bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractDirect 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

AbstractThis 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

AbstractThis 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

AbstractTi3C2Tz 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

AbstractThis 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

AbstractWhile 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

AbstractA 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

AbstractHalide‐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

AbstractImmobilization 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

AbstractThe 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

AbstractProcess 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

AbstractTurbulent 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 SummaryInvestigating 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 SummaryThe 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

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