bluuebunny/crossref_metadata_2025 huggingface dataset:
Combining the Nonnatural Activity of Lipase and Electrocatalysis in One Pot: Sustainable and Regioselective Synthesis of C‐3 Alkylated Oxindoles
Authors: Singh Kirti , Tyagi Vikas
Published: October 2024

In this study, we report an environment‐friendly protocol by integrating the nonnatural catalytic activity of lipase with electrocatalysis for synthesizing C‐3 alkylated oxindoles, which are part of many natural and pharmaceuticals products. Gratifyingly, Candida antarctica lipase B (CALB) is found to be highly active and regioselective for catalyzing the nonnatural C‐3 alkylation reaction at indole when combined with an electrochemical C‐2 oxidation process in the same vessels. Further, the generality and feasibility of the developed protocol are shown by employing several functional groups on the indole moiety and obtaining the desired products in moderate to good yield. Besides, the control experiments are set up along with the molecular docking studies to substantiate the role of the active site of Candida antarctica lipase B (CALB) in carrying out the regioselective C‐3 alkylation reaction. In addition, control experiments and cyclic voltammetry are performed to get insight into the electrochemical C‐2 oxidation process and as a result, a plausible mechanism for the integrated process is presented.
CO2 Reduction by Transition‐Metal Complex Systems: Effect of Hydrogen Bonding on the Second Coordination Sphere
Authors: Liang Xiang‐Ming , Ruan Zhi‐Jun , Guo Gui‐Quan , Lin Jun‐Qi , Zhong Di‐Chang
Published: October 2024

Homogeneous electrocatalysts typified by transition‐metal complex show transcendent potency in efficient energy catalysis through molecular design. For example, metal complexes with elaborate design performed wonderful activity and selectivity for electrocatalytic CO2 reduction. Primary coordination sphere of metal complexes plays a key role in regulating its intrinsic redox properties and catalytic activity. However, the overall reduction efficiency of CO2 is also bound up with the substrate activation process. Transition‐metal complexes are hoped to exhibit reasonable redox potential, reactive activity, and stability, while binding and activating CO2 molecules to achieve efficient CO2 reduction. Construction of second coordination sphere, especially hydrogen‐bonding network of transition‐metal complexes, is reported to be the “kill two birds with one stone” strategy to realize efficient CO2 reduction catalysis via systematic catalyst properties modulation and substrate activation. Herein, we present recent progress on the construction of hydrogen‐bonding network in the second coordination sphere of metal complexes by ligand modification or the introduction of exogenous organic ligand, and the resulted productive enhancement of the catalytic performance of metal complexes by the improvement of adsorption capacity and activation of CO2, proton transfer rate, and stability of reaction intermediates, and so forth.
High‐Entropy‐Stabilized Platinum Diborides for Poison‐Resistant Catalysis
Authors: Rosenberg Abraham A. , Li Juncheng , Zhang Yiren , Doane Joseph T. , Rice William , Wang Ting , Yeung Michael T.
Published: October 2024

Alloying and solid‐solution formation is a powerful technique that enhances and adds properties through elemental mixing, but unfortunately, some elements simply cannot mix as their chemical nature prevents a thermodynamically stable structure. For example, the inherent nobility of platinum group metals does not favor bond formation and precludes their incorporation into higher (boron‐rich) metal borides. However, we demonstrate that when using five or more constituents, the higher mixing entropy will overcome these chemical limitations and form a stable high‐entropy alloy, demonstrating the formation of new compounds with substituents that are seemingly impossible with a traditional metal alloying approach. The high‐entropy boride (HEB) Al0.2Nb0.2Pt0.2Ta0.2Ti0.2B2 was synthesized, where platinum was forced to occupy a 12‐coordinate site, sandwiched between honeycomb borophene sheets. In addition to the unusual coordination, the boron serves as a poison panacea. Pure platinum is strongly susceptible to sulfur poisoning by adsorption, rendering a platinum catalyst ineffective. Boron is known to be resistant to sulfur poisoning. The boron sheets present in the HEB shield the platinum from sulfur while maintaining high catalytic activity. This is confirmed with the facile hydrogenation of thiol‐containing nitro compounds, where the HEB resists sulfur poisoning while retaining its high catalytic activity.
Insights Into Electrocatalytic Hydrogenation of Furfural on Nanoparticulate Pd/C Under Acidic Conditions
Authors: Maselj Nik , Jovanovski Vasko , Trputec Jan , Šala Martin , Mervič Kristina , Hodnik Nejc , Jovanovič Primož
Published: October 2024

In this work, we present an insight into the mechanism of electrochemical hydrogenation of furfural on carbon supported palladium nanoparticles. By directly coupling electrochemistry with mass spectrometry, we were able to, for the first time, deconvolute the hydrogen evolution reaction and electrochemical hydrogenation by measuring the mass signal for hydrogen and 2‐methylfuran. This approach also allowed us to extract the Tafel slopes for each reaction and get insights into mechanisms. The results indicate that the hydrogenation occurs by a Langmuir–Hinshelwood type process rather than by proton‐coupled electron transfer. Further findings recognize the blocking character of furfuryl alcohol (FA) where the latter or one of its intermediates blocks the electrochemical hydrogenation. Additionally, FA is shown to be a precursor for 2‐methyl furan formation. Accordingly, specific guidelines towards improvement of reaction performance are suggested.
ZIF‐67 Derived Cobalt Catalysts for the Hydroformylation of Liquid Olefins
Authors: Almeida Leandro D. , Patiño Alejandra R. , Cerrillo Jose L. , Telalovic Selvedin , Garzon‐Tovar Luis , Gascon Jorge
Published: October 2024

In this work, we described a general monometallic cobalt heterogeneous catalyst for the hydroformylation of olefins, achieving good yields and recyclability up to five times with no loss in catalytic activity. These catalysts were prepared through the pyrolysis of the well‐defined metal–organic framework ZIF‐67. The addition of steam during the pyrolysis did not affect the final phase composition of the cobalt particles; nonetheless, it resulted in an increase of the cobalt particle size and the partial removal of the carbonaceous matrix. The materials were extensively characterized by several techniques, and it was observed that the N‐doped carbon matrix played a crucial role in terms of activity and stability. Different liquid olefins, including internal, terminal, and cyclic were successfully tested in our hydroformylation protocol. Aldehydes yields of 48%–77% for different liquid olefins were achieved with the optimal catalyst. No leaching of the active sites was observed over five catalytic cycles. The high stability of the catalyst is attributed to the presence of stabilizing nitrogen atoms bearing the cobalt sites.
Scenario Design for the Evaluation of Human–Machine Interaction in Modular Process Plants
Authors: Miesen Felix , Lorenz Julius , Klose Anselm , Pelzer Florian , Narciss Susanne , Urbas Leon
Published: October 2024

Operators in modular process plants face new demands due to features like increasing automation and digitalization combined with an architecture allowing for reconfigurations in short time spans. However, operators must be able to master process control tasks at all times. For research purposes on topics like supporting operators in their performance in process control of modular process plants, this article aims at developing scenarios of such plants. Based on three conceptual levels describing the relation of chemical processes and their modularized realization and a neutralization process as use case, four scenarios were developed. Having the common task to increase the throughput, the scenarios differ in terms of complexity and constraints that need to be considered for process control.
Proton exchange membrane‐based electrocatalytic systems for hydrogen production
Authors: Zhou Yangyang , Zhong Hongjing , Chen Shanhu , Wen Guobin , Shen Liang , Wang Yanyong , Chen Ru , Tao Li , Wang Shuangyin
Published: October 2024

Hydrogen energy from electrocatalysis driven by sustainable energy has emerged as a solution against the background of carbon neutrality. Proton exchange membrane (PEM)‐based electrocatalytic systems represent a promising technology for hydrogen production, which is equipped to combine efficiently with intermittent electricity from renewable energy sources. In this review, PEM‐based electrocatalytic systems for H2 production are summarized systematically from low to high operating temperature systems. When the operating temperature is below 130°C, the representative device is a PEM water electrolyzer; its core components and respective functions, research status, and design strategies of key materials especially in electrocatalysts are presented and discussed. However, strong acidity, highly oxidative operating conditions, and the sluggish kinetics of the anode reaction of PEM water electrolyzers have limited their further development and shifted our attention to higher operating temperature PEM systems. Increasing the temperature of PEM‐based electrocatalytic systems can cause an increase in current density, accelerate reaction kinetics and gas transport and reduce the ohmic value, activation losses, ΔGH*, and power consumption. Moreover, further increasing the operating temperature (120–300°C) of PEM‐based devices endows various hydrogen carriers (e.g., methanol, ethanol, and ammonia) with electrolysis, offering a new opportunity to produce hydrogen using PEM‐based electrocatalytic systems. Finally, several future directions and prospects for developing PEM‐based electrocatalytic systems for H2 production are proposed through devoting more efforts to the key components of devices and reduction of costs.
Progress and prospect of flexible MXene‐based energy storage
Authors: Yuan Hongxin , Hua Jianxin , Wei Wei , Zhang Miao , Hao Yue , Chang Jingjing
Published: October 2024

The growing need for flexible and wearable electronics, such as smartwatches and foldable displays, highlights the shortcomings of traditional energy storage methods. In response, scientists are developing compact, flexible, and foldable energy devices to overcome these challenges. MXenes—a family of two‐dimensional nanomaterials—are a promising solution because of their unique properties, including a large surface area, excellent electrical conductivity, numerous functional groups, and distinctive layered structures. These attributes make MXenes attractive options for flexible energy storage. This paper reviews recent advances in using flexible MXene‐based materials for flexible Li−S batteries, metal‐ion batteries (Zn and Na), and supercapacitors. The development of MXene‐based composites is explored, with a detailed electrochemical performance analysis of various flexible devices. The review addresses significant challenges and outlines strategic objectives for advancing robust and flexible MXene‐based energy storage devices.
From Double‐Stranded Helicates to Abiotic Double Helical Supramolecular Assemblies
Authors: Koehler Victor
Published: October 2024

The folding of oligomeric strands is the method that nature has selected to generate ordered assemblies presenting spectacular functions. In the purpose to mimic these biomacromolecules and extend their properties and functions, chemists make important efforts to prepare artificial secondary, tertiary, and even quarternary structures based on folded abiotic backbones. A large variety of oligomers and polymers, encoded with chemical informations, were designed, synthesized and characterized, and the establishment of non‐covalent interactions lead to complex and functional supramolecular architectures resulting from a spontaneous self‐assembly process. The association of complementary molecular strands into double helical structures is a common structural pattern of nucleic acids and proteins, so the synthesis of bio‐inspired double helices has emerged as an important subject. In recent years, a number of synthetic oligomers have been reported to form stable double helices and it was shown that the equilibrium between single and double helices can be controlled via different stimuli like the modification of the solvent or the temperature. This kind of structure presents highly interesting functions, such as molecular recognition within the cavity of double helices, and some other potential applications will emerge in the future.
Syn vs. Anti? What Controls Addition Stereochemistry in Chlorolactonization
Authors: Dzurka Camelio Emily R. , Maday Mitchell , Sarkar Aritra , Jackson James E. , Borhan Babak
Published: October 2024

The stereochemistry of the uncatalyzed chlorolactonization of 4‐phenylpent‐4‐enoic acid at room temperature was examined to probe the reaction's intrinsic diastereoselectivities as a function of chlorenium ion donor, solvent polarity, and reactant concentration ranges. Kinetic studies using Variable Time Normalization Analysis (VTNA) revealed differing reaction orders for the syn and anti alkene addition processes. Aided and illustrated by quantum chemical modeling, this detailed mechanistic analysis of the substrate's intrinsic chlorolactonization reactions points to concerted AdE3‐type paths for both syn and anti additions. By illuminating the factors selecting for syn‐ vs anti‐addition paths, the results provide key reference points for future studies of stereocontrol in halofunctionalization reactions.
Physicochemical Analysis of Cu(II)‐Driven Electrochemical CO2 Reduction and its Competition with Proton Reduction
Authors: Samim Akhter Sk , Srivastava Diship , Mishra Aman , Patra Niladri , Kumar Pankaj , Kumar Padhi Sumanta
Published: October 2024

The reduction of CO2 has become a key role in reducing greenhouse gas emissions in efforts to search for long‐term responses to climate change. We report a couple of CO2‐reducing molecular catalysts based on earth‐abundant copper complexes. These are [Cu(DPA)(PyNAP)] (1) and [Cu(DPA)(PyQl)] (2) (where, DPA=pyridine‐2,6‐dicarboxylate, PyNAP=2‐(pyridin‐2‐yl)‐1,8‐naphthyridine, and PyQl=2‐(pyridin‐2‐yl)quinoline). The copper metal‐catalysed 2‐electron reduction of CO2 to CO in the presence of 2‐protons is challenging. These catalysts exhibit the production of CO gas in DMF/water mixtures, achieving an impressive Faradaic efficiency of 84 % and 72 % for complex 1 and 2 at −1.7 V vs. SCE, respectively, for selective CO2 reduction. The production of H2 due to 2H++2e− was also observed as a byproduct through the competitive proton reduction reaction. This was cross‐verified by online gas and mass analysis. A comprehensive series of electrochemical experiments have substantiated the homogeneous behaviour exhibited by these molecular electrocatalysts. Our investigations confirmed the stability of the electrocatalysts under the electrocatalytic conditions. The mechanistic pathways were proposed to work with the EECC and ECEC (E: electrochemical and C: chemical) mechanisms. A CO2 insertion into an in‐situ generated hydride from the Cu‐center generates CO through the favourable path. This critical path kinetically favors excess Faradaic efficiency in 1 than 2, which agrees with the computational investigation.
Pure Shift NMR in Continuous Flow
Authors: Bazzoni Margherita , Régheasse Armand , Caytan Elsa , Felpin François‐Xavier , Giraudeau Patrick , Bernard Aurélie , Adams Ralph W. , Morris Gareth A. , Nilsson Mathias , Dumez Jean‐Nicolas
Published: October 2024

Flow NMR is an expanding analytical approach with applications that include in‐line analysis for process control and optimisation, and real‐time reaction monitoring. The samples monitored by flow NMR are typically mixtures that yield complex 1D 1H spectra. “Pure shift” NMR is a powerful approach to simplifying 1H NMR spectra, but its standard implementation is not compatible with continuous flow because of interference between sample motion and the position‐dependent spin manipulations that are required in pure shift NMR. Here we show that pure shift NMR spectra can be successfully collected for continuously flowing samples, thanks to an adapted acquisition scheme, robust solvent suppression, and a velocity‐compensation strategy. The resulting method is used to collect ultrahigh resolution reaction monitoring data. Pure shift NMR spectra are expected to benefit many applications of flow NMR.
Regulatory Mechanisms and Synergistic Enhancement of the Diiron YtfE Protein in Nitric Oxide Reduction
Authors: Tsai Ruei‐Fong , Chen Hung‐Ying , Cheng Yang‐Chun , Lo Feng‐Chun , Lu Tsai‐Te , Liaw Wen‐Feng , Chiang Yun‐Wei
Published: October 2024

The diiron‐containing YtfE protein in Escherichia coli is pivotal in counteracting nitrosative stress, a critical barrier to bacterial viability. This study delves into the biochemical complexity governing YtfE's conversion of nitric oxide (NO) to nitrous oxide, a key process for alleviating nitrosative stress. Through site‐directed mutagenesis, we explored YtfE's molecular structure, with a particular focus on two internal transport tunnels important for its activity. Our findings illuminate Tunnel 1 as the primary conduit for substrate transport, regulated by conformational shifts within the N‐terminal domain that enable substrate access to the diiron core in the C‐terminal domain. Tunnel 2 emerges as a secondary, supportive route, activated when Tunnel 1 is compromised. This result challenges a previous model of distinct tunnels for substrate entry and product exit, suggesting both tunnels are capable of transporting substrates and products. Our engineering efforts enhanced the role of Tunnel 2, enabling a synergistic operation with Tunnel 1 and tripling YtfE's enzymatic activity compared to its wild‐type form. This research not only deepens our understanding of YtfE's regulatory mechanism for NO reduction but also introduces a strategy to amplify its enzymatic efficiency. The outcomes offer new ravenues for modulating bacterial stress responses.
Experimental and Computational Studies of Steric Factors in the Isomerization of Internal Alkynes within the Coordination Environment of Half‐Sandwich Metal Complexes
Authors: Korb Marcus , Ghazvini Seyed M. B. H. , Karton Amir , Low Paul J.
Published: October 2024

The isomerization of internal alkynes Ar1C≡CAr2 within the coordination environment of low‐valent half‐sandwich [Ru(dppe)Cp]+ complexes via a 1,2‐migration process affords vinylidene species [Ru{=C=C(Ar1)Ar2}(dppe)Cp]+. The rearrangement reactions of symmetrically and asymmetrically substituted substrates featuring different electron‐donating and ‐withdrawing groups and of varying steric bulk were modelled using density functional theory (DFT), and the conclusions supported by experimental observations. Examination of the reaction pathway and associated activation barriers reveal a high solvent dependency for the generation of the key intermediate species [Ru(dppe)Cp]+ from [RuCl(dppe)Cp] by halide dissociation in the presence of Na+ salts of weakly coordinating anions, with the lattice enthalpy of the NaCl by‐product playing a critical role in the overall thermochemical balance of the reaction. The activation barriers associated with the reaction of [Ru(dppe)Cp]+ with Ar1C≡CAr2, and the relative energies of the alkyne complexes [Ru(η2‐Ar1C≡CAr2)(dppe)Cp]+, are sensitive to the electron density of the alkyne and conformational changes associated with the ‘bend‐back’ of the substrate. The latter differs by up to 66.1 kJ/mol, which in turn impacts the barrier height of the subsequent 1,2‐migration step involved in the rearrangement process and ultimately the overall thermochemical nature of the complete reaction. The relative importance of these factors is evinced by the successful rearrangement of the very sterically congested 1(9‐anthryl)‐2(9‐phenanthryl) acetylene into the fully characterized diaryl vinylidene complex, which was isolated in 89 % yield.
LDL‐C and hs‐CRP Jointly Modify the Effect of Lp(a) on 5‐Year Death in Patients With Percutaneous Coronary Intervention
Authors: Li Jiawen , Yan Kailun , Zhu Pei , Tang Xiaofang , Yang Yuejin , Gao Runlin , Yuan Jinqing , Zhao Xueyan
Published: October 2024

Background

Recent studies have suggested that adverse events associated with lipoprotein(a) [Lp(a)] might be modified by low‐density lipoprotein cholesterol (LDL‐C) or high‐sensitivity C‐reactive protein (hs‐CRP) levels, but whether LDL‐C and hs‐CRP jointly mediate the outcome of Lp(a) remains unknown in patients with coronary artery disease.

Methods and Results

A prospective study was conducted, enrolling consecutive 10 724 patients with percutaneous coronary intervention (PCI) in 2013. The endpoint event was all‐cause death. A total of 10 000 patients with complete baseline data were finally included. During a median follow‐up of 5.1 years, Lp(a) ≥ 30 mg/dL was an independent risk factor of all‐cause death in the overall population, LDL‐C ≥ 70 mg/dL, and hs‐CRP ≥ 2 mg/L population, respectively. According to concurrent LDL‐C (70 mg/dL) and hs‐CRP (2 mg/L) levels, further analysis revealed that when LDL‐C < 70 mg/dL regardless of hs‐CRP levels, Lp(a) ≥ 30 mg/dL was not an independent predictor of all‐cause death. However, when LDL‐C ≥ 70 mg/dL, Lp(a) ≥ 30 mg/dL was independently associated with a higher risk of all‐cause death in hs‐CRP ≥ 2 mg/L (HR: 1.488, 95% CI: 1.059‒2.092), but not in hs‐CRP < 2 mg/L (HR: 1.303, 95% CI: 0.914‒1.856).

Conclusion

Among PCI patients, Lp(a)‐associated outcome was jointly affected by LDL‐C and hs‐CRP. As long as LDL‐C is well controlled, the adverse effects of increased Lp(a) on cardiovascular risk seem to be weakened, and only when LDL‐C and hs‐CRP increase at the same time, elevated Lp(a) is associated with poorer long‐term outcome.
Incorporating Inflammation Biomarker‐Driven Multivariate Predictive Model for Coronary Microcirculatory Dysfunction in Acute Myocardial Infarction Following Emergency Percutaneous Coronary Intervention
Authors: Yao Zhuoya , Ding Bin , Wang Jun , Qian Shaohuan , Song Xilong , Li Yao , Ding Siyu , Wang Hongju , Li Miaonan
Published: October 2024

Background

Despite patients with successful revascularization as evidenced by angiographic findings, inadequate clinical management of coronary microcirculatory dysfunction (CMD) may result in preventable adverse outcomes. Therefore, it is imperative to use a multimodal data‑driven predictive model for the occurrence of CMD in patients with acute myocardial infarction (AMI) following emergency percutaneous coronary intervention (PCI).

Methods

A prospective case−control analysis was conducted on a cohort of 77 patients with AMI who underwent PCI. The most informative predictors were selected for the predictive model through the application of LASSO analysis and multi‐factor logistic regression. The diagnosis of CMD is based on findings from cardiac magnetic resonance (CMR).

Results

Based on the findings from LASSO analysis and multi‐factor logistic regression, variables including sex, neutrophil‐to‐lymphocyte ratio (NLR), Gensini score, and diabetes mellitus were identified as independent predictors for the development of CMD in AMI patients who underwent emergency PCI. The predictive model was evaluated using bootstrap self‐sampling 500 times. The resulting predictive model demonstrated an AUC value of 0.897 (95% CI: 0.827−0.958). The calibration curves exhibited good concordance between the predictions generated by the model and the CMR analysis. Furthermore, decision curve analysis revealed that the predictive model provided valuable clinical benefit in predicting CMD.

Conclusions

The multivariate predictive model, constructed using readily available clinical variables in patients with AMI who underwent PCI, demonstrates satisfactory predictability for identifying comorbid CMD, thereby facilitating the identification of high‐risk patients.
Insights into Molecular Interactions and Biological Effect of Natural Stilbenoids at the TRPA1 Ion Channel
Authors: Saadabadi Atefeh , Rantanen Marja , Marimuthu Parthiban , Koivisto Ari‐Pekka , Eklund Patrik C. , Salo‐Ahen Outi M. H.
Published: October 2024

Natural stilbenoids, polyphenolic compounds notably found in Scots pine and Norway spruce, have been shown to exhibit analgesic and anti‐inflammatory effects through the TRPA1 channel, making them promising hits for the development of novel agents to treat inflammatory diseases and pain. In this study, we computationally investigated the putative binding sites of natural stilbenoids at the TRPA1 channel. Specifically, we employed molecular docking and MD simulation approaches to explore three known ligand binding sites at TRPA1. Furthermore, the biological effect of the studied compounds on TRPA1 was assessed in vitro using a fluorescent imaging plate reader (FLIPR™) calcium assay. Our modeling results suggest the stilbenoids exhibit higher affinity to the two agonist binding sites than the antagonistic site. Consistent with this, the in vitro results showed that the stilbenoids act as moderate TRPA1 channel agonists and likely inhibit the channel through a desensitization mechanism rather than act as pure TRPA1 antagonists. Additionally, our bias‐force pulling simulations proposed an additional binding pocket for the natural stilbenoids that is distinct from the known ligand binding sites at TRPA1. The results of the study give useful insights into structure‐based design and development of novel therapeutic TRPA1 modulators.
Aerobic exercise and CogniTIVe functioning in women with breAsT cancEr (ACTIVATE): A randomized controlled trial
Authors: Brunet Jennifer , Sharma Sitara , Zadravec Kendra , Taljaard Monica , LeVasseur Nathalie , Srikanthan Amirrtha , Bland Kelcey A. , Sabri Elham , Collins Barbara , Hayden Sherri , Simmons Christine , Smith Andra M. , Campbell Kristin L.
Published: October 2024

Background

As the prevalence of chemotherapy‐related cognitive impairment rises, investigation into treatment options is critical. The objectives of this study were to test the effects of an aerobic exercise intervention initiated during chemotherapy compared to usual care (wait list control condition) on (1) objectively measured cognitive function and self‐reported cognitive function, as well as on (2) the impact of cognitive impairment on quality of life (QOL) postintervention (commensurate with chemotherapy completion).

Methods

The Aerobic exercise and CogniTIVe functioning in women with breAsT cancEr (ACTIVATE) trial was a two‐arm, two‐center randomized controlled trial conducted in Ottawa and Vancouver (Canada). Fifty‐seven women (Mage, 48.8 ± 10 years) diagnosed with stage I–III breast cancer and awaiting chemotherapy were randomized to aerobic exercise initiated with chemotherapy (nEX = 28) or usual care during chemotherapy with aerobic exercise after chemotherapy completion (nUC = 29). The intervention lasted 12–24 weeks and consisted of supervised aerobic training and at‐home exercise. The primary outcome was objective cognitive function measured via 13 neuropsychological tests (standardized to M ± SD, 0 ± 1); secondary outcomes of self‐reported cognitive function and its impact on QOL were assessed via questionnaires. Data collected pre‐ and postintervention (the primary end point) were analyzed.

Results

Although no significant differences between groups were found for objective cognitive function outcomes postintervention after accounting for multiple testing, four of six self‐reported cognitive function outcomes showed significant differences favoring the aerobic exercise group.

Conclusions

Among women initiating chemotherapy for breast cancer, aerobic exercise did not result in significant differences in objective cognitive function postintervention after chemotherapy completion; however, the results do support the use of this intervention for improving self‐reported cognitive function and its impact on QOL.
Ketamine and Esketamine in Clinical Trials: FDA‐Approved and Emerging Indications, Trial Trends With Putative Mechanistic Explanations
Authors: Vekhova Ksenia A. , Namiot Eugenia D. , Jonsson Jörgen , Schiöth Helgi B.
Published: October 2024

Ketamine has a long and very eventful pharmacological history. Its enantiomer, esketamine ((S)‐ketamine), was approved by the US Food and Drug Administration (FDA) and EMA for patients with treatment‐resistant depression (TRD) in 2019. The number of approved indications for ketamine and esketamine continues to increase, as well as the number of clinical trials. This analysis provides a quantitative overview of the use of ketamine and its enantiomers in clinical trials during 2014–2024. A total of 363 trials were manually assessed from clinicaltrial.gov with the search term “Ketamine.” The highest number of trials were found for the FDA‐approved indications: anesthesia (~22%) and pain management (~28%) for ketamine and TRD for esketamine (~29%). Clinical trials on TRD for both ketamine and esketamine also comprised a large proportion of these trials, and interestingly, have reached phase III and phase IV status. Combinatorial treatment of psychiatric disorders and non‐psychiatric conditions with pharmacological and non‐pharmacological combinations (electroconvulsive therapy, psychotherapeutic techniques, virtual reality, and transcranial magnetic stimulation) is prevalent. Sub‐anesthetic doses of ketamine may represent novel therapeutic avenues in neuropsychiatric conditions, that is, major depression, schizophrenia, and bipolar disorder, where glutamate excitotoxicity and oxidative stress are likely to be involved. The study suggests that the number of ketamine studies will continue to grow and possible ketamine variants can be approved for treatment of additional indications.
Risk of Opioid Overdose Associated with Concomitant Use of Methadone and Statins
Authors: Chen Cheng , Miano Todd A. , Brensinger Colleen M. , Leonard Charles E. , Bilker Warren B. , Hennessy Sean
Published: October 2024

Methadone has a high potential for risky drug–drug interactions that can lead to opioid overdose, yet evidence on the magnitude of this risk remains limited. Since methadone is transported via P‐glycoprotein (P‐gp), the use of statins that inhibit P‐gp may elevate methadone plasma concentrations, potentially leading to opioid overdose. We explored this hypothesis by examining whether concomitant use of methadone and P‐gp‐inhibiting statins was associated with opioid overdose. Using Medicaid claims data from 2003 to 2020, we conducted a cohort study among new concomitant users of methadone and statins. We compared overdose rates among individuals exposed to P‐gp‐inhibiting statins (simvastatin, atorvastatin, or lovastatin) vs. those exposed to rosuvastatin (negative control), adjusting for baseline covariates. We identified 69,263 individuals newly exposed to methadone and a statin of interest; the overall incidence rate of opioid overdose was 26.0 per 1,000 person‐years. Adjusted hazard ratios (HRs) for methadone + P‐gp‐inhibiting statins consistently showed no association, ranging from 0.76 (95% CI = 0.48–1.22) for atorvastatin to 0.78 (95% CI = 0.50–1.22) for simvastatin, compared with methadone + rosuvastatin. Similar results were observed in sensitivity analysis that treated all P‐gp‐inhibiting statins as a single exposure group, as well as analyses stratified by baseline diagnosis of opioid use disorder or overdose, the duration of baseline methadone use, and calendar year intervals. Our findings suggest that concomitant use of methadone with simvastatin, atorvastatin, or lovastatin is not associated with the risk of opioid overdose compared to concomitant use of methadone and rosuvastatin.
Hydrogen Evolution Reaction of Electrodeposited Ni‐W Films in Acidic Medium and Performance Optimization Using Machine Learning
Authors: de Paz‐Castany Roger , Eiler Konrad , Nicolenco Aliona , Lekka Maria , García‐Lecina Eva , Brunin Guillaume , Rignanese Gian‐Marco , Waroquiers David , Collet Thomas , Hubin Annick , Pellicer Eva
Published: October 2024

Ni−W alloy films were electrodeposited from a gluconate aqueous bath at pH=5.0, at varying current densities and temperatures. While there is little to no difference in composition, i. e., all films possess ~12 at.% W, their activity at hydrogen evolution reaction (HER) in acidic medium is greatly influenced by differences in surface morphology. The kinetics of HER in 0.5 M H2SO4 indicates that the best performing film was obtained at a current density of −4.8 mA/cm2 and 50 °C. The Tafel slopes (b) and the overpotentials at a geometric current density of −10 mA/cm2 (η10) obtained for 200 cycles of linear sweep voltammetry (LSV) from a set of films deposited using different parameters were fed into a machine learning algorithm to predict optimum deposition conditions to minimize b, η10, and the degradation of samples over time. The optimum deposition conditions predicted by the machine learning model led to the electrodeposition of Ni−W films with superior performance, exhibiting b of 33–45 mV/dec and an η10 of 0.09–0.10 V after 200 LSVs.
Bifunctional MoNi4/Nickel Foam Electro‐Catalyst for Ultra‐Efficient Oxidation of High‐Concentration 5‐Hydroxymethylfurfural and HER
Authors: Liu Hao , Xia Jie , Liu Xiaohui , Hu Yongfeng , Shakouri Mohsen , Wu Haoran , Zhu Minghui , Guo Yong , Chen Jingye , Wang Haifeng , Wang Yanqin
Published: October 2024

The electro‐catalytic oxidation of biomass‐derived 5‐hydroxymethylfurfural (HMF) provides an attractive route to produce 2, 5‐furandicarboxylic acid (FDCA) as a substitute for terephthalic acid used in the plastics industry. Herein, we prepared MoNi4 alloy on nickel foam (NF) using a simple hydrothermal method followed by hydrogen reduction. Applied MoNi4/NF as the bifunctional electrodes for the electro‐catalytic HMF oxidation reaction (HMFOR) and HER, 98.7 % FDCA yield and 97.3 % Faraday efficiency (FE) can be achieved even with HMF concentration as high as 200 mM. Notably, no obvious deactivation was observed after ten consecutive cycles. In‐situ Raman, XANES and EXAFS results show that the nickel species of MoNi4/NF is first oxidized to Ni3+ species under the applied voltage, and after undergoing the electro‐catalytic HMFOR, then reduced to Ni2−δ state (with a valence between 0 and +2) due to the electron‐donating effect from Mo. MoNi4/NF with more than one electron transfer between Ni3+ and Ni2−δ during the HMFOR enables it to have excellent electro‐catalytic oxidation ability toward HMFOR.
Unleashing the Synergistic Potential of 2D‐2D Nanosheet Based S‐Scheme Heterojunction: Cooperative Boosting of CO2 Reduction to Solar Fuel and Biomass Valorization
Authors: Dhingra Shivali , Jain Ayushi , Jaryal Arpna , Bera Chandan , Kailasam Kamalakannan
Published: October 2024

Harnessing inexhaustible solar energy for CO2 valorization is a substantial step toward achieving a carbon‐neutral energy cycle. However, CO2 conversion often exhibits slow kinetics, necessitating the utilization of sacrificial agents making the process economically unfeasible. In the ongoing quest for sustainable and economically feasible CO2 valorization, herein the photoreduction of CO2 to CO coupled with biomass‐based alcohol oxidation to fine chemicals is reported via Bi2WO6/g‐C3N4 (BWO/g‐CN) 2D‐2D nanosheet based S‐scheme heterojunction. Importantly, BWO/g‐CN‐60 exhibits highest photocatalytic activity with CO production rate of 6.87 mmol g−1 h−1, accompanied by >98 % selectivity and selective oxidation of veratryl alcohol to veratraldehyde, with notable yield of 42 % in 6 h under simulated solar light. The apparent quantum yield (AQY) of 14.3 % is achieved for CO production at the wavelength of 420 nm. Additionally, the formed heterostructure results in enhanced charge separation and accelerated charge transfer kinetics as validated by PL, EIS, and photocurrent studies. EPR, 13CO2 labeling, DFT studies, and various controlled experiments provided a deeper insight into the mechanism of underlying photo‐redox process. Thus, the current study presents a sustainable paradigm for CO2 mitigation by converting it into solar fuel, while synergistically producing the fine chemicals through effectively harnessing the full potential of charge carriers.
Ni‐Metalized Covalent Organic Cage as a Photocatalyst for Selective Photoreduction of CO2 to CO
Authors: Miao Rongbin , Niu Qing , Li Liuyi , Yu Yan
Published: October 2024

Metal complex‐based photocatalysts are promising for CO2 reduction. Their catalytic performances greatly rely on the synergy of ligands and metal ions. Here, we demonstrate an assembly of covalent organic cage (COC) and metal ions for photocatalytic CO2 reduction. The coordinated metal serves as catalytically active site for CO2 reduction, while the cage not only chelates the metal site, but also enhances the local concentration of CO2 around metal site, and decreases the key intermediate reaction energy barrier, thereby promoting the CO2 reduction reaction kinetically and thermodynamically. Accordingly, a Ni metalized COC exhibited outstanding photocatalytic performance in CO2‐to‐CO conversion under visible light irradiation. This study highlights the feasibility and advantage of organic cages for the construction of photocatalysts for artificial photosynthesis.
RuCo@C Hollow Nanoprisms Derived from ZIF‐67 for Enhanced Hydrogen and Oxygen Evolution Reactions
Authors: Salah Abdulwahab , Ren Hong‐Da , Al‐Ansi Nabilah , Al‐Salihy Adel , Mahyoub Samah A. , Qaraah Fahim A. , Hezam Abdo , Drmosh Qasem A.
Published: October 2024

Zeolitic imidazolate frameworks (ZIFs) are commonly used to create complex hollow structures for energy applications. This study presents a simple method to produce a novel hollow nanoprism Co@C hierarchical composite from ZIF‐67 through high‐temperature treatment at 800 °C. This composite serves as a platform for Ru nanoparticle deposition, forming RuCo@C hollow nanoprism (RuCo@C HNP). As an electrocatalyst in 1 M KOH, RuCo@C HNP exhibits excellent hydrogen evolution reaction (HER) performance, with a low overpotential of 32 mV to reach 10 mA cm−2, a Tafel slope of 39.67 mV dec−1, a high turnover frequency (TOF) of 3.83 s−1 at η200, and stable performance over 50 h. It also achieves a low η10 of 266 mV for the oxygen evolution reaction (OER) with a Tafel slope of 45.22 mV dec−1. Density functional theory (DFT) calculations reveal that Ru doping in Ni/Co maintains a low water dissociation barrier, reduces the energy barrier for the OER rate‐determining step, and creates active sites for H*, enhancing adsorption/desorption abilities. These results are attributed to the synergy between Co and Ru and the hollow prism structure′s increased surface area. This method for synthesizing hollow structures using ZIF composites shows promise for applications in the energy sector.
Distillery‐Waste‐Derived C−SiO2 Catalyst Support Reinforces Phenol Adsorption and Selective Hydrogenation
Authors: Xu Xiuzhen , Feng Weiqin , Liu Xudong , Jiang Zhicheng , Shi Bi
Published: October 2024

Selective hydrogenation of lignin‐derived phenolic compounds is an essential process for developing the sustainable chemical industry and reducing dependence on nonrenewable resources. Herein, a composite C−SiO2 material (DGC) was prepared via the stepwise pyrolysis and steam activation of the distiller′s grains, a fermentation solid waste from the Chinese liquor industry. After Ru loading, Ru/DGC was used for the catalytic hydrogenation of phenol to cyclohexanol. Steam activation remarkably increased the hydrophilicity and specific surface area of DGC, introducing oxygen‐containing functional groups on the surface of DGC, thereby promoting the adsorption of Ru3+ and phenol. Additionally, the large specific surface area facilitated the dispersion of the active metal. Furthermore, the steam activation of DGC promoted the graphitization of the carbon matrix and formed Si−H/Si−OH bonds on the SiO2 surface. The benzene ring of phenol interacted with the carbon matrix via π–π stacking, and the hydroxyl group of phenol interacted with SiO2 via hydrogen bonding. The synergistic interactions of phenol at the C−SiO2 interface enhanced phenol adsorption to promote the hydrogenation. Consequently, 100 % of phenol was hydrogenated to cyclohexanol at 60 °C within 30 min. Furthermore, the optimized catalyst exhibited high activity for phenol hydrogenation even after four reuse cycles. The outstanding stability of the catalyst and its requirement for mild reaction conditions favor its large‐scale industrial applications.
Prospective associations of interleukin‐6 and APOE allele with cognitive decline in biracial community‐dwelling older adults: The Chicago Health and Aging Project (CHAP)
Authors: Ng Ted K. S. , Beck Todd , Desai Pankaja , Dhana Klodian , Wilson Robert S. , Evans Denis A. , Rajan Kumar B.
Published: October 2024

INTRODUCTION

It is unclear whether inflammation, that is, high interleukin‐6 (IL‐6) levels, and genetic risk, that is, apolipoprotein E (APOE) ε4 allele, have a compounding effect on cognitive decline (CD).

METHODS

We analyzed a subset of participants from the longitudinal cohort study, Chicago Health and Aging Project, comprising 1120 biracial community‐dwelling older adults (60% Black and 62% women), and mean follow‐up = 6.4 years. We ran adjusted mixed‐effects models on2 longitudinal CD.

RESULTS

In APOE ε4 carriers, higher serum IL‐6 was not associated with the rate of CD (β = –0.0091 [standard deviation (SD) = 0.0165, p = 0.5800]). Conversely, in non‐ε4 carriers, compared to the lower tertile, those with the upper tertile of serum IL‐6 levels experienced significantly accelerated CD (β = –0.0257 [SD = 0.0084, p = 0.0023]).

DISCUSSION

Even without the largest genetic risk factor for late‐onset Alzheimer's disease/Alzheimer's disease and related dementias (AD/ADRD), elevated serum IL‐6 still accelerate the rate of CD in non‐APOE ε4 carriers. Hence, interventions ameliorating inflammation may prevent AD/ADRD.

Highlights

Interleukin‐6 (IL‐6) and the apolipoprotein E (APOE) ε4 allele have been separately associated with an increased risk for cognitive decline, but their interaction remains unclear.

In ε4 carriers, IL‐6 was not associated with cognitive decline. However, even without the biggest genetic risk factor for Alzheimer's disease (AD), that is, APOE ε4, elevated serum IL‐6 still could confer accelerated rate of cognitive decline, with a detrimental effect half of that imposed by APOE ε4 alone.

We found no racial differences in these associations.

These findings contribute complementary evidence on non–APOE ε4‐dependent and non‐AD biological pathways through which cognitive decline can still be accelerated in non‐APOE ε4 carriers and highlight a specific subgroup of older adults who are at a higher risk of AD and thus may benefit from anti‐inflammatory interventions.
Developing Solutions to the Waitlist Problem for Eating Disorder Treatments
Authors: Wade Tracey D. , Jabs Maya , Keegan Ella , Long Randall , McGregor Andrew , Pellizzer Mia , de Valle Madelaine , Radunz Marcela
Published: October 2024

Objective

We examine the small amount of research to date that describes and/or evaluates waitlist interventions as a precursor to treatment for an eating disorder (ED) with the intent to provide recommendations for future research that can further test the efficacy and effectiveness of waitlist interventions.

Method

A review of published studies showed the standard of proof about the usefulness of waitlist interventions to be slight, with important gaps in our knowledge. One such gap was whether recovered people with lived experience could provide support to adults waiting for treatment. We briefly present new research evaluating this approach (N = 40), where people waiting for treatment were randomized to waitlist as usual or guided self‐help with a trainee psychologist or a person with lived experience.

Results

Eight published studies across 10 different programs are described; N = 7 addressed waitlists for children and adolescents, and only three were randomized controlled trials. Our new research did not support the involvement of people with lived experience at this stage of the treatment journey.

Discussion

The results suggest some promise of waitlist interventions. Parents waiting for family‐based treatment were able to improve weight and nutritional health in their children and experienced improved self‐efficacy with respect to managing the ED. Provision of a waitlist intervention to adults may increase the probability of later engagement in treatment. It is still not possible to conclude whether waitlist interventions improve outcomes over treatment compared to those who did not receive such an intervention. We make five recommendations for future research.
Evaluating variation of respiration:photosynthesis ratio in sagebrush species: Implications for carbon flux modeling
Authors: Sharma Harmandeep , Reinhardt Keith , Lohse Kathleen A. , Aho Ken
Published: October 2024

Plant respiration and photosynthesis are the two main processes influencing carbon (C) flux balance at leaf‐to‐ecosystem scales. The ratio of respiration to photosynthesis (R:A) or carbon use efficiency (CUE) is considered an important trait for determining global carbon storage in the near future. One school of thought assumes that R:A is constant in terrestrial productivity models, irrespective of biomass, climate, and species. Others believe it is variable, although within a limited range. Semiarid systems dominated by woody vegetation, such as sagebrush steppe, have been recognized as potentially important C sinks on regional to global scales in the context of future climate scenarios. Therefore, there is a critical need to study R:A over different organizational scales (i.e., at the leaf, whole plant, and ecosystem scales) to use this approach for future C flux predictions under climate change scenarios. The objective of this study was to compare leaf‐, shrub‐, and ecosystem‐scale R:A among three sagebrush (Artemisia spp.) communities, and to determine how R:A varies throughout the growing season (i.e., early, mid‐, and late summer) among these communities. We measured photosynthesis and respiration monthly in three sagebrush communities spanning a 685‐m elevation gradient at the Reynolds Creek Experimental Watershed and Critical Zone Observatory in southwestern Idaho. Consistent with our expectations, we found large seasonal variations in R and A at all scales, but with differences in A among the three sagebrush communities significant only at the leaf scale. The R:A ratio was not significantly different among the three species at all organizational scales. However, the R:A ratio did vary among months at the leaf level and there was a statistical interaction between species and month at both leaf and shrub levels. Our study indicates that the R:A ratio is generally conservative, although not tightly constrained (range: 0.12–0.77) among three sagebrush species. Therefore, approaches that assume conservative R:A ratios in terrestrial productivity models need to be considered carefully to evaluate the impact of projected climatic changes on future C cycling in shrub‐dominated rangeland ecosystems.