Moderate Interaction Research Articles

Synthesis, characterization and magnetic properties of a hexanuclear copper (II) complex with hydroxido, alkoxido and phenoxido bridges

A new CuII6 complex, formulated as [Cu6(L)3(µ3-OH)(H2O)(OH)(NO3)]·2H2O·7CH3OH (1) has been prepared using the symmetrical N2O3-donor Schiff-base ligand H3L = N,N′-(2-hydroxypropane-1,3-diyl)bis(2-hydroxyacetophenimine). Compound 1 has been structurally and spectroscopically characterized. Single crystal X-ray diffraction analysis reveals that 1 crystallizes in the triclinic space group P-1 and consists of a CuII6 complex where each deprotonated ligand chelates two CuII centres. Three of the six independent CuII centres are arranged in an almost equilateral triangle with double Cu-O-Cu bridges, formed by a μ3-hydroxido and phenoxido bridges. Each of the three CuII centres in the triangle is further connected to one CuII centre through a single alkoxido bridge. The magnetic properties indicate the presence of moderate and weak antiferromagnetic interactions through the double and single oxido bridges, respectively.

Tribological behaviour of DIN 1.2740 hot working tool steel during mandrel mill stretching process

This study evaluates the tribological properties of DIN 1.2740 hot tool steel against Super Cr13 martensitic stainless steel at 700 °C. The results show that the coefficient of friction (COF) ranged from 0.15 to 0.63, indicating moderate frictional interaction. The wear rate of DIN 1.2740 was observed to be low, suggesting good resistance to wear at high temperatures. The complex surface oxide layer that formed on the pin’s top surface, significantly reducing the COF and acting as a solid lubricant at elevated temperatures. The oxide layer was also fragile and unable to withstand the high sliding velocities and high loads. The steel exhibited a high surface roughness when subjected to increasing normal loads and increasing sliding velocities.

Evolution of cooperation in heterogeneous populations with asymmetric payoff distribution.

The emergence and maintenance of cooperation is a complex and intriguing issue, especially in the context of widespread asymmetries in interactions that arise from individual differences in real-world scenarios. This study investigates how asymmetric payoff distribution affects cooperation in public goods games by considering a population composed of two types of individuals: strong and weak. The asymmetry is reflected in the fact that strong players receive a larger share of the public pool compared to weak players. Our results demonstrate that asymmetric payoff distribution can promote cooperation in well-mixed populations and trigger the co-evolution of cooperation between sub-populations of strong and weak players. In structured populations, however, the effect of asymmetric payoff distribution on cooperation is contingent on the proportion of strong players and the extent of their payoff share, which can either foster or inhibit cooperation. By adjusting the interaction probability between strong and weak players based on their spatial arrangement on lattice networks, we find that moderate interaction probabilities most effectively maintain cooperation. This study provides valuable insights into the dynamics of cooperation under asymmetric conditions, highlighting the complex role of asymmetrical interactions in the evolution of cooperation.

“Hydroethanol extract and triterpenoids of Senegalia ataxacantha show antiplasmodial activity and the compounds are predicted to inhibit parasite lactate dehydrogenase (pfLDH) as indicated by molecular docking studies”

Malaria claims over 600,000 deaths annually with a disproportionately high burden in the WHO African Region. The development of parasite resistance has warranted the search for novel anti-plasmodial drug candidates. This research aimed at validating the efficacy of Senegalia ataxacantha and tracking down its bioactive constituents. In vivo antiplasmodial activity of the extract was assessed using suppressive and curative protocols. Yeast-induced pyrexia was employed to evaluate the antipyretic activity of the extract. In vitro anti-plasmodial activity of isolated compounds was done using SYBR green I fluorescence assay on chloroquine sensitive (3D7) and resistant (Dd2) strains of P falciparum. In silico pharmacokinetic and interactions with parasites lactate dehydrogenase predictions of isolated compounds was conducted through molecular docking studies. Ethanol (70 %) extract of the plant showed in vitro and in vivo anti-plasmodial effect. The extract demonstrated significant (p < 0.05) dose-dependent suppression of 63.39 % and 63.32 % respectively at the highest dose (300 mg kg-1). Artesunate (4 mg kg-1/day) had considerably better curative potential (85.25%). The compounds showed in vitro anti-plasmodial activity in the order lupeol> friedelin/ friedelinol mixture>friedelin>β-sitosterol based on IC50 measurement. Friedelinol and lupeol exhibited higher binding affinities with pfLDH compared to Chloroquine. The extract and acetaminophen (positve control) showed significant (p < 0.05) reduction in rectal temperature compared to the control group. In silico studies of the compounds revealed moderate interactions with some cytochrome P450 metabolizing enzymes. S. ataxacantha stem extract shows anti-plasmodial and antipyretic activities which may be due to its pentacyclic triterpenoid constituents inhibiting pfLDH.

On the role of non-equilibrium heat transfer in the filled fracture-rock matrix system

Understanding heat transfer processes in fractured porous media is critical for characterizing thermal behaviors and improving the operation efficiency of geothermal energy. The field observations have shown that many fractures are filled with sediment infilling rather than being fully open, but heat transfer in such a filled fracture-rock matrix system has received less attention to date. Since multiple domains are involved in such a system and the fracture is highly permeable even with sediment infilling, local thermal equilibrium may not be reached instantaneously. In this study, a fully coupled analytical model is proposed and developed to investigate the role of transient local heat transfer in the filled fracture-rock matrix system and analyze the spatiotemporal thermal distributions in each domain. The results indicate that multiple thermal properties of the rock matrix, such as average volumetric thermal capacity and thermal conductivity, have significant impacts on the spatiotemporal thermal distribution in the fracture. The temperatures of the pore water and sediment infilling in the fracture are sensitive to flow velocity, thermal conductivity of the rock matrix, and volumetric thermal capacities of the fluid and rock matrix. The thermal transfer coefficient has moderate interaction effects with other parameters according to the sensitivity analysis.

Structure and Energetics of PET-Hydrolyzing Enzyme Complexes: A Systematic Comparison from Molecular Dynamics Simulations.

Discovered in 2016, the enzyme PETase, secreted by bacterial Ideonella Sakaiensis 201-F6, has an excellent hydrolytic activity toward poly(ethylene terephthalate) (PET) at room temperature, while it decreases at higher temperatures due to the low thermostability. Many variants have been engineered to overcome this limitation, which hinders industrial application. In this work, we systematically compare PETase wild-type (WT) and four mutants (DuraPETase, ThermoPETase, FastPETase, and HotPETase) using standard molecular dynamics (MD) simulations and unbinding free energy calculations. In particular, we analyze the enzymes' structural characteristics and binding to a tetrameric PET chain (PET4) under two temperature conditions: T1─300 K and T2─350 K. Our results indicate that (i) PET4 forms stable complexes with the five enzymes at room temperature (∼300 K) and (ii) most of the interactions are localized close to the active site of the protein, where the W185 and Y87 residues interact with the aromatic rings of the substrate. Specifically, (iii) the W185 side-chain explores different conformations in each variant (a phenomenon known in the literature as "W185 wobbling"). This suggests that the binding pocket retains structural plasticity and flexibility among the variants, facilitating substrate recognition and localization events at moderate temperatures. Moreover, (iv) PET4 establishes aromatic interactions with the catalytic H237 residue, stabilizing the catalytic triad composed of residues S160-H237-D206, and helping the system achieve an effective configuration for the hydrolysis reaction. Conversely, (v) the binding affinity decreases at a higher temperature (∼350 K), retaining moderate interactions only for HotPETase. Finally, (vi) MD simulations of complexes formed with poly(ethylene-2,5-furan dicarboxylate) (PEF) show no persistent interactions, suggesting that these enzymes are not yet optimized for binding this alternative semiaromatic plastic polymer. Our study offers valuable insights into the structural stability of these enzymes and the molecular determinants driving PET binding onto their surfaces, sheds light on the mechanistic steps that precede the onset of hydrolysis, and provides a foundation for future enzyme optimization.

Molecular design and characterization of the PANI/yttrium oxide multifunctional nanocomposite material

A detailed density functional theory study was conducted on the nanocomposites formed by polyaniline and yttrium oxide clusters, employing the mixed 6-311G(d,p)/LANL2DZ basis set. The investigation identified the formation of the nanocomposites through strong covalent bonding and moderate electrostatic interactions, resulting in significant binding energies. These interactions contributed to a reduction in the band gap, increased electron activity, and higher chemical reactivity compared to pure polyaniline. The formation of the nanocomposites induced a redshift in the UV–vis absorption spectra, moving the maximum absorption wavelength from the ultraviolet to the visible region, indicating n-type doping. Natural bond orbital analysis confirmed the role of yttrium oxide clusters as electron acceptors, with polyaniline serving as an electron donor.

Pharmacokinetic predictions of ROS-mediated targets and genotoxin combinations via multiple ligand simultaneous docking and ROS evaluation in vitro using HepG2 cell lines.

Although combination therapy is known for its high efficacy, reduced side effects and drug resistance, toxicity remains a major drawback. Some of the genes are likely to induce hepatotoxicity through ROS-mediated mechanisms when a drug is metabolized alone or in combination in the liver. To address this, we have developed a scientific approach to predict the toxicity of different genotoxin combinations and validate their interactions with various targets. The current study is an extensive study of our previous set of in vivo rat liver microarray data processed using R studio for their functional analysis. About five combinations of genotoxins such as CPT/ETP, CPT/CPL, ETP/CPL, CP/CPT and EES/CP along with their differential gene expression targeting Chemical carcinogenesis-ROS are chosen for this study. We aim to examine the binding affinity of different genotoxin combinations using in silico multiple ligand simultaneous docking (MLSD) and are then bio-evaluated for cytotoxicity in vitro using human hepatocellular carcinoma cell lines (HepG2) with the MTT assay. As a result, dose-response cytotoxicity with its strength of interactions and a significant variance in ROS levels in the treated cells is observed compared to their IC50 values. Out of 5 combinations such as CPT/CPL, ETP/CPL and EES/CP are found not only to be significantly cytotoxic but also induce oxidative stress specifically above their IC50 values with good and moderate binding interactions ensuring their toxicity. On the contrary, the safe combinations are found to be CTP/ETP and CP/CPT possibly with no and tolerable adverse effects standing as preliminary information for researchers in drug design and development.

Moderators of the Effects of a Digital Parenting Intervention on Child Conduct and Emotional Problems Implemented During the COVID-19 Pandemic: Results From a Secondary Analysis of Data From the Supporting Parents and Kids Through Lockdown Experiences (SPARKLE) Randomized Controlled Trial.

A smartphone app, Parent Positive, was developed to help parents manage their children's conduct and emotional problems during the COVID-19 pandemic. A randomized controlled trial, Supporting Parents and Kids Through Lockdown Experiences (SPARKLE), found Parent Positive to be effective in reducing children's emotional problems. However, app effectiveness may be influenced by a range of child, family, socioeconomic, and pandemic-related factors. This study examined whether baseline factors related to the child, family, and socioeconomic status, as well as pandemic-related disruption circumstances, moderated Parent Positive's effects on child conduct and emotional problems at 1- and 2-month follow-up. This study was a secondary exploratory analysis of SPARKLE data. The data set included 646 children (4-10 years of age) with parents randomized to either Parent Positive (n=320) or follow-up as usual (n=326). Candidate baseline moderators included child age, gender, attention-deficit/hyperactivity disorder symptoms, parental psychological distress, family conflict, household income, employment status, household overcrowding, and pandemic-related disruption risk (ie, homeschooling, lockdown status, and isolation status). Child conduct and emotional problem outcomes measured at 1- (T2) and 2-months (T3) post randomization were analyzed using linear mixed-effects analysis of covariance models adjusting for baseline (T1) measure of outcome and including intervention and intervention by time point interaction terms allowing for different effects at the 2 time points. Moderation of intervention effects by baseline factors was assessed by replacing the intervention by time interaction terms with intervention by time point by baseline moderator interaction terms. Child gender was a significant moderator of the Parent Positive versus follow-up as usual effect on emotional problems (B=0.72, 95% CI 0.12-1.33; P=.02). Specifically, the effect of Parent Positive was close to significant (T2: B=-0.41, 95% CI -0.82 to 0.0004; P=.05) or significant (T3: B=-0.76, 95% CI -1.22 to -0.30; P<.001) in males only when compared with females, and males experienced a significantly larger reduction in emotional problems than females in the Parent Positive arm at the 2-month post randomization time point. None of the other investigated baseline factors moderated effects on emotional problems, and no factors moderated effects on conduct problems. This study highlights Parent Positive's potential for effectively reducing emotional problems in primary school-aged male children across a wide range of families. However, due to limited variability in the demographic background of the families, cautious interpretation is required, and replications are necessary in diverse samples with longer follow-up times. ClinicalTrials.gov NCT04786080; https://clinicaltrials.gov/ct2/show/NCT04786080.

Do social cash transfers bridge the wellbeing gender gap in developing countries? The case of Ghana’s LEAP programme

ABSTRACT Gender inequality remains a significant problem in Ghana with many women socially and economically disadvantaged. Social protection interventions, in particular cash transfer programmes, have the potential to increase wellbeing and reduce gender gaps in poor households. This article analyses the wellbeing differences between men and women beneficiaries of Ghana's Livelihood Empowerment Against Poverty (LEAP) programme. Using a multiple regression moderation interaction model, we analyse six wellbeing dimensions (financial, health, education, food, housing and social) of 322 LEAP cash transfer beneficiaries in Ghana's KEEA district. We found that female-headed households achieve better wellbeing than male-headed households when LEAP income is paid at regular intervals. Regular LEAP payments also reduce gender gaps in wellbeing. These findings contribute to the design of policies seeking to bridge the wellbeing gap between men and women.

Enantioselective Separation and Pharmacokinetics of a Chiral 1,4-Dihydropyrimidine Derivative in Rats: A Combined Chromatography and Docking Approach.

Chirality in 1,4-Dihydropyrimidines influences their pharmacological properties and synthetic strategies. Enantiomers of chiral drugs often exhibit different pharmacokinetic profiles. Therefore, separating and studying individual enantiomers is crucial to optimize drug efficacy and safety. Enantiomeric separation of ±4-(4-chlorophenyl)-6-methyl-2-oxo-N-(O-toyl)-1,2,3,4-tetrahydropyrimidine-5-carboxamide (DP-1), which is a 1,4-Dihydropyrimidine derivative is achieved on CHIRALCEL® OD-H column (particle size: 5 μm, inner diameter: 4.6 mm, length:150 mm), following by investigating the kinetic properties of (R) and (S) enantiomers. The separation was achieved with a mobile phase composed of 70% (v/v) isopropyl alcohol and 30% (v/v) n-hexane. For the bioanalytical study, acetonitrile was used to precipitate the rat plasma samples and validated the method according to USFDA guidelines. The validated bioanalytical method was then successfully applied to determine the pharmacokinetic parameters of the drug in biological samples. Molecular modeling techniques, specifically docking simulations, were employed to predict the elution order of DP-1 enantiomers. The docking results revealed moderate binding interactions between the enantiomers and the chiral stationary phase (CSP), which aligns with the theoretical expectation that stronger interactions lead to longer retention times on the column.

Hydrophobic surface modification and morphology tuning of supported KNiMoS-based catalyst for synergistically enhanced higher alcohols synthesis via CO hydrogenation

MoS2-based catalysts have gained significant attention in higher alcohols synthesis (HAS) via CO hydrogenation. However, the water–gas shift (WGS) to produce CO2 in HAS is undesirable reaction, which will reduce the efficiency of carbon utilization. Here, we provide a facile strategy with hydrophobic surface modification and metal-support interaction modulation to design a series of KNiMoS/MgAl catalysts. The organic modified SiO2 shell with excellent hydrophobicity effectively shortens the residence of water formed in HAS, and further suppress the generation of CO2 and low-chain hydrocarbons. Moreover, the moderate metal-support interaction between MoS2-based active species and MgAl support can regulate the dispersion and sulfidation extent of MoS2 slabs to provide more active sites for alcohol formation. The MoS2 slabs with predominant double-layer structure enhance the C–C propagation and CO insertion in HAS. And as a result, the optimal KNiMoS/MgAl@Si(c)-5 achieves total alcohols selectivity of 74.7 %, C2+OH selectivity of 85.8 % in total alcohols, and C2+ alcohols space–time yield of 107.8 mg gcat-1h−1, where C2+ alcohols space–time yield is 3.50 and 2.71 times than those on KNiMoS/MgAl(H) and KNiMoS/MgAl, respectively. Notably, the total selectivity of CO2 and hydrocarbons is less than 23.2 %, and selectivity ratio of C2-4OH to methanol can be overturned from 1.9 to 6.0. The dependence of HAS performance on the morphology of MoS2 slabs were also demonstrated to get insight into the structure-performance relationship. This work provides a facile strategy with tunable hydrophobic surface and metal-support interaction of MoS2-based catalysts for further improvement of catalytic performance.

Interactions of per- and polyfluoroalkyl substances with polypropylene plastic and borosilicate glass: Resolving key uncertainties for accurate analysis

This study addresses critical uncertainties regarding the interactions of per- and polyfluoroalkyl substances (PFAS) with plastic (e.g., polypropylene, PP) and borosilicate glass materials, which are either recommended or advised against by prevalent analytical methods. Our results indicate that borosilicate glass minimally adsorbs short-chain, moderate-chain, and some long-chain PFAS with <11 perfluorinated carbons, maintaining the integrity of PFAS solutions. The ratios of PFAS concentrations in solutions contained in borosilicate glass compared to those in solutions unaffected by laboratory ware interaction showed minimal deviation, with most compounds displaying values within the established acceptable limits of 87 % to 107 % for C3‒C10 PFAS. Similarly, PP tubes, syringes, and pipette tips also demonstrated minimal or moderate interactions: perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) showed relatively consistent recoveries in PP syringes and pipette tips, ranging from 96 % to 107 % and minimal adsorption to PP centrifuge tubes during a 105-h contact period. Both materials, however, showed significant adsorption of the longest-chain PFAS in this study (C11), pointing to enhanced adsorption due to their hydrophobic nature. However, microfilters demonstrate significant adsorption of long-chain PFAS, including PFOA and PFOS. We developed a Gradient Flush Syringe Method to mitigate adsorption losses on syringe filters, achieved a significant reduction in C11 PFAS retention on filters from >90 % to nearly 0.01 %. Methanol-induced matrix effects were also studied, showed that increasing methanol concentrations led to artificially increasing the analyzed concentration of short-chain PFAS from the true concentration.

Modulating Interfacial Zn2+ Desolvation and Transport Kinetics through Coordination Interaction toward Stable Anodes in Aqueous Zn-Ion Batteries.

Aqueous Zn-ion batteries (AZIBs) are promising candidates for grid-scale energy-storage applications, but uneven Zn2+ flux distribution and undesirable water-related interfacial side reactions seriously hinder their practical application. Herein, a strategy of regulating the coordination interaction between Zn2+ and artificial interphase layers (AILs) to modulate the interfacial Zn2+ desolvation/transport behaviors and relieve side reactions for building stable Zn anodes is proposed. By selectively choosing appropriate polymers with different functional groups, it is shown that compared with the strong interaction offered by aryl groups in polystyrene-based AILs, cyano groups in polyacrylonitrile (PAN)-based AILs provide a moderate coordination interaction with Zn2+, which not only accelerates interfacial Zn2+desolvation kinetics but also enables efficient Zn2+ transport within AILs. Moreover, the Zn2+ transport kinetics of PAN-based AILs can be further enhanced with the incorporation of an ionic conductor, zinc phosphate (ZP). Because of these advantages, the Zn anodes decorated with the hybrid AILs composed of PAN and ZP can steadily operate for >2000h at 0.2mA cm-2 and >350h at a high current density of 10mA cm-2. This work provides a valuable guideline for selective design of AILs at the molecular level for durable AZIBs.

Copper (II) halide compounds with cationic N-donor ligands: Design, synthesis, structure and magnetism

Copper (II) complexes of the cationic ligands 1-(4′-pyridyl)-pyridinium (L1) and 1-(4′-pyridyl)-pyridin-4-ol (L2) have been prepared and characterized by single crystal X-ray diffraction and variable temperature magnetic susceptibility measurements: [Cu(L1)2X2]X2 [where X = Cl (1), Br (2)], and [Cu(L2)2X2]X2 [where X = Cl (3), Br (4)]. The complexes are fundamentally square planar with L2X2 coordination planes and long, semi-coordinate bonds to the additional halide ions. All compounds crystallize in monoclinic systems with 1 and 2 in the P21/n space group and 3 and 4 in the P21/c space group. The crystal structures are stabilized by both non-classical (in the case of 1 and 2) and classical (3 and 4) hydrogen bonds. EPR data for 1–4 support a rhombohedral structure, in good agreement with the local geometry as seen in the crystal structures. Magnetic susceptibility measurements show the presence of very weak antiferromagnetic interactions. In addition, the syntheses and magnetic properties of two neutral complexes, [Cu(L3)2X2]·2H2O [L3 = 1-(4′-pyridino)-4-pyridone; X = Cl (5), Br (6)] are reported. Magnetic susceptibility data indicate the presence of moderate antiferromagnetic exchange interactions [J ∼ 28 K (5), 60 K (6)] which were well modeled by the S = 1/2 Heisenberg uniform chain model.

The Role of Inflation in Moderate Interaction of Gold Rolling Spots and Macroeconomic Variables on the ICDX Exchange

The Role of Inflation in Moderate Interaction of Gold Rolling Spots and Macroeconomic Variables on the ICDX Exchange

Transcriptomic analyses of differentially expressed human genes, micro RNAs and long-non-coding RNAs in severe, symptomatic and asymptomatic malaria infection

Malaria transmission and endemicity in Africa remains hugely disproportionate compared to the rest of the world. The complex life cycle of P. falciparum (Pf) between the vertebrate human host and the anopheline vector results in differential expression of genes within and between hosts. An in-depth understanding of Pf interaction with various human genes through regulatory elements will pave way for identification of newer tools in the arsenal for malaria control. Therefore, the regulatory elements (REs) involved in the over- or under-expression of various host immune genes hold the key to elucidating alternative control measures that can be applied for disease surveillance, prompt diagnosis and treatment. We carried out an RNAseq analysis to identify differentially expressed genes and network elucidation of non-coding RNAs and target genes associated with immune response in individuals with different clinical outcomes. Raw RNAseq datasets, retrieved for analyses include individuals with severe (Gambia—20), symptomatic (Burkina Faso—15), asymptomatic (Mali—16) malaria as well as uninfected controls (Tanzania—20; Mali—36). Of the total 107 datasets retrieved, we identified 5534 differentially expressed genes (DEGs) among disease and control groups. A peculiar pattern of DEGs was observed, with individuals presenting with severe/symptomatic malaria having the highest and most diverse upregulated genes, while a reverse phenomenon was recorded among asymptomatic and uninfected individuals. In addition, we identified 141 differentially expressed micro RNA (miRNA), of which 78 and 63 were upregulated and downregulated respectively. Interactome analysis revealed a moderate interaction between DEGs and miRNAs. Of all identified miRNA, five were unique (hsa-mir-32, hsa-mir-25, hsa-mir-221, hsa-mir-29 and hsa-mir-148) because of their connectivity to several genes, including hsa-mir-221 connected to 16 genes. Six-hundred and eight differentially expressed long non coding RNA (lncRNA) were also identified, including SLC7A11, LINC01524 among the upregulated ones. Our study provides important insight into host immune genes undergoing differential expression under different malaria conditions. It also identified unique miRNAs and lncRNAs that modify and/or regulate the expression of various immune genes. These regulatory elements we surmise, have the potential to serve a diagnostic purpose in discriminating between individuals with severe/symptomatic malaria and those with asymptomatic infection or uninfected, following further clinical validation from field isolates.

Pengaruh Interaksi Sosial dan Social Support terhadap Kinerja Karyawan dengan Kepuasan Kerja sebagai Moderasi

The aim of this research is to analyze the influence of social interaction and social support on employee performance with job satisfaction as moderation. The analysis used in this research is a quantitative approach. The population of this study was employees from several companies totaling 65 people. The data collection techniques used in this research were questionnaires, interviews and literature studies, and the analysis method used Smart PLS software. The findings in this research are that social interaction and social support influence employee performance. Job satisfaction as a moderating variable is able to moderate social interaction and social support on employee performance.

Assembly/disassembly control of gold nanorods with uniform orientation on anionic polymer brush substrates

Abstract Sophisticated control of the spatial arrangement of gold nanorods provides significant advantages in the design of plasmonic systems. However, dynamic modulation of the gold nanorod spatial arrangements remains challenging. Here, we present a novel strategy for dynamic control of thermo-responsive gold nanorods with uniform alignment on a solid substrate using polymer brushes. In this system, cationic and thermo-responsive gold nanorods were immobilized into anionic polymer brushes via moderate electrostatic interactions, providing vertically aligned gold nanorod arrays. Upon heating, the gold nanorods were assembled while maintaining their vertical orientation within the polymer brushes. They returned to the original state upon cooling, indicating reversible assembly/disassembly. It is noticeable that this system exhibits rapid changes in nanostructure arrangement even when immobilized in the polymer brush substrate on a solid substrate rather than those dispersed in solution. Importantly, the gold nanorods showed good adhesion stability in polymer brushes without any significant detachment during washing and thermal cycling processes but performed assembly formation even at largely separated conditions, indicating the traveling of considerable distances similar to the lateral diffusion of membrane proteins in cell membranes. In addition to providing unprecedented control over gold nanorod spatial configurations, our approach introduces a versatile platform for developing advanced plasmonic devices.

Telluronium-Catalyzed Halogenation Reactions: Chalcogen-Bond Activation of N-Halosuccinimides and Catalysis.

The ability of triaryltelluronium salts to interact with N-halosuccinimides (NXS) through chalcogen bonding (ChB) in the solid state and in solution is demonstrated herein. Cocrystals of the triaryltelluronium bearing two CF3 electron-withdrawing groups per aryl ring with N-chloro-, N-bromo- and N-iodosuccinimide (respectively NCS, NBS and NIS) were analyzed by X-ray diffraction, evidencing a ChB between tellurium and the carbonyl group of NXS. This ChB was confirmed in solution by NMR spectroscopy, especially by 125Te NMR titration experiment, which allowed the determination of the association constant (Ka) between the telluronium and NBS. The so-obtained Ka value of 17.3±0.6 M-1 indicated a moderate interaction in solution because of the competitive role of the solvent. The strength of the Te⋅⋅⋅O ChB was however sufficient enough to promote the catalytic halofunctionalization of aromatics and of alkenes such as the intra- and intermolecular haloalkoxylation and haloesterification of alkenes.