bluuebunny/crossref_metadata_2025 huggingface dataset:
Efficient Amplification of Large‐Signal Spoof Surface Plasmon Polaritons in a Subwavelength Size
Authors: Liao Zhen , Wu Shaofei , Guo Jia , Liu Leilei , Cai Jialin
Published: January 2024

The advancement of communication systems demands ever‐smaller sizes, leading to the integration of more circuits in compact forms. A promising solution lies in Spoof Surface Plasmon Polaritons (SSPPs), which enable strong confinement, low interference, and a significant wave vector, thereby facilitating smaller sizes. However, the amplification of large plasmonic signals in a compact size remains a daunting scientific challenge for the further development of SSPPs communication systems. In this study, this challenge is tackled by selecting GaN High Electron Mobility Transistors (HEMTs) and load/source‐pull technologies. To ensure efficient operation, impedance‐matching networks are designed, resulting in a remarkably small amplifier structure. The approach involves utilizing the Bayesian optimization (BO) algorithm to fine‐tune the matching network, leading to exceptional amplification performance. The results obtained in the frequency range of 1–3 GHz are highly promising, with both simulated and measured results demonstrating an impressive output power exceeding 40 dBm, a power added efficiency (PAE) surpassing 60%, and a gain exceeding 10 dB. These remarkable achievements underscore the viability of amplifying large‐signal SSPPs and outputting high‐power SSPPs waves within a subwavelength size, opening exciting possibilities for SSPPs communication, sensing, and imaging systems.
Direct Site‐Selective Difunctionalization of Pyrazoles
Authors: Liu Biao , Wang Cheng , Wang Ziyu , Zhou Junqi , Wen Jian
Published: January 2024

This study presents a protocol for the direct site‐selective difunctionalization of pyrazoles under mild reaction conditions. This protocol showcase a notable site‐selectivity and encompasses a wide substrate scope. Detailed mechanistic investigations elucidate the dual role of the sulfonium salt acting both as the reaction substrate and acid donor, thereby effectively catalyzing the reaction. The demonstrated one‐pot synthesis, scale‐up reaction and subsequent product modifications can assist in advancing the potential application of this protocol in organic synthesis and its associated domains.
A Silica‐Supported Yttrium Triflate Packed Bed Reactor for Continuous Flow Michael Addition of Indoles to Benzylidene Malonates
Authors: Donato Emanuela , Chiroli Valerio , Puglisi Alessandra , Benaglia Maurizio
Published: January 2024

The catalytic properties of packed bed reactors filled with Y(OTf)3 immobilised onto functionalised silica have been tested in the Michael addition of indoles to benzylidene malonates under flow conditions, providing improved productivity over the batch conditions, a greater ease of recovery of the final products and a prolonged life of the catalyst. Noteworthy, the same catalytic reactor, after being used for five days, was employed to perform a different reaction, a stereoselective Diels Alder cycloaddition in flow, with a 24 times higher productivity compared to the in‐batch reaction.
Synthesis and Organo‐Catalyzed Ring‐Opening of a Six‐Membered Heterocycle Combining Phosphonate and Ester Functions
Authors: Ungpittagul Thasanaporn , Virachotikul Arnut , Monot Julien , Martín‐Vaca Blanca , Bourissou Didier
Published: January 2024

The synthesis of a difunctional P‐heterocycle combining phosphonate and ester moieties in a six‐membered ring is described. Using trifluoromethane sulfonic acid HOTf as organocatalyst, ring‐opening with neopentyl alcohol readily occurs with complete selectivity for O‐acyl bond cleavage. In turn, ring‐opening polymerization proceeds in a controlled manner when an excess of P‐heterocycle is used. Copolymerization with ϵ‐caprolactone is also reported and semi‐batch conditions are shown to enable regular incorporation of the phosphonate moieties along the polymer chains.
Selective Synthesis of Tetrahydro Oxepines by Cu‐Catalyzed Condensations of Diazomalonates and gem‐Dialkyl Vinyl Oxetanes
Authors: Montagnon Claire , Pertschi Romain , Besnard Céline , Lacour Jérôme
Published: January 2024

Thanks to an unprecedented gem‐dialkyl substituent effect, an efficient synthesis of tetrahydro oxepine derivatives is achieved by ring expansion of vinyl oxetanes using acceptor(−acceptor) diazo reagents under Cu(II)‐catalysis. A large scope of 2‐vinyl oxetanes and either diazo mono or diester reagents give access to a series of functionalized oxepines.
Understanding and Tuning Magnetism in Layered Ising‐Type Antiferromagnet FePSe3 for Potential 2D Magnet
Authors: Basnet Rabindra , Patel Taksh , Wang Jian , Upreti Dinesh , Chhetri Santosh Karki , Acharya Gokul , Nabi Md Rafique Un , Sakon Josh , Hu Jin
Published: January 2024

Recent developments in 2D magnetic materials have motivated the search for new van der Waals magnetic materials, especially Ising‐type magnets with strong magnetic anisotropy. Fe‐based MPX3 (M = transition metal, X = chalcogen) compounds such as FePS3 and FePSe3 both exhibit an Ising‐type magnetic order, but FePSe3 receives much less attention compared to FePS3. This work focuses on establishing the strategy to engineer magnetic anisotropy and exchange interactions in this less‐explored compound. Through chalcogen and metal substitutions, the magnetic anisotropy is found to be immune against S substitution for Se whereas tunable only with heavy Mn substitution for Fe. In particular, Mn substitution leads to a continuous rotation of magnetic moments from the out‐of‐plane direction toward the in‐plane. Furthermore, the magnetic ordering temperature displays non‐monotonic doping dependence for both chalcogen and metal substitutions but due to different mechanisms. These findings provide deeper insight into the Ising‐type magnetism in this important van der Waals material, shedding light on the study of other Ising‐type magnetic systems as well as discovering novel 2D magnets for potential applications in spintronics.
DNA nanostructures prevent the formation of and convert toxic amyloid proteospecies into cytocompatible and biodegradable spherical complexes
Authors: Kihal Nadjib , Nguyen Phuong Trang , Nazemi Ali , Greschner Andrea A. , Gauthier Marc A. , Bourgault Steve
Published: January 2024

The deposition of insoluble proteinaceous aggregates in the form of amyloid fibrils within the extracellular space of tissues is associated with numerous diseases. The development of molecular approaches to arrest amyloid formation and prevent cellular degeneration remains very challenging due to the complexity of the process of protein aggregation, which encompasses an infinite array of conformations and quaternary structures. Polyanionic biopolymers, such as glycosaminoglycans and RNAs, have been shown to modulate the self‐assembly of amyloidogenic polypeptides and to reduce the toxicity induced by the formation of oligomeric and/or pre‐fibrillar proteospecies. This study evaluates the effects of double‐stranded DNA (dsDNA) nanostructures (1D, 2D, and 3D) on amyloid self‐assembly, fibril disaggregation, and the cytotoxicity associated with amyloidogenesis. Using the islet amyloid polypeptide (IAPP) whose pancreatic accumulation is the hallmark of type 2 diabetes, it was observed that dsDNA nanostructures inhibit amyloid formation by inducing the formation of spherical complexes in which the peptide adopts a random coil conformation. Interestingly, the DNA nanostructures showed a persistent ability to disassemble enzymatically and thermodynamically stable amyloid fibrils into nanoscale DNA/IAPP entities that are fully compatible with β‐pancreatic cells and are biodegradable by proteolysis. Notably, dsDNA nanostructures avidly trapped highly toxic soluble oligomeric species in complete cell culture media and converted them into non‐toxic binary complexes. Overall, these results expose the potent modulatory effects of dsDNA on amyloidogenic pathways, and these DNA nanoscaffolds could be used as a source of inspiration for the design of molecules to fight amyloid‐related disorders.
Predictors and outcomes of fluctuations in the clinical dementia rating scale
Authors: Wilks Hannah , Benzinger Tammie L. S. , Schindler Suzanne E. , Cruchaga Carlos , Morris John C. , Hassenstab Jason
Published: January 2024

INTRODUCTION

Reversion, or change in cognitive status from impaired to normal, is common in aging and dementia studies, but it remains unclear what factors predict reversion.

METHODS

We investigated whether reverters, defined as those who revert from a Clinical Dementia Rating® (CDR®) scale score of 0.5 to CDR 0) differed on cognition and biomarkers from unimpaired participants (always CDR 0) and impaired participants (converted to CDR > 0 and had no reversion events). Models evaluated relationships between biomarker status, apolipoprotein E (APOE) ε4 status, and cognition. Additional models described predictors of reversion and predictors of eventual progression to CDR > 0.

RESULTS

CDR reversion was associated with younger age, better cognition, and negative amyloid biomarker status. Reverters that eventually progressed to CDR > 0 had more visits, were older, and were more likely to have an APOE ε4 allele.

DISCUSSION

CDR reversion occupies a transitional phase in disease progression between cognitive normality and overt dementia. Reverters may be ideal candidates for secondary prevention Alzheimer's disease (AD) trials.

Highlights

Reverters had more longitudinal cognitive decline than those who remained cognitively normal.

Predictors of reversion: younger age, better cognition, and negative amyloid biomarker status.

Reverting from CDR 0.5 to 0 is a risk factor for future conversion to CDR > 0.

CDR reversion may be a transitional phase in Alzheimer's Disease progression.

CDR reverters may be ideal for Alzheimer's disease secondary prevention trials.
Scalable plasma and digital cognitive markers for diagnosis and prognosis of Alzheimer's disease and related dementias
Authors: Tsoy Elena , La Joie Renaud , VandeVrede Lawren , Rojas Julio C. , Yballa Claire , Chan Brandon , Lago Argentina Lario , Rodriguez Anne‐Marie , Goode Collette A. , Erlhoff Sabrina J. , Tee Boon Lead , Windon Charles , Lanata Serggio , Kramer Joel H. , Miller Bruce L. , Dilworth‐Anderson Peggye , Boxer Adam L. , Rabinovici Gil D. , Possin Katherine L.
Published: January 2024

INTRODUCTION

With emergence of disease‐modifying therapies, efficient diagnostic pathways are critically needed to identify treatment candidates, evaluate disease severity, and support prognosis. A combination of plasma biomarkers and brief digital cognitive assessments could provide a scalable alternative to current diagnostic work‐up.

METHODS

We examined the accuracy of plasma biomarkers and a 10‐minute supervised tablet‐based cognitive assessment (Tablet‐based Cognitive Assessment Tool Brain Health Assessment [TabCAT‐BHA]) in predicting amyloid β positive (Aβ+) status on positron emission tomography (PET), concurrent disease severity, and functional decline in 309 older adults with subjective cognitive impairment (n = 49), mild cognitive impairment (n = 159), and dementia (n = 101).

RESULTS

Combination of plasma pTau181, Aβ42/40, neurofilament light (NfL), and TabCAT‐BHA was optimal for predicting Aβ‐PET positivity (AUC = 0.962). Whereas NfL and TabCAT‐BHA optimally predicted concurrent disease severity, combining these with pTau181 and glial fibrillary acidic protein was most accurate in predicting functional decline.

DISCUSSION

Combinations of plasma and digital cognitive markers show promise for scalable diagnosis and prognosis of ADRD.

Highlights

The need for cost‐efficient diagnostic and prognostic markers of AD is urgent.

Plasma and digital cognitive markers provide complementary diagnostic contributions.

Combination of these markers holds promise for scalable diagnosis and prognosis.

Future validation in community cohorts is needed to inform clinical implementation.
Enhancing Plasmonic Hot Electron Energy on Ag Surface by Amine Coordination
Authors: Wang Ying , Li Yonglong , Yang Xian , Wang Teng , Du Xiaomeng , Zhu Aonan , Xie Weiwei , Xie Wei
Published: January 2024

Plasmonic catalysis has emerged as a promising approach to solar‐chemical energy conversion. Notably, hot carriers play a decisive role in plasmonic catalysis since only when their energy matches with the LUMO or HOMO energy of the reactant molecule, can the reaction be activated. However, the hot carrier energy depends on the intrinsic physicochemical properties of the plasmonic metal substrate and the interaction with incident light. Tuning the hot carrier energy is of great significance for plasmonic catalysis but remains challenging. Here, we demonstrate that the energy of hot electrons can be significantly elevated to an unprecedented level through the coordination of amines on Ag surface. The bonding of amines and Ag reduces the work function of nanoparticles, leading to the increase of hot electron energy by 0.4 eV. This enhancement of energy promotes the cleavage of C−X (X=Cl, F) bonds upon excitation by visible light. This study provides new insights for promoting plasmonic charge transfer and enhancing the photocatalytic performance of plasmon‐mediated systems.
Pulmonary aspiration of gastric contents in two patients taking semaglutide for weight loss
Authors: Avraham S. A. , Hossein J. , Somri F. , Hawash N. , Hochman O.
Published: January 2024

Semaglutide is a new weight loss treatment that has received substantial media attention in recent years. Anaesthetists must be aware of a potentially dangerous side effect of the drug: decreased gastric emptying. This is caused by effects on gastric smooth muscle, mediated by the vagal afferent nerves. This is especially relevant in the peri‐operative setting where pulmonary aspiration of gastric contents is a recognised complication. Here, we report two cases of peri‐operative regurgitation of gastric contents in patients taking semaglutide. A patient taking semaglutide may have a full stomach despite compliance with routine pre‐operative fasting guidelines. We consider how to manage patients receiving glucagon‐like peptide‐1 agonist therapy in the peri‐operative period, including identifying those at high risk of regurgitation. Precautions such as rapid sequence induction and tracheal intubation can be used, but gastric ultrasound may also be useful in the pre‐operative environment to help identify patients at high risk of aspiration.
Thiosemicarbazone ligands based transition metal complexes: A multifaceted investigation of antituberculosis, anti‐inflammatory, antibacterial, antifungal activities, and molecular docking, density functional theory, molecular electrostatic potential, absorption, distribution, metabolism, excretion, and toxicity studies
Authors: Kumar Binesh , Devi Jai , Dubey Amit , Tufail Nasir , Khurana Daksh
Published: January 2024

Infectious diseases have held a prominent place in the history of humanity, shaping societies, influencing medical advances, and affecting the lives of individuals on a global scale and are caused by a variety of pathogens that lead to a wide range of illnesses. Among this diverse group of ailments, tuberculosis (TB), inflammatory conditions, and various bacterial and fungal diseases stand out as major challenges that have long plagued humanity. Thus, the aim of this research is delve a significant combatting agent against TB, inflammation, bacterial and fungal deformities. To explore the above facts and to examine the therapeutic potential, the previously synthesized thiosemicarbazones (1–2) and their Co (II), Ni (II), Cu (II), Zn (II) complexes (3–10) of benzaldehydes and 4‐(4‐ethylphenyl)‐3‐thiosemicarbazide were proposed for in vitro investigation by microplate Alamar Blue, bovine serum albumin, and serial dilution methods. The compound (10) demonstrates almost double effectiveness in controlling TB dysfunction (minimum inhibitory concentration [MIC] value 0.006 ± 0.001 μmol/mL), surpassing streptomycin, whereas (6) and (9) have comparable TB inhibition efficacy to streptomycin. The compound (10) also has the highest potency for inflammation (6.75 ± 0.09 μM), bacterial (0.0066 μmol/mL), and fungal (0.0066 μmol/mL) ailments among the tested compounds with comparable inhibition abilities to their respective standard drugs. Moreover, molecular docking (targeting the PDB ID 6H53 and 1CX2 proteins), density functional theory (DFT), molecular electrostatic potential (MESP), and absorption, distribution, metabolism, excretion, and toxicity (ADMET) evaluations were performed against the highly efficient ligand (2) and its complexes (7–10) to validate the in vitro results. In this endeavor, our aim is to actively participate in the continuous initiatives aimed at fighting infectious diseases and enhancing global health and overall well‐being.
Interfacial Activity of Janus Particle: Unity of Molecular Surfactant and Homogeneous Particle
Authors: Liu Haipeng , Long Yingchun , Liang Fuxin
Published: January 2024

Janus particles with different compositions and properties segmented to different regions on the surface of one objector provide more opportunities for interfacial engineering. As a novel interfacial active material, Janus particles integrate the amphiphilic properties of molecular surfactants and the Pickering effect of homogeneous particles. In this research, the outstanding properties of Janus particles on various interfaces are examined from both theoretical and practical perspectives, and the advantages of Janus particles over molecular surfactants and homogeneous particle surfactants are analyzed. We believe that Janus particles are ideal tools for interface regulation and functionalization in the future.
Modeling and control of drug assignment for pharmaceutical cabinets using discrete event systems approaches
Authors: Soumatia Maroua , Amari Saïd , Hachemi Khalid
Published: January 2024

The public health sector, considered to be vital, especially in this pandemic crisis of COVID‐19, requires automation and control of drug distribution in pharmacies commonly called: “Dispensing.” In this paper, we address the medication assignment problem for automated dispensing cabinets (ADCs). First, we use a network of conflicting timed event graphs (CTEGs), a class of timed Petri nets with shared resources, to model pharmaceutical cabinets. Second, we develop a new method for controlling CTEGs under mutual exclusion constraints (MECs) to solve the problem of drug assignment, using a control approach based on Min‐Plus algebra. Finally, a case study of assigning drugs is given to illustrate the proposed methodology and show the efficiency of the developed control laws.
Finite‐time robust simultaneous stabilization control for two nonlinear singular time‐delay systems
Authors: Li Qi , Yang Renming , Wang Yongliang , Liu Feng
Published: January 2024

In this paper, the finite‐time simultaneous stabilization problem of two nonlinear singular time‐delay Hamiltonian systems is investigated. Firstly, the two general nonlinear singular time‐delay Hamiltonian systems are transformed into their Hamiltonian differential‐algebraic forms by equivalent transformation, respectively, they are then converted to two strictly dissipative Hamiltonian forms via the state feedback method, and two strictly dissipative Hamiltonian systems are extended into a Hamiltonian one. Based on which, a suitable Hamiltonian function is constructed to analyze the finite‐time simultaneous stability and finite‐time robust simultaneous stabilization problem. Finally, an illustrative example is given to show the effectiveness of the results obtained. It should be pointed out that since there does not exist a finite‐time stability criterion on the nonlinear singular delay system, we adopt a new double compound asymptotic method.
Contactless face video based vital signs detection framework for continuous health monitoring using feature optimization and hybrid neural network
Authors: Anil Jalaja Anju , Kavitha Maruthai
Published: January 2024

Continuous monitoring of vital signs such as respiration and heart rate is essential to detect and predict conditions that may affect the patient's well‐being. To detect these vital signs most medical systems use contact sensors. They are not feasible for long term monitoring and are not repeatable. Vital signs using facial video‐noncontact monitoring are becoming increasingly important. Researchers in the last few years although considerable progress has been made, challenging datasets absence timing of assessment process and the technology still has some limitations such as time consuming nature and lack of computer portability. To solve those problems, we propose a contactless video based vital signs detection framework for continuous health monitoring using feature optimization and hybrid neural network. In the proposed technique, modified war strategy optimization algorithm is proposed to segment the face portion from the input video frames. Then, we utilize the known data acquisition models to extract vital signs from the segmented face portions are heart rate, blood pressure, respiratory rate and oxygen saturation. An improved neural network structure (Lifting Net) is further used to achieve the adaptive extraction of deep hidden features for specific signs, for realizing the high precision of human health monitoring. The Hughes effect or dimensionality issue affects detection accuracy in sign classification when there are fewer training instances relative to the number of spectral features. The problem can be overcome through feature optimization here Northern goshawk optimization algorithm is used to select optimal best features which reduces the data dimensionality issue. Furthermore, hybrid deep ensemble reinforcement learning classifier is proposed for the human vital sign detection and classification which ensures the early detection of patient abnormality. Finally, we validate our framework using benchmark video datasets such as TokyoTechrPPG, PURE and COHFACE. To proves the effectiveness of proposed technique using simulation results and comparative analysis.
In Vitro Determination of Nitric Oxide Synthase Inhibition, Antioxidant Capacity and Phenolic Content of Various Natural Products (Bee and Herbal Products)
Authors: Yaylaci Karahalil Fatma , Bakirhan Fatma , Kara Yakup
Published: January 2024

It is obvious that the oxidation process is an undeniable fact and when it comes to aging, one of the first solutions that come to mind is natural products. When it comes to natural products, both plants and bee products play an important, almost combative role against oxidation. For this purpose, natural products of both plant and animal origin were considered together in our study: Linden, green tea, aronia, wild grapes, myrtle, blueberries and basil, honey, pollen and propolis. Total phenolic content values of the extracts ranged between 49.28 and 3859.06 mg gallic acid equivalent/100 g, and propolis, green tea, chestnut flower and aronia samples were found to have the highest values. When looking at the NOS inhibition potential, it was determined that propolis, pollen and aronia samples had the highest percentage inhibition values of 98.11, 92.29, 83.44, respectively. Antioxidant activities of methanolic extracts were investigated using iron(III) reducing/antioxidant capacity (FRAP), 2,2‐Diphenyl‐1‐picrylhydrazyl (DPPH) radical scavenging activity test and NOS inhibition tests. The phenolic composition of methanolic extracts was tested using the RP‐HPLC‐UV (high‐performance liquid chromatographic method with ultraviolet) method with 19 phenolic standards.
Therapeutic Potential of Benzimidazoisoquinoline Derivatives in Alleviating Murine Hepatic Fibrosis
Authors: Mekala Sowmya , Sukumar Genji , Chawla Shilpa , Geesala Ramasatyaveni , Prashanth Jupally , Reddy B. Jagan Mohan , Mainkar Prathama , Das Amitava
Published: January 2024

Short Title: Benzimidazoisoquinoline derivatives as potent antifibrotics Hepatic fibrosis is a pathological condition of liver disease with an increasing number of cases worldwide. Therapeutic strategies are warranted to target the activated hepatic stellate cells (HSCs), the collagen‐producing cells, an effective strategy for controlling the disease progression. Benzimidazoisoquinoline derivatives were synthesized as hybrid molecules by the combination of benzimidazoles and isoquinolines to evaluate their anti‐fibrotic potential using an in‐vitro and in‐vivo model of hepatic fibrosis. A small library of benzimidazoisoquinoline derivatives (1–17 and 18–21) was synthesized from 2‐aryl benzimidazole and acetylene functionalities through C−H and N−H activation. Compounds (10 and its recently synthesized derivatives 18–21) depicted a significant decrease in PDGF‐BB and/or TGFβ‐induced proliferation (1.7–1.9 ‐fold), migration (3.5–5.0 ‐fold), and fibrosis‐related gene expressions in HSCs. These compounds could revert the hepatic damage caused by chronic exposure to hepatotoxicants, ethanol, and/or carbon tetrachloride as evident from the histological, biochemical, and molecular analysis. Anti‐fibrotic effect of the compounds was supported by the decrease in the malondialdehyde level, collagen deposition, and gene expression levels of fibrosis‐related markers such as α‐SMA, COL1α1, PDGFRβ, and TGFRIIβ in the preclinical models of hepatic fibrosis. In conclusion, the synthesized benzimidazoisoquinoline derivatives (compounds 18, 19, 20, and 21) possess anti‐fibrotic therapeutic potential against liver fibrosis.
Synthesis, Thermal Stability and Antifungal Evaluation of Two New Pyrrole Esters
Authors: Gao Ziting , Fan Wenpeng , Zhang Ruiting , Li Pengyu , Yang Xiaopeng , Gao Xue , Ji Xiaoming , Wei Yuewei , Lai Miao
Published: January 2024

To develop new chemicals that are stable at high temperatures with biological activity, a pyrrole intermediate was firstly synthesized using glucosamine hydrochloride as raw materials through cyclization and oxidation. Further, two novel pyrrole ester derivatives were prepared via Steglich esterification from pyrrole intermediate with vanillin and ethyl maltol, respectively. Nuclear magnetic resonance (1H‐NMR, 13C NMR), infrared spectroscopy (IR) and high resolution mass spectrometry (HRMS) were used to confirm the target compounds. Thermal behavior of the compounds was investigated by thermogravimetry (TG), differential scanning calorimeter (DSC) and the pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS) methods. The plausible pyrolytic mechanism was proposed. Additionally, their biological activities against the pathogens Fusarium graminearum, Fusarium oxysporum, Fusarium moniliforme, Phytophthora nicotianae, and Rhizoctonia solani were assessed. These target compounds showed outstanding antifungal activities and the highest inhibitor rates of 62.50 % and 68.75 % against R. solani with EC50 values of 0.0296 and 0.0200 mg mL−1, respectively. SDHI protein sequence was molecularly docked to identify the binding mechanisms in the active pocket and examine the interactions between both the molecules and the SDHI protein.
Transition Metal and Photocatalyst Free Arylation via Photoexcitable Electron Donor Acceptor Complexes:Mediation and Catalysis
Authors: Volkov Alexey A. , Bugaenko Dmitry I. , Karchava Alexander V.
Published: January 2024

Visible‐light‐activated organic reactions unlock novel avenues for complex molecular transformations, impossible under standard “thermal” conditions, which makes them powerful tools in the arsenal of synthetic chemistry. However, transition metal‐based or organic photoredox catalysts are often used to ensure productive absorption of visible light, which might be not desirable to medicinal chemistry and industry due to toxicity, low sustainability, and high cost of most photocatalysts. A more environmentally and economically benign approach is based on the formation of transient electron donor‐acceptor (EDA) complexes between two reagents or a reagent and an additive, that readily absorb visible light, acting as internal photosensitizers. Within the EDA complex‐based arylation strategies, chemical transformations are mediated by noncovalent interaction between two molecules, namely between electron‐poor aryl halides or their synthetic equivalents and electron‐rich nucleophilic reagents or additives. Moreover, besides stoichiometric EDA complexes between two molecules, EDA complex based organocatalysis can be achieved in certain cases through regeneration of the donor molecules in the course of the reaction. Photoexcitation of the EDA complexes induces a single electron transfer (SET) process to generate aryl radical species for the arylation step. This Review will focus on the state‐of‐the‐art EDA complex‐based arylation strategies utilizing aryl halides, aryldiazonium, diaryliodonium, arylsulfonium and arylphosphonium salts as reactants, published mainly in the last five years.
Photo‐electrochemical O2 Reduction to H2O2 Using a Co‐Porphyrin Based Metal‐Organic Framework
Authors: Ifraemov Raya , Binyamin Shahar , Pearlmutter Yanai , Liberman Itamar , Shimoni Ran , Hod Idan
Published: January 2024

Metal‐Organic Frameworks (MOFs) hold great potential to be used as porous (photo)‐electrocatalytic platforms containing large concentration of immobilized molecular catalysts. Indeed, the use of MOFs in a photo‐electrochemical devices was recently demonstrated. However, so far there are no reports of MOFs used for photo‐electrochemical O2 reduction to H2O2. Herein, we utilize a Co‐porphyrin based MOF (Co‐MOF‐525), that produces H2O2 at high faradaic efficiency (95 %), both electrochemically and photo‐electrochemically. Electrochemical characterization show that the active catalytic site is a MOF‐tethered Co(I)‐porphyrin. Additionally, under light illumination, the MOF's intrinsic catalytic rate is significantly accelerated compared to dark electrolysis conditions. Thus, this work could open a path for future implementation of photoactive MOFs in solar fuel schemes.
Enhanced Oxygen Reduction Activity of Platinum Micropore
Authors: Nakahara Kota , Ikezawa Atsunori , Okajima Takeyoshi , Arai Hajime
Published: January 2024

The high overpotential of oxygen reduction reaction (ORR) prevents the wide commercialization of fuel cells and metal‐air batteries. To accelerate the reaction rate, porous electrocatalysts draw attention to obtain a higher specific surface area. However, the effect of micropores on ORR kinetics has not been understood because of the non‐uniform pore sizes, length, and tortuosity of practical electrocatalysts. In this study, we evaluate ORR activity in a micropore using platinum model electrodes with arrays of cylindrical pores with a uniform pore diameter of 1.8 nm. The model electrodes having pore lengths of 45, 100, and 380 nm are fabricated, and their ORR performances are examined by electrochemical measurements and numerical simulations in 0.1 mol dm−3 KOH aqueous solution. The intrinsic ORR activity of the micropore is successfully obtained with the electrode having a pore length of 45 nm, where oxygen transport resistance in the micropore has little effect on ORR. It is found that the intrinsic ORR activity of the micropore is higher than that of a planar Pt surface. X‐ray photoelectron spectroscopy and CO stripping voltammetry indicate a downshift of the d‐band center, which can be the origin of the high intrinsic ORR activity.
Proton transfer and regulation across chemical interfaces by small‐molecule assemblies
Authors: Nguyen Lynn , Aquino Joseline , Mao Cindy , Tavassol Hadi
Published: January 2024

We report on measurements and control of proton gradient across interfaces of water and dichloroethane. Such interfaces are interesting as mimics of biological membranes. We use impedance spectroscopy to quantify interfacial proton gradient and identify proton transfer modes. We quantify proton movement using reciprocal of time constant (τ−1) acquired from electrochemical impedance modeling. We show that proton gradient across interfaces of water/dichloroethane and τ−1 correlate with the aqueous phase pH, changing from ca. 1 s−1 at pH 1 to 0.2 s−1 at pH 7. τ−1 changes in the presence of proton shuttling fat‐soluble molecules. Dinitrophenol acts as a pH activated proton coupler which is active at around neutral pH and inert at pH <4. However, quinone type cofactors change the interfacial proton transport when activated by redox reactions with ferrocene type molecules, such as decamethyl ferrocence (DMFc). Quinone type cofactors show distinct features in their impedance response assigned to a proton coupled electron transfer (PCET) process, different from the uncoupled proton transfer activity of dinitrophenol. The observed PCET reaction significantly changes τ−1. We use τ−1 as a proton transport descriptor. In particular, CoQ10‐DMFc shows a τ−1 of 3.5 s−1 at pH 7, indicating how small‐molecule assemblies change proton availability.
Electrocatalytic Reduction of CO2 and H2O with Zn(II) Complexes Through Metal‐Ligand Cooperation
Authors: Norouziyanlakvan Somayeh , Berro Patrick , Rao Gyandshwar Kumar , Gabidullin Bulat , Richeson Darrin
Published: January 2024

Air and water‐stable zinc (II) complexes of neutral pincer bis(diphenylphosphino)‐2,6‐di(amino)pyridine (“PN3P”) ligands are reported. These compounds, [Zn(κ2‐2,6‐{Ph2PNR}2(NC5H3))Br2] (R=Me, 1; R=H, 2), were shown to be capable of electrocatalytic reduction of CO2 at −2.3 V vs. Fc+/0 to selectively yield CO in mixed water/acetonitrile solutions. These complexes also electrocatalytically generate H2 from water in acetonitrile solutions, at the same potential, with Faradaic efficiencies of up to 90 %. DFT computations support a proposed mechanism involving the first reduction of 1 or 2 occurring at the PN3P ligand. Furthermore, computational analysis suggested a mechanism involving metal‐ligand cooperation of a Lewis acidic Zn(II) and a basic ligand.
Application of quasi solid electrolytes in organic based electrochromic devices: A mini review
Authors: Orimolade Benjamin O. , Draper Emily R.
Published: January 2024

The interest in all solid organic based electrochromic devices (ECDs) is on the increase. This is because these devices offer the applicability of electrochromic materials in products such as smart sensors, smart windows, flexible wearables and energy storage devices. The use of quasi‐solid electrolytes for the construction of these ECDs is attractive because of their ease of preparation, availability, low cost, improve electrochromic performance, good ionic conductivity and prevention of leakages in ECDs. Hence, in this review, a detailed discussion is presented on the progress in the development of semi‐solid electrolytes for ECDs fabrication. The preparation of the most common electrolytes that have been applied for organic based ECDs are summarized. Particular attention is given to efforts and strategies that have been adopted to improve the efficiency of quasi‐solid electrolytes. Importantly, knowledge gaps that warrant further research are clearly identified and recommendations for future works are suggested. This review will be very beneficial for both established and new researchers in the field of electrochromic devices and material science.
Modeling Amine Methylation in Methyl Ester Cavitand
Authors: Norjmaa Gantulga , Rebek Julius , Himo Fahmi
Published: January 2024

Methylation of amines inside an introverted resorcinarene‐based deep methyl ester cavitand is investigated by means of molecular dynamics simulations and quantum chemical calculations. Experimentally, the cavitand has been shown to bind a number of amines and accelerate the methylation reaction by more than four orders of magnitude for some of them. Eight different amines are considered in the present study, and the geometries and energies of their binding to the cavitand are first characterized and analyzed. Next, the methyl transfer reactions are investigated and the calculated barriers are found to be in generally good agreement with experimental results. In particular, the experimentally‐observed rate acceleration in the cavitand as compared to the solution reaction is well reproduced by the calculations. The origins of this rate acceleration are analyzed by computational modifications made to the structure of the cavitand, and the role of the solvent is discussed.
Metal Influence on Cyaphide‐Azide 1,3‐Dipolar Cycloaddition Reactions: Aromaticity and Activation Strain
Authors: González‐Pinardo Daniel , Goicoechea Jose M. , Fernández Israel
Published: January 2024

The factors governing 1,3‐dipolar cycloaddition reactions involving C≡P‐containing compounds are computationally explored in detail using quantum chemical tools. To this end, the parent process involving tBuN3 and tBuCP is analyzed and compared to the analogous reaction involving organometallic cyaphide complexes (metal=Au, Pt, Ge, Mg), in order to understand the role of the metal fragment in such transformations. It is found that while the metal fragment does not significantly influence the aromaticity of the corresponding concerted transition states or the regioselectivity of the transformation, it may modify the reactivity of the cyaphide complexes (i. e. Ge and Mg cyaphide complexes are comparatively more reactive). The computed reactivity trends and the factors behind the regioselectivity of the cycloaddition reaction are quantitatively analyzed with the help of the activation strain model in combination with the energy decomposition analysis method.
Starfruit‐Shaped Zirconium Metal–Organic Frameworks: From 3D Intermediates to 2D Nanosheet Petals with Enhanced Catalytic Activity
Authors: Tao Cheng‐an , Wang Beibei , Zhao He , Yang Xuheng , Huang Jian , Wang Jianfang
Published: January 2024

Invited for the cover of this issue is the group of Cheng‐an Tao, Jianfang Wang and co‐workers at the University of Defense Technology. The image depicts a novel starfruit‐shaped metal–organic framework composed of zirconium and tetra(4‐carboxyphenyl)porphine linkers and characterized by 2D nanosheet petals grown through edge‐sharing that showcases superior catalytic activity. Read the full text of the article at 10.1002/chem.202302835.
A review of just‐in‐time learning‐based soft sensor in industrial process
Authors: Sheng Weiwei , Qian Jinchuan , Song Zhihuan , Zhang Xinmin
Published: January 2024

Data‐driven soft sensing approaches have been a hot research field for decades and are increasingly used in industrial processes due to their advantages of easy implementation and high efficiency. However, nonlinear and time‐varying problems widely exist in practical industrial processes. Just‐in‐time learning (JITL) was proposed to solve these problems and has attracted great attention in practical applications. To present a comprehensive review of JITL‐based soft sensor studies and provide detailed technical guidance for new researchers, this paper introduces the recent research on JITL‐based soft sensor modelling methods in the industrial process from three aspects: similarity criterion, sample subset, and local model, which include the whole process of establishing a JITL‐based soft sensor. Moreover, the future research and innovation directions of JITL‐based soft sensors in industrial processes are also prospected.
Assembly of FAP93 at the proximal axoneme in Chlamydomonas cilia
Authors: Hwang Juyeon , Yanagisawa Haruaki , Davis Keira C. , Hunter Emily L. , Fox Laura A. , Jimenez Ariana R. , Goodwin Reagan E. , Gordon Sarah A. , Stuart Courtney D. E. , Bower Raqual , Porter Mary E. , Dutcher Susan K. , Sale Winfield S. , Lechtreck Karl F. , Alford Lea M.
Published: January 2024

To identify proteins specific to the proximal ciliary axoneme, we used iTRAQ to compare short (~2 μm) and full‐length (~11 μm) axonemes of Chlamydomonas. Known components of the proximal axoneme such as minor dynein heavy chains and LF5 kinase as well as the ciliary tip proteins FAP256 (CEP104) and EB1 were enriched in short axonemes whereas proteins present along the length of the axoneme were of similar abundance in both samples. The iTRAQ analysis revealed that FAP93, a protein of unknown function, and protein phosphatase 2A (PP2A) are enriched in the short axonemes. Consistently, immunoblots show enrichment of FAP93 and PP2A in short axonemes and immunofluorescence confirms the localization of FAP93 and enrichment of PP2A at the proximal axoneme. Ciliary regeneration reveals that FAP93 assembles continuously but more slowly than other axonemal structures and terminates at 1.03 μm in steady‐state axonemes. The length of FAP93 assembly correlates with ciliary length, demonstrating ciliary length‐dependent assembly of FAP93. Dikaryon rescue experiments show that FAP93 can assemble independently of IFT transport. In addition, FRAP analysis of GFP‐tagged FAP93 demonstrates that FAP93 is stably anchored in the axoneme. FAP93 may function as a scaffold for assembly of other specific proteins at the proximal axoneme.
Duchenne and Becker muscular dystrophy: Cellular mechanisms, image analysis, and computational models: A review
Authors: Escobar‐Huertas J. F. , Vaca‐González Juan Jairo , Guevara Johana María , Ramirez‐Martinez Angelica M. , Trabelsi Olfa , Garzón‐Alvarado D. A.
Published: January 2024

The muscle is the principal tissue that is capable to transform potential energy into kinetic energy. This process is due to the transformation of chemical energy into mechanical energy to enhance the movements and all the daily activities. However, muscular tissues can be affected by some pathologies associated with genetic alterations that affect the expression of proteins. As the muscle is a highly organized structure in which most of the signaling pathways and proteins are related to one another, pathologies may overlap. Duchenne muscular dystrophy (DMD) is one of the most severe muscle pathologies triggering degeneration and muscle necrosis. Several mathematical models have been developed to predict muscle response to different scenarios and pathologies. The aim of this review is to describe DMD and Becker muscular dystrophy in terms of cellular behavior and molecular disorders and to present an overview of the computational models implemented to understand muscle behavior with the aim of improving regenerative therapy.
Mechanochemical Hydrolysis of Polysaccharide Biomass: Scope and Mechanistic Insights
Authors: Kobayashi Hirokazu , Fukuoka Atsushi
Published: January 2024

Mechanical forces can affect chemical reactions in a way that thermal reactions cannot do, which may have a variety of applications. In biomass conversion, the selective conversion of cellulose and chitin is a grand challenge because they are the top two most abundant resources and recalcitrant materials that are insoluble in common solvents. However, recent works have clarified that mechanical forces enable the depolymerization of these polysaccharides, leading to the selective production of corresponding monomers and oligomers. This article reviews the mechanochemical hydrolysis of cellulose and chitin, particularly focusing on the scope and mechanisms to show a landscape of this research field and future subjects. We introduce the background of mechanochemistry and biomass conversion, followed by recent progress on the mechanochemical hydrolysis of the polysaccharides. Afterwards, a considerable space is devoted to the mechanistic consideration on the mechanochemical reactions.
Measuring Protein‐Protein Interactions and Quantifying Their Dissociation Constants with Mass Photometry
Authors: Kofinova Zornitsa , Karunanithy Gogulan , Ferreira Ana Sofia , Struwe Weston B.
Published: January 2024

Protein‐protein interactions underlie most biological processes, and determining the affinity and abundance of binding partners for each interaction is often a challenging task because these interactions often involve multiple ligands and binding sites. Standard methods for determining the affinity of protein interactions often require a large amount of starting material in addition to potentially disruptive labeling or immobilization of the binding partners. Mass photometry is a bioanalytical technique that measures the mass of single biomolecules in solution, quickly and with minimal sample requirements. This article describes how mass photometry can be used to determine the mass distribution of binding partners, the complexes they form, the relative abundance of each species, and, accordingly, the dissociation constant (KD) of their interactions. © 2024 Refeyn Ltd. Current Protocols published by Wiley Periodicals LLC.

Basic Protocol: Using mass photometry to measure protein‐protein binding and quantify the KD of this interaction
Tuning Carbon Dioxide Reduction Reaction Selectivity of Bi Single‐Atom Electrocatalysts with Controlled Coordination Environments
Authors: Santra Saswati , Streibel Verena , Wagner Laura I. , Cheng Ningyan , Ding Pan , Zhou Guanda , Sirotti Elise , Kisslinger Ryan , Rieth Tim , Zhang Siyuan , Sharp Ian D.
Published: January 2024

Control over product selectivity of the electrocatalytic CO2 reduction reaction (CO2RR) is a crucial challenge for the sustainable production of carbon‐based chemical feedstocks. In this regard, single‐atom catalysts (SACs) are promising materials due to their tunable coordination environments, which could enable tailored catalytic activities and selectivities, as well as new insights into structure‐activity relationships. However, direct evidence for selectivity control via systematic tuning of the SAC coordination environment is scarce. In this work, we have synthesized two differently coordinated Bi SACs anchored to the same host material (carbon black) and characterized their CO2RR activities and selectivities. We find that oxophilic, oxygen‐coordinated Bi atoms produce HCOOH, while nitrogen‐coordinated Bi atoms generate CO. Importantly, use of the same support material assured that alternation of the coordination environment is the dominant factor for controlling the CO2RR product selectivity. Overall, this work demonstrates the structure‐activity relationship of Bi SACs, which can be utilized to establish control over CO2RR product distributions, and highlights the promise for engineering atomic coordination environments of SACs to tune reaction pathways.