Effect Of Substitution Research Articles

Insights into Ultrafast Relaxation Dynamics of Electronically Excited Furfural and 5-Methylfurfural.

The ultrafast relaxation dynamics of furfural and 5-methylfurfural following excitation in the ultraviolet range is investigated using the femtosecond time-resolved photoelectron spectroscopy method. Specifically, the pump wavelength-dependent decay dynamics of electronically excited furfural and 5-methylfurfural is discussed on the basis of a detailed analysis of our measured time-resolved photoelectron spectroscopy spectra. Irradiation at all pump wavelengths prepares both furfural and 5-methylfurfural molecules with different vibrational levels in the first optically bright S2 (1ππ*) state, the lifetime of which is measured to be at least hundreds of femtoseconds. Besides the prominent deactivation channels of ring-opening and ring-puckering pathways for the S2(1ππ*) state, we propose that there is a minor decay channel of internal conversion from the initially prepared S2(1ππ*) state to the S1(1nπ*) state. The wavepacket decays out of the Franck-Condon region on the S2(1ππ*) state potential energy surface and bifurcates into different parts somewhere. A small fraction of the wavepacket funnels down to the S1(1nπ*) state via internal conversion. The subsequently populated S1(1nπ*) state contains large vibrational excess energy and decays over a lifetime of 2.5-2.8 ps. One of the deactivation channels of the S1(1nπ*) state is intersystem crossing to the 3ππ* triplet state. In addition, methyl substitution effects on the excited-state dynamics of furfural are also discussed. This experimental study provides new insights into the excitation energy-dependent decay dynamics of photoexcited furfural and 5-methylfurfural.

Reducing Interfacial Recombination in Inverted Perovskite Solar Cells With Selenophene-Substituted PCBM: Comparison With Thiophene and Furan Substitution.

Reducing the interfacial recombination and improving the charge transfer capability of charge transport layers are effective strategies to enhance the efficiency and stability of perovskite solar cells (PSCs). This study evaluates, for the first time, the effects of selenophene substitution in the chemical structure of phenyl-butyric acid methyl ester (PCBM) on the performance and stability of inverted PSCs. Selenophene substitution was compared to thiophene and furan substitutions, and the reference PCBM without chalcogenophene moiety. Additionally, this study investigates the differences between using the fullerene cages C70 and C60 in the PCBM chemical structure. The photovoltaic results demonstrate that, with an adequate control of the thickness of the electron transport layer (ETL), incorporating the selenophene moiety in the structures of fullerenes enhances the photovoltaic parameters of PSCs. This improvement results from the reduction in trap-assisted recombination, an increase in electron mobility, and the improved charge extraction processes. The use of C70, as opposed to C60, allows for the preparation of a series of ETLs with comparable thicknesses, although slightly lower efficiencies. This feature facilitates a systematic comparative analysis focused on variations in the electron properties of ETLs, thereby avoiding the inclusion of issues related to thickness and charge recombination processes.

Wealth Taxation and Household Saving: Evidence from Assessment Discontinuities in Norway

Abstract Neither theory nor existing empirical evidence support the notion that wealth taxation reduces saving. Theoretically, the effect is ambiguous due to opposing income and substitution effects, and empirically, the effect may be masked by misreporting responses. Using geographic discontinuities in the Norwegian annual net-wealth tax and third-party-reported data on savings, I find that wealth taxation causes households to save more. Each additional NOK of wealth tax increases annual net financial saving by 3.76, implying that households increase saving enough to offset both current and future wealth taxes. This positive effect on saving is primarily financed by increases in labor earnings. These responses are the combination of small negative effects of increasing the marginal tax rates and larger positive effects of increasing average rates. My findings imply that income effects may dominate substitution effects in household responses to rate-of-return shocks, which has implications for both optimal taxation and macroeconomic modeling.

An investigation of economic interactions between social reinforcement and heroin or cocaine in rats.

The primary goal of the present study was to determine the economic relationship between heroin and social reinforcement in rats: are they substitutes, independents, or complements? In Experiment 1, one group of rats was given a budget of responses that they could allocate between heroin and social reinforcement offered at various combinations of prices. A second group chose between two levers that each resulted in social reinforcement at varying prices when pressed. There was no relationship between the relative allocation of responses between heroin and social reinforcement and changes in their relative prices, indicating that these reinforcers are best viewed as independents. In contrast, when choosing between two sources of social reinforcement, rats increased the allocation of behavior to the cheaper option, confirming that the method used here was sensitive to detecting substitution effects. In Experiment 2, the same method was used to compare one group that chose between heroin and social reinforcement with a second group that chose between cocaine and social reinforcement. The finding that heroin and social reinforcement were independents was replicated. Additionally, there was some evidence that cocaine and social reinforcement were substitutes, at least when the first few minutes of the session were excluded. These results add to our knowledge of how drug and nondrug reinforcers interact in choice situations in rats and may model factors that influence drug use in humans.

Photo‐Curable Fluorinated High‐k Polyimide Dielectrics by Polar Side Substitution Effect for Low‐Voltage Operating Flexible Printed Electronics

AbstractPolyimide‐based dielectric films are widely used in various thin film devices including organic field‐effect transistors (OFETs) owing to their promising thermal/chemical stability, mechanical flexibility, and insulating properties. On the other hand, considerable attention is paid to lowering the process temperature to allow coating on plastic substrates because high‐temperature annealing (≈200 °C) is usually required to convert precursors to polyimide films with those excellent properties. In addition, polyimide‐based dielectric films have low dielectric constants (k) (<4). Therefore, modifying the k properties of polyimide is a critical issue for applications as an insulating thin film for practical transistors. This paper reports a new type of polyimide‐based gate dielectric comprising methacryloyl moiety (PI‐MA) as a side chain for photo‐pattern/processability and high‐k properties. This study shows that the photocured PI‐MA thin films show excellent insulating properties (leakage current densities < 10−8 A cm⁻2 at 4 MV cm⁻1) and high‐k properties (≈8) even without a post‐annealing process. Finally, the use of PI‐MA in printed field‐effect transistors results in high performance with low‐voltage operation (within 5 V) and integrated logic‐gate devices (NOT, NAND, and NOR gates).

Effect of replacing ground corn with cactus pear Nopalea cochenillifera (L.) on feed intake and digestibility, water intake, milk production and composition in Holstein × Gyr cows.

The objective of this study was to evaluate the intake and digestibility of nutrients, production and composition of milk, and water intake of lactating dairy cows fed standard diets in which ground corn (C) was replaced by up to 100% in the diet by cactus pear (CP). Eight Girolando cows (½ Gyr x ½ Holstein), 3rd calf multiparous, with 60 to 80 days of lactation and an average weight of 450.0 ± 30.0kg, were randomly distributed in a double Latin square (4 × 4). Four experimental diets were evaluated: (100% C + 0% CP), (66.6% C + 33.3% CP), (33.3% C + 66.6% CP), and (0% C + 100% CP). There was a difference (P < 0.05) in the intake of CP and EE (kg.day- 1), with a quadratic effect and a linear reduction, respectively, with substitution. The maximum CP intake of 3.05kg.day- 1 was found at 46.07% and EE intake fell by 3.81g for each percentage unit of cactus pear added to the diet. There was a quadratic difference (P < 0.05) for DM intake in %BW and g.kg BW0,75, with maximum values of 3.97%BW and 186.8g.kg BW0,75 with the substitution of 54.83 and 53.17%, respectively. There was a quadratic effect (P < 0.05) for the intake of NDF in %BW, with the maximum intake of 1.3% at the 74.69% substitution level. There was a linear reduction (P < 0.05) in the digestibility of DM, NDF, and TDN, and for the other nutrients there was no substitution effect (P > 0.05). There was no difference (P > 0.05) in milk production and composition. There was a linear reduction (P < 0.05) in water intake. Cactus pear can be used in a promising way to replace ground corn up to 100% in the diet of lactating dairy cows.

Ab Initio Neural Network Potential Energy Surface and Quantum Dynamics Calculations on Na(2S) + H2 → NaH + H Reaction.

The collisions between Na atoms and H2 molecules are of great significance in the field of chemical reaction dynamics, but the corresponding dynamics results of ground-state reactions have not been reported experimentally or theoretically. Herein, a global and high-precision potential energy surface (PES) of NaH2 (12A') is constructed by the neural network model based on 21,873 high-level ab initio points. On the newly constructed PES, the quantum dynamics calculations on the Na(2S) + H2(v0 = 0, j0 = 0) → NaH + H reaction are carried out using the time-dependent wave packet method to study the microscopic reaction mechanism at the state-to-state level. The calculated results show that the low-vibrational products are mainly formed by the dissociation of the triatomic complex; whereas, the direct reaction process dominates the generation of the products with high-vibrational states. The reaction generally follows the direct H-abstraction process, and there is also the short-lived complex-forming mechanism that occurs when the collision energy exceeds the reaction threshold slightly. The PES could be used to further study the stereodynamics effects of isotope substitution and rovibrational excitations on the title reaction, and the presented dynamics data would provide an important reference on the corresponding experimental research at a higher level.

Molecular Dynamics Study of Hydrogen Bond Structure and Tensile Strength for Hydrated Amorphous Cellulose.

Molecular dynamics (MD) simulations were conducted to investigate the hydrogen-bond (H-bond) structure and its impact on the tensile strength of hydrated amorphous cellulose. The study identifies a stable intramolecular H-bond between the hydroxyl group at position 3 and the ether oxygen at position 5 (OH3···O5). Intermolecularly, the hydroxyl groups at positions 2 (OH2) and 6 (OH6) form stable H-bonds. Young's modulus, maximum tensile strength, and corresponding strain were calculated as functions of moisture content, while the H-bond network, water cluster formation, and cellulose chain orientation during tensile simulations were analyzed to elucidate mechanical properties. The substitution effect of cellulose on Young's modulus is also examined, revealing that the substitution of OH3 for a hydrophobic group minimally affects Young's modulus, but substitutions at OH2 and OH6 significantly reduce tensile strength due to their roles as key intermolecular H-bond donor sites.

Unraveling the structural and thermoelectric properties of the Sn-doped filled skutterudite Smy(FexNi1-x)Sb11.5Sn0.5 (y = 0.17–0.34, x = 0.43–0.64)

A systematic study of the filled skutterudite system Smy(FexNi1-x)4Sb11.5Sn0.5 was carried out with the aim of investigating the effect of the partial substitution of Sb by Sn on the structural and thermoelectric properties of the material. The presence of Sn induces a shift of the p/n crossover toward lower values of x compared to the corresponding Sn-free system, as a consequence of the smaller number of electrons supplied. Moreover, a discontinuity at the p/n crossover is observed in the cell parameter and related structural features. The thermoelectric properties suggest lower thermal conductivity values in comparison to similar Sn-free skutterudite systems, resulting in higher ZT. This result highlights the significant role of Sn in creating new scattering centers able to affect the phonon transmission through the crystal lattice.

PH–Assisted Strength Gain Projection for Green Cement Mortar Composite Containing Marble Powder By-Product: Substitution and Intergrinding Methods

This manuscript reports the effects of substitution and interground of MP on the pH of cement and bending and compressive strengths of mortar composite as well as strength projection of green mortar composite from pH of green cement. It also presents the relationships between pH of cement and strength of mortar composite to compute strength gain from pH of cement. The feature of sample made with MP–cement is examined and compared to those made with pure Portland cement– including bending and compressive strengths at 7d, 28d, and 90d, and pHs of cement. Projection of strength gain from pHs of cement is also discussed, and the numeric equations, the coefficients, and the r squares, which are essential elements of the strength projection, are given in the experimental study proficiently. Regularly, this study results indicate that the projection for strength gains of green mortar composite could be computed from pHs of green cement properly.

BMI Mediates the Association between Macronutrient Subtypes and Phenotypic Age Acceleration.

Background: There is growing evidence that diet and aging are associated; however, few studies have examined the relationship between macronutrient subtypes and phenotypic age acceleration, and the extent to which BMI (body mass index) mediates this association is unclear. Methods: This study included 6911 individuals who were 20 years or older and had participated in the National Health and Nutrition Examination Survey. Daily macronutrient intakes were calculated and classified by the quartile of their subtypes. PhenoAgeAccel was calculated as an aging index using nine chemistry biomarkers. Multivariable linear regression and isocaloric substitution effects were used to evaluate the association of macronutrients with PhenoAgeAccel. Mediation analyses were used to examine the mediation role of BMI in the association. Results: After adjusting for the potential covariates, the consumption of high-quality carbohydrates (β = -1.01, 95% CI: -1.91, -0.12), total protein (β = -2.00, 95% CI: -3.16, -0.84), and plant protein (β = -1.65, 95% CI: -2.52, -0.78) was negatively correlated with PhenoAgeAccel; the consumption of SFAs (β = 1.77, 95% CI: 0.72, 2.81) was positively correlated with PhenoAgeAccel. For every serving of low-quality carbohydrates/animal protein and other calories replaced by one serving of high-quality carbohydrates/plant protein, PhenoAgeAccel would be reduced by about 25 percent. The ratio between BMI-mediated high-quality carbohydrates and PhenoAgeAccel accounted for 19.76% of the total effect, while the ratio between BMI-mediated total fat and PhenoAgeAccel accounted for 30.78% of the total effect. Conclusions: Different macronutrient consumption subtypes are related to PhenoAgeAccel, which is partially mediated by BMI, depending on the quality of macronutrients. Replacing low-quality macronutrients with high-quality macronutrients might slow aging.

Association between 24-hour movement behavior and depression in college students: A compositional data analysis

BackgroundEvidence strongly suggests that moderate-to-vigorous physical activity (MVPA) can help reduce symptoms of depression. However, the relationship between 24-h movement behaviors and depressive symptoms, as well as the potential substitution effects between different behaviors, remains unclear. Therefore, this study seeks to investigate how the time spent in one behavior relative to others is associated with depressive symptoms. MethodsThe study recruited 366 participants, who had their levels of MVPA, light PA (LPA), and sedentary behavior (SB) recorded using tri-axial accelerometers over 7 consecutive days. Participants also self-reported their sleep duration (SLP). Depression scores were measured using the Center for Epidemiological Studies Depression Scale (CESD). Using compositional linear regression, the study explored the connections between different compositions of time spent in movement behaviors and depression symptom scores. ResultsSpending more time on LPA and MVPA relative to other behaviors were associated with lower depression scores, whereas a higher proportion of SB relative to other activities was linked to increased depression scores. Reallocating time spent on SB to LPA and MVPA was associated with decreased depression scores. LimitationThis study is a cross-sectional research design, and causality cannot be inferred. In addition, the sampling method of this study may have imposed some limitations on the representativeness of the sample. Further longitudinal studies could be conducted by selecting a large, representative sample. ConclusionWithin the spectrum of 24-h movement behaviors, increasing the duration of LPA and MVPA emerges as advantageous for reducing depression scores, suggesting a potential benefit in reallocating SB to PA, especially MVPA.

Tuning the circularly polarized luminescence in homoleptic and heteroleptic chiral CrIII complexes.

A series of highly emissive inert and chiral CrIII complexes displaying positive and negative circularly polarized luminescence (CPL) within the near-infrared (NIR) region at room temperature have been prepared and characterized to decipher the effect of ligand substitution on the photophysical properties, more specifically on the chiroptical properties. The helical homoleptic [Cr(dqp-R)2]3+ (dqp = 2,6-di(quinolin-8-yl)pyridine; R = Ph, ≡-Ph, DMA, ≡-DMA (DMA = N,N-dimethylaniline)) and heteroleptic [Cr(dqp)(L)]3+ (L = 4-methoxy-2,6-di(quinolin-8-yl)pyridine (dqp-OMe) or L = N 2,N 6-dimethyl-N 2,N 6-di(pyridin-2-yl)pyridine-2,6-diamine (ddpd)) molecular rubies were synthesized as racemic mixtures and then resolved and isolated into their respective pure PP and MM enantiomeric forms by chiral stationary phase HPLC. The corresponding enantiomers show two opposite polarized emission bands within the 700-780nm range corresponding to the characteristic metal-centered Cr(2E'→4A2) and Cr(2T1 '→4A2) transitions with large g lum ranging from 0.14 to 0.20 for the former transition. In summary, this study reports the rational use of different ligands on CrIII and their effect on the chiroptical properties of the complexes.

Effects of Cr Substitution on the Structural, Optical, and Electrical Properties of Mg-Co Spinel Ferrites Synthesized via the Sol–Gel Method

Effects of Cr Substitution on the Structural, Optical, and Electrical Properties of Mg-Co Spinel Ferrites Synthesized via the Sol–Gel Method

Quantum oscillation study of the large magnetoresistance in Mo substituted WTe2 single crystals

The list of interesting electrical properties exhibited by transition metal dichalcogenides has grown with the discovery of extremely large magnetoresistance (MR) and type-II Weyl semimetal behavior in WTe2 and MoTe2. The extremely large MR in WTe2 is still not adequately understood. Here, we systematically study the effect of Mo substitution on the quantum oscillations in the MR in WTe2. The MR decreases with Mo substitution, however, the carrier concentrations extracted from the quantum oscillations show that the charge compensation improves. We believe that earlier interpretations based on the two-band theory, which attribute the decrease in MR to charge imbalance, could be incorrect due to overparametrization. We attribute the decrease in MR in the presence of charge compensation to a fall in transport mobility, which is evident from the residual resistivity ratio data. The quantum scattering time and the effective masses do not change within experimental errors upon substitution. Published by the American Physical Society 2024

Effect of Potassium Substitution on Structural, Magnetic, Magnetocaloric, and Critical Properties of La0.65Sr0.35−xKxMnO3(x = 0.075 and 0.15) Manganites

Effect of Potassium Substitution on Structural, Magnetic, Magnetocaloric, and Critical Properties of La0.65Sr0.35−xKxMnO3(x = 0.075 and 0.15) Manganites

Financial Mechanism for Sustainable Development of the Marine Economy with Respect to Technology, Digitalization, and Low Carbonization

This study explores the impact of regional financial development on the sustainable growth of the marine economy across 14 coastal cities in Guangdong Province from 2004 to 2022. To assess this, a comprehensive index system was developed to measure marine economic sustainability, incorporating key factors such as capital investment, production efficiency, and processing and trade. The findings indicate that financial development significantly enhances the sustainable growth of the marine economy. However, the interaction between financial development, technology digitalization, and low-carbon initiatives leads to diminishing returns in terms of sustainability. Through the use of the Moran index and the spatial Durbin model, the analysis reveals a dual outcome: while financial development positively influences a city’s marine economic sustainability, it exerts negative spillover effects on neighboring cities. Previous studies have primarily focused on the relationship between financial development and the marine economy at the national or provincial level, leaving a gap in understanding these dynamics at the city level. Furthermore, the coordination between financial development and marine economic sustainability across cities within the same region remains largely unexplored. This study addresses these gaps by investigating city-level dynamics and examining intercity coordination between financial development and marine economic growth. The results offer a novel perspective for policymakers, highlighting strategies to balance regional financing for the marine economy with targeted investments in science, technology, digitalization, and low-carbon initiatives. This approach seeks to optimize resource allocation and mitigate potential substitution effects. Ultimately, this research contributes to a more nuanced understanding of the complex interplay between financial development and the marine economy at both city and regional levels.

Data-Driven Shelf Stocking: Robustness and Vertical-Location Effect

In this article, we study a shelf-stock allocation problem in a data-driven setting where the demand distribution is unknown. The retailer needs to decide which commodities to place on each level of the shelf (location decision), and determine the stock level for each selected commodity at the shelf (stock decision) that can be adjusted based on updated demand prediction, under constraints on allocation and capacity, so as to maximize total expected profit. Key issues of the problem include demand endogeneity on vertical-location effect and the demand ambiguity that may arise from the ever shorter life cycles of commodities and other complicated determinants. We address the problem in a rolling-horizon fashion and develop a two-phase data-driven robust optimization model leveraging a decision-dependent Wasserstein metric that incorporates time-series demand forecasts and captures vertical-location effect under demand ambiguity. We derive tractable solution schemes for the model, in which the phase-I model determines the optimal location decision by solving one instance of mixed-integer linear program, while the phase-II model admits an analytical solution for updating the optimal stock. Furthermore, we discuss the sensitivity implications on how the ambiguity aversion impacts the optimal stock, and prove the consistency of the model solution under regularity condition on the underlying demand process that well justifies the asymptotic performance of the proposed data-driven approach. Finally, we extend our model to incorporate substitution effect, and conduct sufficient numerical experiments with real-life data that demonstrate the performance of our model.

Uptake of biosimilars in China: a retrospective analysis of the case of trastuzumab from 2018 to 2023

BackgroundThe Chinese biosimilar industry has demonstrated rapid growth in recent years. Limited evidence is available about biosimilar uptake at the national level. This study aimed to assess biosimilar uptake in the case of trastuzumab and to explore potential factors influencing the biosimilar penetration at national and provincial levels.MethodsThis study employed an interrupted time series analysis to assess the level and trend changes of national trastuzumab originator consumption and the overall trastuzumab consumption after the price reduction of the originator and the introduction of the first biosimilar using the China Hospital Pharmacy Audit procurement data from March 2018 to February 2023. A latent class trajectory model (LCTM) was also adopted to estimate the biosimilar penetration across 30 provincial-level administrative divisions (PLADs). Based on the LCTM grouping results, provincial characteristics were analyzed.ResultsAfter rapid growth, the penetration of biosimilars demonstrated a moderate ascending trend at the national level, reaching 27% in February 2023. Following the introduction of the first biosimilar in July 2021, the consumption of the originator decreased by 0.5% per month (P = 0.008), and the growth rate of overall trastuzumab consumption decreased by 1.1% per month (P = 0.014). LCTM fit the best when the number of trajectory classes was two, dividing 30 PLADs into a group demonstrating a faster increase in biosimilar penetration and the other with a slower increase. The PLADs in the fast-increasing group had a higher proportion of the population covered by the national basic health insurance, a lower proportion of the urban population, a lower proportion of the population covered by the urban employee health insurance program, a lower gross domestic product per capita, a lower total health expenditure per capita, and a lower out-of-pocket expenditure.ConclusionsThe uptake of trastuzumab biosimilars in China was lower compared with major European countries. The introduction of trastuzumab biosimilars presented a substitutional effect. Perceptions of physicians and patients, the medicines procurement model, competition from other biologics, and health insurance payment methods may influence biosimilar uptake. Enhancing a comprehensive understanding of biosimilars among physicians and patients, including biologics with biosimilars in the national pooled procurement, and implementing provider payment reforms could foster biosimilar penetration.

Adoption of green production technologies by farmers through traditional and digital agro-technology promotion–An example of physical versus biological control technologies

Traditional and digital agro-technology promotion are two critical methods for disseminating agricultural technology information, which effectively encourages farmers to employ green production technologies. This paper empirically examines the effects of traditional and digital agro-technology promotion on the adoption of green production technologies by 619 apple producers in the primary apple production area of Guanzhong Plain, China, using micro-survey data. The study's findings suggest that both promotion models significantly influence the adoption of green production technologies by farmers. This conclusion remains valid after the instrumental variables approach and a series of robustness tests are implemented to address endogeneity concerns. The heterogeneity analysis revealed that the impact of the two promotion modes on the adoption behavior of green production technologies by farmers varied by scale. Specifically, digital agro-technology promotion had a greater impact on the adoption of physical control technologies by small-scale farmers, while traditional agro-technology promotion had a greater impact on the adoption of biological control technologies by large-scale households. In addition, the technological differences between traditional agrotechnology promotion and digital agrotechnology promotion result in clear complementary and substitution effects. The two modes of promotion have evident complementary effects for biological control technologies. The two modalities of promotion for physical control technologies exhibit complementary effects between social communication-type promotions and traditional agro-technology promotions, as well as substitution effects between short-video promotions and traditional agro-technology promotions.