnostic Transient Transfection Protocol
Authors: Nair Vasudha S. , Watson Kinnari
Published: February 2024

Transfection is a potent technique to introduce foreign nucleic acids into eukaryotic cells. The capacity of the technique to alter the genetic content of host cells means it is useful for a wide range of applications, including the study of typical cellular processes, disease molecular mechanisms, and gene therapy effects. Here, we discuss a highly reliable and fully automated transient transfection protocol that utilizes an open‐source liquid handler and accompanying HEPA Module. Two commonly used transfection reagents are employed to study the transfection efficiency in two cell lines with a GFP plasmid construct. The detailed method of the protocol, image acquisition, and analysis for evaluating transfection efficacy is provided. With HeLa cells, the transfection efficiency of the reagents ranges from 40.92% to 73.26%, while with the difficult‐to‐transfect A549 cells, the transfection efficiency is between 42.15% and 54%. The efficiency achieved is comparable to similar experiments performed manually. © 2024 Wiley Periodicals LLC.

Basic Protocol 1: Seeding of adherent cells (A549 and HeLa) for transient transfection on a Costar 6‐well plate using a liquid handler on Day 0

Basic Protocol 2: Transfection of the cell lines using the transfection reagents Lipofectamine 3000 and FuGENE HD on Day 1

Support Protocol: Image acquisition and semi‐quantitative analysis of transfection after 24 hr to calculate the transfection efficiency
Efficient Visible‐Light‐Driven Carbon Dioxide Reduction using a Bioinspired Nickel Molecular Catalyst
Authors: Zhang Jing , She Ping , Xu Qiang , Tian Fengkun , Rao Heng , Qin Jun‐Sheng , Bonin Julien , Robert Marc
Published: February 2024

Inspired by natural enzymes, this study presents a nickel‐based molecular catalyst, [Ni‖(N2S2)]Cl2 (NiN2S2, N2S2=2,11‐dithia[3,3](2,6)pyridinophane), for the photochemical catalytic reduction of CO2 under visible light. The catalyst was synthesized and characterized using various techniques, including liquid chromatography‐high resolution mass spectrometry (LC‐HRMS), UV‐Visible spectroscopy, and X‐ray crystallography. The crystallographic analysis revealed a slightly distorted octahedral coordination geometry with a mononuclear Ni2+ cation, two nitrogen atoms and two sulfur atoms. Photocatalytic CO2 reduction experiments were performed in homogeneous conditions using the catalyst in combination with [Ru(bpy)3]Cl2 (bpy=2,2’‐bipyridine) as a photosensitizer and 1,3‐dimethyl‐2‐phenyl‐2,3‐dihydro‐1H‐benzo[d]imidazole (BIH) as a sacrificial electron donor. The catalyst achieved a high selectivity of 89 % towards CO and a remarkable turnover number (TON) of 7991 during 8 h of visible light irradiation under CO2 in the presence of phenol as a co‐substrate. The turnover frequency (TOF) in the initial 6 h was 1079 h−1, with an apparent quantum yield (AQY) of 1.08 %. Controlled experiments confirmed the dependency on the catalyst, light, and sacrificial electron donor for the CO2 reduction process. These findings demonstrate this bioinspired nickel molecular catalyst could be effective for fast and efficient photochemical catalytic reduction of CO2 to CO.