Functional Framework Research Articles

"Smells like team spirit" the association between running club membership and performance in the London Marathon: An economic analysis.

This study examines the association between club membership and marathon performance using a dataset of 206,653 London Marathon runners. Our results show a statistically significant association between club membership and marathon performance for both males and females which sees club membership potentially mitigating pace decline with age and resulting in substantial improvements in finishing times of up to 40 minutes. We implement a production function framework and align with three principles of economic organisation. The findings have relevance for marathon participants, coaches, and athletic associations as well as implications beyond athletics to other sports or cooperative activities.

Self-Organizing Optimization Based on Caputo’s Fractional Order Gradients

This paper analyses the condition necessary to guarantee no divergence for Caputo’s fractional order gradient descent (C-FOG) algorithm on multivariate functions. C-FOG is self-organizing, computationally efficient, simple, and understandable. It converges faster than the classical gradient-based optimization algorithms and converges to slightly different points when the order of the fractional derivative is different. The additional freedom of the order is very useful in situations where the diversity of convergence is required, and it also allows for more precise convergence. Comparative experiments on a typical poor conditioned function and adversarial sample generation frameworks demonstrate the convergence performance of C-FOG, showing that it outperforms currently popular algorithms in terms of convergence speed, and more excitingly, the diversity of convergence allows it to exhibit stronger and more stable attack capability in adversarial sample generation procedures (The code for experiments is available at: https://github.com/mulertan/self_optimizing/tree/main, accessed on 30 April 2024).

Bottom-up versus Top-down designed rehabilitation sessions in chronic stroke survivors: a pilot randomized controlled trial

Purpose The present study aimed to compare the effectiveness of Top-down and Bottom-up approaches on levels of the International Classification of Functioning, Disability and Health Framework (ICF), including impairments, activities, and participation. Materials and methods Thirty-nine chronic stroke survivors were recruited for this single-blinded randomized clinical trial. Participants were assigned to Top-down, Bottom-up interventions, or control group, and received a 6-week intervention. They were assessed before/after treatments and at follow-up (6 weeks later). Impairments were measured through kinematic analysis, Trail Making Tests (TMT), and Fugl-Meyer Assessment (FMA). Activity and participation were evaluated via Box and Block Test, Motor Activity Log (MAL), and Canadian Occupational Performance Measure (COPM), respectively. Results We found significant improvements in impairment (FMA) and participation (COPM) in all groups, however, COPM scores improved beyond the MCID only in the Top-down, and FMA scores exceeded the MCID in Top-down and Bottom-up groups. Use of the upper limb in daily activities (MAL) enhanced in the Top-down group, although was not clinically significant. Conclusion In most of the outcome measures, no significant difference was observed between groups. It seems that Top-down, Bottom-up, and traditional interventions have relatively comparable effectiveness in chronic stroke survivors. Trial Registration IRCT20150721023277N2

The Role of the Table of Games in the Discrete Thermostatted Kinetic Theory

This paper is concerned with the mathematical modeling of complex living systems whose element microscopic state contains variables which can attain discrete values. Specifically, the main mathematical frameworks of the discrete thermostatted kinetic theory for active particles are reviewed and generalized. In the generalized thermostatted frameworks, which are based on nonlinear ordinary or partial differential equations, the elements of the system are viewed as active particles that are able to perform certain strategies modeled by introducing a functional-state variable called activity. Interactions, which are responsible of the evolution of the system, are modeled using the fundamentals of stochastic game theory and may be influenced by the action of an external force field coupled to a Gaussian-type thermostat. In particular, the interaction domain is modeled by introducing a weighted function and different non-homogeneous discrete frameworks are proposed and coupled with a specific thermostat. Two recent models derived within this approach are reviewed and refer to vehicular and pedestrian dynamics. Future research perspectives are discussed in the whole paper from theoretical and modeling viewpoints.

Influence of atomistic features in plasmon-exciton coupling and charge transfer driven by a single molecule in a metallic nanocavity.

When an organic molecule is placed inside a plasmonic cavity formed by two metallic nanoparticles (MNP) under illumination, the electronic excitations of the molecule couple to the plasmonic electromagnetic modes of the cavity, inducing new hybrid light-matter states called polaritons. Atomistic abinitio methods accurately describe the coupling between MNPs and molecules at the nanometer scale and allow us to analyze how atomistic features influence the interaction. In this work, we study the optical response of a porphine molecule coupled to a silver nanoparticle dimer from first principles, within the linear-response time-dependent density functional theory framework, using the recently developed Python Numeric Atomic Orbitals implementation to compute the optical excitations. The optical spectra show the splitting of the resonances of the plasmonic dimer and the molecule into two distinct polaritons, a characteristic feature of the strong light-matter coupling regime. Our results stress the importance of atomistic features, such as the gap configuration in determining the plasmon-exciton coupling strength and in the emergence of molecule-mediated charge-transfer plasmon (CTP) resonances at lower frequencies. Moreover, we show that the strength of the CTP resonance can be tuned by shifting the alignment of the molecular energy levels with respect to the Fermi level of the MNPs.

Functional Framework of Amino Acid Transporters in Quinoa: Genome-Wide Survey, Homology, and Stress Response

Functional Framework of Amino Acid Transporters in Quinoa: Genome-Wide Survey, Homology, and Stress Response

Robust Support Vector Data Description with Truncated Loss Function for Outliers Depression.

Support vector data description (SVDD) is widely regarded as an effective technique for addressing anomaly detection problems. However, its performance can significantly deteriorate when the training data are affected by outliers or mislabeled observations. This study introduces a universal truncated loss function framework into the SVDD model to enhance its robustness and employs the fast alternating direction method of multipliers (ADMM) algorithm to solve various truncated loss functions. Moreover, the convergence of the fast ADMM algorithm is analyzed theoretically. Within this framework, we developed the truncated generalized ramp, truncated binary cross entropy, and truncated linear exponential loss functions for SVDD. We conducted extensive experiments on synthetic and real-world datasets to validate the effectiveness of these three SVDD models in handling data with different noise levels, demonstrating their superior robustness and generalization capabilities compared to other SVDD models.

A random forest approach for interval selection in functional regression

AbstractIn this article, we focus on the problem of variable selection in a functional regression framework. This question is motivated by practical applications in the field of agronomy: In this field, identifying the temporal periods during which weather measurements have the greatest impact on yield is critical for guiding agriculture practices in a changing environment. From a methodological point of view, our goal is to identify consecutive measurement points in the definition domain of the functional predictors, which correspond to the most important intervals for the prediction of a numeric output from the functional variables. We propose an approach based on the versatile random forest method that benefits from its good performances for variable selection and prediction. Our method builds in three steps (interval creation, summary, and selection). Different variants for each of the steps are proposed and compared on both simulated and real‐life datasets. The performances of our method compared to alternative approaches highlight its usefulness to select relevant intervals while maintaining good prediction capabilities. All variants of our method are available in the R package SISIR.

Asymmetric Cu-N1O3 Sites Coupling Atop-type and Bridge-type Adsorbed *C1 for Electrocatalytic CO2-to-C2 Conversion.

2D functional porous frameworks offer a platform for studying the structure-activity relationships during electrocatalytic CO2 reduction reaction (CO2RR). Yet challenges still exist to breakthrough key limitations on site configuration (typical M-O4 or M-N4 units) and product selectivity (common CO2-to-CO conversion). Herein, a novel 2D metal-organic framework (MOF) with planar asymmetric N/O mixed coordinated Cu-N1O3 unit is constructed, labeled as BIT-119. When applied to CO2RR, BIT-119 could reach a CO2-to-C2 conversion with C2 partial current density ranging from 36.9 to 165.0 mA cm-2 in flow cell. Compared to the typical symmetric Cu-O4 units, asymmetric Cu-N1O3 units lead to the re-distribution of local electron structure, regulating the adsorption strength of several key adsorbates and the following catalytic selectivity. From experimental and theoretical analyses, Cu-N1O3 sites could simultaneously couple the atop-type (on Cu site) and bridge-type (on Cu-N site) adsorption of *C1 species to reach the CO2-to-C2 conversion. This work broadens the feasible C-C coupling mechanism on 2D functional porous frameworks.

Harnessing Bromo/Acyloxy Transposition (BrAcT) and Excited-State Copper Catalysis for Styrene Difunctionalization.

1,2-Difunctionalization of styrenes, adding two distinct functional groups across the C═C double bond, has emerged as a powerful tool for enhancing molecular complexity. Herein, we report the development of a regioconvergent β-acyloxylation-α-ketonylation of styrenes through bromo/acyloxy transposition (BrAcT) and excited-state copper catalysis. This approach is amenable to gram-scale synthesis and tolerates a wide range of functional groups and complex molecular frameworks, including derivatives of natural products and marketed drugs. Our experimental and computational studies suggest a unique mechanism featuring a dynamic, ionic BrAcT process and excited-state copper-catalyzed redox reactions. We anticipate that this BrAcT process could serve as a broadly applicable and versatile strategy for β-acyloxylation-α-functionalization of styrenes, creating valuable intermediates for preparing new pharmaceuticals, agrochemicals, and functional materials.

Transmetalation in Surface-Confined Single-Layer Organometallic Networks with Alkynyl-Metal-Alkynyl Linkages.

Transmetalation represents an appealing strategy toward fabricating and tuning functional metal-organic polymers and frameworks for diverse applications. In particular, building two-dimensional metal-organic and organometallic networks affords versatile nanoarchitectures of potential interest for nanodevices and quantum technology. The controlled replacement of embedded metal centers holds promise for exploring versatile material varieties by serial modification and different functionalization. Herein, we introduce a protocol for the modification of a single-layer carbon-metal-based organometallic network via transmetalation. By integrating external Cu atoms into the alkynyl-Ag organometallic network constructed with 1,3,5-triethynylbenzene precursors, we successfully realized in situ its highly regular alkynyl-Cu counterpart on the Ag(111) surface. While maintaining a similar lattice periodicity and pore morphology to the original alkynyl-Ag sheet, the Cu-based network exhibits increased thermal stability, guaranteeing improved robustness for practical implementation.

Synthesis of a cysteine functional covalent organic framework via facile click reaction for the efficient solid phase extraction of substituted p-phenylenediamine-derived quinones

N,N′-Substituted p-phenylenediamine quinones (PPD-Qs) are the emerging toxicant, which transform from the rubber tire antioxidant N,N′-substituted p-phenylenediamines (PPDs). Because of their potential toxic and widespread occurrence in the environment, PPD-Qs have received great attention. However, efficiently extracting PPD-Qs from complex samples is still a challenge. Herein, a cysteine functional covalent organic framework (Cys-COF) designed according to the “donor-acceptor” sites of hydrogen bonding of PPD-Qs was synthesized via click reaction and then used as solid-phase extraction (SPE) adsorbent. Cys-COF can form the seven-member ring adsorption structure with PPD-Qs via hydrogen bonding. The adsorption mechanism was tentatively revealed by density functional theory (DFT). After optimizing the Cys-COF-SPE parameters, PPD-Qs were efficiently extracted from water, soil, sediment, and fish, followed by detection using ultra-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The Cys-COF-SPE-UHPLC-MS/MS method exhibited ideal linearity (R2 ≥ 0.9932), high relative recoveries (80.4–111 %), and low limits of detection (0.0001–0.0013 ng mL−1). In addition, the bioconcentration kinetics in goldfish provides a feasible platform to investigate the toxicity and accumulated ability of PPD-Qs.

Protein semisynthesis reveals plasticity in HECT E3 ubiquitin ligase mechanisms.

Lys ubiquitination is catalysed by E3 ubiquitin ligases and is central to the regulation of protein stability and cell signalling in normal and disease states. There are gaps in our understanding of E3 mechanisms, and here we use protein semisynthesis, chemical rescue, microscale thermophoresis and other biochemical approaches to dissect the role of catalytic base/acid function and conformational interconversion in HECT-domain E3 catalysis. We demonstrate that there is plasticity in the use of the terminal side chain or backbone carboxylate for proton transfer in HECT E3 ubiquitin ligase reactions, with yeast Rsp5 orthologues appearing to be possible evolutionary intermediates. We also show that the HECT-domain ubiquitin covalent intermediate appears to eject the E2 conjugating enzyme, promoting catalytic turnover. These findings provide key mechanistic insights into how protein ubiquitination occurs and provide a framework for understanding E3 functions and regulation.

Code-Switching in “Kongsi Raya”: Unveiling Communication Patterns in Cinema

Code-switching, a prevalent phenomenon in societies, especially among multilingual individuals, involves effortlessly transitioning between languages. Some scholars argue that code-switching signals a lack of language proficiency, while others believe it is an additional tool for achieving specific interactive goals when conversing with others. This behavior is not limited to real-life interactions but also appears in various creative mediums such as talk shows, music, films, and other artistic expressions. The primary objective of this research was to identify and analyze instances of code-switching in the film "Kongsi Raya." Using a qualitative descriptive methodology, the study collected and thoroughly examined selected scenes and dialogues from the movie, applying Malik's (1994) code-switching functions framework. The findings showed that code-switching was used either unconsciously or deliberately as an essential communication strategy to effectively convey the speakers' intended meaning, including emotions or simply providing information. This behavior reflects real-life communication scenarios in a culturally diverse country like Malaysia.

Defect-engineered chiral metal-organic frameworks.

Chirality has an important impact on chemical and biological research, as most active substances are chiral. In recent decades, metal-organic frameworks (MOFs), which are assembled from metal ions or clusters and organic linkers via metal-ligand bonding, have attracted considerable scientific interest due to their high crystallinity, exceptional porosity and tunable pore sizes, high modularity, and diverse functionalities. Since the discovery of the first functional chiral metal-organic frameworks (CMOFs), CMOFs have been involved in a variety of disciplines such as chemistry, physics, optics, medicine, and pharmacology. The introduction of defect engineering theory into CMOFs allows the construction of a class of defective CMOFs with high hydrothermal stability and multi-stage pore structure. The introduction of defects not only increases the active sites but also enlarges the pore sizes of the materials, which improves chiral recognition, separation, and catalytic reactions, and has been widely investigated in various fields. This review describes the design and synthesis of various defective CMOFs, their characterization, and applications. Finally, the development of the materials is summarized, and an outlook is given. This review should provide researchers with an insight into the design and study of complex defective CMOFs.

Effect of strain on the photoelectric properties of molybdenum ditelluride under vacancy defects: a DFT investigation.

This study explores the impact of deformation on the electrical and optical characteristics of monolayer cadmium telluride (MoTe2) with vacancies, using the foundational principles of density functional theory. It was discovered that both strain and imperfections alter the electrical characteristics of monolayer MoTe2. Under VTe-MoTe2, a direct-to-indirect band-gap transition occurs. In DTe-MoTe2, the band-gap value reduces dramatically, the conduction band changes downward, and the carrier concentration rises. The DVTe-induced band gap state is closer to the Fermi energy level than the VTe-induced band gap state. In this paper, DTe-MoTe2 is chosen for tensile deformation. The results show that the band-gap value tends to decrease by increasing tensile deformation. When the stretching value reaches 10%, the lower bound of the conduction band and the top of the valence band overlap, and the system is converted from a semiconductor to a metal. Considering the density of states, the missing state MoTe2 is mainly contributed by the participation of Te-s, Te-p, and Mo-d orbitals. In terms of optical qualities, the absorption and reflection peaks are red-shifted and blue-shifted, respectively. It is hoped that these effects on the optoelectronic properties will be widely applied. In this study, we utilize the generalized gradient approximation plane-wave pseudopotential method, incorporating Perdew-Burke Ernzerhof (PBE) generalized functions and following the fundamental principles of the density functional theory framework. A 3 × 3 × 1 supercell was constructed as an undoped model based on a MoTe2 monolayer, which consists of 9 Mo atoms and 18 Te atoms. The vacuum flat plate was set to 15Å along the z-direction to avoid interactions between the monolayers. For electronic structure calculations, the energy cutoff was set to 450eV. Each model's computational process and structural optimization were carried out using the Monkhorst-Pack specialized K-point sampling approach. Crystal optimization computations used a 3 × 3 × 1 Monkhorst-Pack K-point grid for molybdenum ditelluride monolayers and a 9 × 9 × 1K-point grid for electronic system analysis, analyzing state density and optical characteristics, respectively. For the structural optimization, the convergence requirements for maximum force, maximum atom displacement, maximum stress, and energy change were defined at 0.03eV/Å, 0.001Å, 0.05 Gpa, and 1.0 × 10-5eV/atom, respectively.

Ultrahigh stable heterometallic InCo-organic framework for efficiently catalyzing cycloaddition of CO2 with epoxides and Knoevenagel condensation

Due to versatile applications and fascinating topologies of heterometallic MOFs, developing new functional frameworks is of great significance and a great challenge. Inspired by this, we target to assemble rarely reported d-p heterometallic MOFs by using 4,4′-(4-(4-carboxyphenyl)pyridine-2,6-diyl)diisophthalic acid (H5CPPDA) as the organic linker, whose N and O donors have different affinities to d and p ions according to the soft-hard theory. Herein, a highly robust nanochannel-based InCo-organic framework of [InCo(CPPDA)(H2O)]·4DMF·6H2O}n (NUC-85) was successfully achieved under the acidic solvothermal condition. In the host framework of NUC-85, the ligand of CPPDA5− utilizes its five deprotonated carboxyl groups with three kinds of coordination modes (μ1-η1:η1, μ2-η1:η1 and μ3-η2:η1) as well as pyridine to combine In3+ and Co2+ ions into scarcely reported one-dimensional chains of [InCo(COO)5(H2O)]n, six of which are further arranged into hexagonal nano-channels (aperature ca. 14.5 Å). After thermal activation, the inner surface of channels in NUC-85a is functionalized by open metal sites of octa-coordinated In3+ and penta-coordinated Co2+ ions. Performed experiments prove that NUC-85a is an excellent heterogeneous catalyst for the cycloaddition of CO2 with epoxides under the mild conditions. Moreover, the Knoevenagel condensation with benzaldehyde and malononitrile as substrates can be efficiently catalyzed by NUC-85a. In the above two kinds of organic reactions, NUC-85a displays the satisfied chemical stability, high selectivity and multiple repeatability. This research demonstrates that nanostructure-based heterometallic MOFs have a bright future as a catalyst for Lewis acid/base supported organic reactions because of their congenital advantages such as sufficient active sites, high stability and convenient recyclability.

Evaluation and management of knee osteoarthritis.

Knee osteoarthritis (KOA) significantly contributes to the global disability burden, with its incidence expected to escalate by 74.9% by 2050. The urgency to comprehend and tackle this condition is critical, necessitating an updated and thorough review of KOA. A systematic review up to February 26, 2024, has elucidated the principal aspects of KOA's pathogenesis, risk factors, clinical manifestations, and contemporary management paradigms. The origins of KOA are intricately linked to mechanical, inflammatory, and metabolic disturbances that impair joint function. Notable risk factors include age, obesity, and previous knee injuries. Diagnosis predominantly relies on clinical assessment, with radiographic evaluation reserved conditionally. The significance of rehabilitation assessments, informed by the International Classification of Functioning, Disability, and Health framework, is highlighted. Treatment strategies are diverse, prioritizing nonpharmacological measures such as patient education, exercise, and weight management, with pharmacological interventions considered adjuncts. Intra-articular injections and surgical options are contemplated for instances where conventional management is inadequate. KOA stands as a predominant disability cause globally, characterized by a complex etiology and profound effects on individuals' quality of life. Early, proactive management focusing on nonpharmacological interventions forms the cornerstone of treatment, aiming to alleviate symptoms and enhance joint function. This comprehensive review underscores the need for early diagnosis, individualized treatment plans, and the integration of rehabilitation assessments to optimize patient outcomes. Further research is needed to refine prevention strategies and improve management outcomes for KOA patients.

Phytochemical drivers of insect herbivory: a functional toolbox to support agroecological diversification.

Plant metabolism is a key feature of biodiversity that remains underexploited in functional frameworks used in agroecology. Here, we study how phytochemical diversity considered at three organizational levels can promote pest control. In a factorial field experiment, we manipulated plant diversity in three monocultures and three mixed crops of oilseed rape to explore how intra- and interspecific phytochemical diversity affects pest infestation. We combined recent progress in metabolomics with classic metrics used in ecology to test a box of hypotheses grounded in plant defence theory. According to the hypothesis of 'phytochemically mediated coevolution', our study stresses the relationships between herbivore infestation and particular classes of specialized metabolites like glucosinolates. Among 178 significant relationships between metabolites and herbivory rates, only 20% were negative. At the plant level, phytochemical abundance and richness had poor predictive power on pest regulation. This challenges the hypothesis of 'synergistic effects'. At the crop cover level, in line with the hypothesis of 'associational resistance', the phytochemical dissimilarity between neighbouring plants limited pest infestation. We discuss the intricate links between associational resistance and bottom-up pest control. Bridging different levels of organization in agroecosystems helps to dissect the multi-scale relationships between phytochemistry and insect herbivory.

Toward Functionality and Deactivation of Metal-Single-Atom in Heterogeneous Photocatalysts.

Single-atom heterogeneous catalysts (SAHCs) provide an enticing platform for understanding catalyst structure-property-performance relationships. The 100% atom utilization and adjustable local coordination configurations make it easy to probe reaction mechanisms at the atomic level. However, the progressive deactivation of metal-single-atom (MSA) with high surface energy leads to frequent limitations on their commercial viability. This review focuses on the atomistic-sensitive reactivity and atomistic-progressive deactivation of MSA to provide a unifying framework for specific functionality and potential deactivation drivers of MSA, thereby bridging function, purpose-modification structure-performance insights with the atomistic-progressive deactivation for sustainable structure-property-performance accessibility. The dominant functionalization of atomically precise MSA acting on properties and reactivity encompassing precise photocatalytic reactions is first systematically explored. Afterward, a detailed analysis of various deactivation modes of MSA and strategies to enhance their durability is presented, providing valuable insights into the design of SAHCs with deactivation-resistant stability. Finally, the remaining challenges and future perspectives of SAHCs toward industrialization, anticipating shedding some light on the next stage of atom-economic chemical/energy transformations are presented.