Development of Group IV Metal Complexes Bearing Thioether-Amido Ligands with Enhanced High-Temperature Catalytic Performance toward Olefin Copolymerization.

The development of homogeneous metal catalysts with both high activity and exceptional thermal stability is crucial for the efficient synthesis of polyolefin elastomers (POEs) through solution-phase olefin polymerization. In this study, a series of Hf (Hf1-Hf5), Zr (Zr1), and Ti (Ti1) complexes featuring thioether-amido ligands were synthesized and carefully characterized using advanced techniques such as 1H and 13C NMR spectroscopy as well as single-crystal X-ray diffraction analysis for Hf4 and Hf5. The results revealed that the catalytic activity and 1-octene incorporation efficiency of these metal complexes followed the trend Hf > Zr > Ti, underscoring the significant impact of the metal center on catalytic performance. Furthermore, the choice of ligands was found to play a critical role in dictating the catalytic properties, with ligands bearing less steric hindrance on the sulfur atom proving to be more favorable for copolymerization reactions. Notably, the Hf complex Hf1, featuring a methyl group on the sulfur atom, displayed exceptional catalytic activity as high as 21,060 kg(polymer)·mol-1(Hf)·h-1 toward ethylene/1-octene copolymerization at 120 °C and produced POE with a high molecular weight (Mw = 6.3 × 104 g·mol-1), relatively narrow distribution (D = 2.4), and high incorporation of 1-octene (34.1 mol %). This study demonstrates the potential of tailored ligand design in developing efficient metal catalysts for the production of high-value-added POEs.

Supramolecular Electronics: Monolayer Assembly of Nonamphiphilic Molecules via Water Surface-Assisted Molecular Deposition.

Utilizing softly confined self-assembly at the water surface represents a promising approach for the fabrication of two-dimensional molecular monolayers (2D MMs), which have predominantly been concentrated on amphiphilic organic compounds before. Herein, we introduce a straightforward method termed "water surface-assisted molecular deposition (WSAMD)" to organize nonamphiphilic molecules into dense monolayers with high reproducibility. To underscore the versatility and merit of this methodology in the field of supramolecular electronics, we have successfully fabricated a range of defect-free, uniform semiconducting polymer monolayers, featuring a thickness reflective of molecular architectures. The charge carrier mobility could reach 0.05 cm2 V-1 s-1 for holes and 3.5 × 10-4 cm2 V-1 s-1 for electrons, respectively, in p-type and n-type polymeric monolayers when tested as the active layer in field-effect transistors. Furthermore, in situ polymerization reactions can be exploited to generate conductive monolayers of macromolecules such as polybenzylaniline (PBnANI) and polypyrrole (PPy), where PBnANI monolayers exhibit channel length-dependent conductivity, up to 0.37 S cm-1. The advent of the WSAMD method heralds a significant leap forward in the advancement of molecular 2D materials, catalyzing new avenues of exploration within material chemistry.

Hyphopodium-Specific Signaling Is Required for Plant Infection by Verticillium dahliae.

For successful colonization, fungal pathogens have evolved specialized infection structures to overcome the barriers present in host plants. The morphology of infection structures and pathogenic mechanisms are diverse according to host specificity. Verticillium dahliae, a soil-borne phytopathogenic fungus, generates hyphopodium with a penetration peg on cotton roots while developing appressoria, that are typically associated with leaf infection on lettuce and fiber flax roots. In this study, we isolated the pathogenic fungus, V. dahliae (VdaSm), from Verticillium wilt eggplants and generated a GFP-labeled isolate to explore the colonization process of VdaSm on eggplants. We found that the formation of hyphopodium with penetration peg is crucial for the initial colonization of VdaSm on eggplant roots, indicating that the colonization processes on eggplant and cotton share a similar feature. Furthermore, we demonstrated that the VdNoxB/VdPls1-dependent Ca2+ elevation activating VdCrz1 signaling is a common genetic pathway to regulate infection-related development in V. dahliae. Our results indicated that VdNoxB/VdPls1-dependent pathway may be a desirable target to develop effective fungicides, to protect crops from V. dahliae infection by interrupting the formation of specialized infection structures.

A Flexible, High-Voltage (>100 V) Generating Device Based on Zebra-Like Asymmetrical Photovoltaic Cascade.

The mutual conversion between light and electricity lies at the heart of optoelectronic and photonic applications. Maximization of the photoelectric conversion is a long-term goal that can be pursued via the fabrication of devices with ad-hoc architectures. In this framework, it is of utter importance to harvest and transform light irradiation into high electric potential in specific area for driving functional dielectrics that respond to pure electric field. Here, a nano-fabrication technology has been devised featuring double self-alignment that is applied to construct zebra-like asymmetric heterojunction arrays. Such nanostructured composite, which covers a surface area of 5 × 4 mm2 and contains 500 periodic repeating units, is capable of photo generating voltages as high as 140 V on a flexible substrate. This approach represents a leap over the traditional functionalization process based on simply embedding materials into devices by demonstrating the disruptive potential of integrating oriented nanoscale device components into meta-material.

Construction of Laterally Asymmetric Heterojunctions with Sub-Micrometer Resolution by Hierarchical Self-Assembly of Polythiophene Nanofibers.

Polymeric semiconductors are crucial candidates for the construction of next-generation flexible and printable electronic devices. By virtue of the successful preparation of monodispersed colloidal solution in orthogonal solvent, poly(3-hexylthiophene) (P3HT) nanofibers are developed into versatile building blocks for nanoelectronics and their compatibilities are verified with photolithographic lift-off technology. Then, the joint efforts from both the bottom-up hierarchical self-assembly and top-down self-alignment technology have led to the realization of lateral asymmetric heterojunctions with resolution better than 1 µm. As a result, planar photovoltaic devices incorporating N,N'-dioctyl-3,4,9,10-perylenedicarboximide and P3HT supramolecular nanowires as active components are constructed with the cathode-to-anode distance being tuned from ≈0.1 to 1-2 µm. Based on such a novel device configuration, an interesting phenomenon of channel-length-dependent photovoltaic efficiency is observed for the first time, strongly suggesting the impact of near-field light intensity on the performance of nanophotonic devices.

Verticillium dahliae chromatin remodeling facilitates the DNA damage repair in response to plant ROS stress.

Reactive oxygen species (ROS) production is one of the earliest responses when plants percept pathogens and acts as antimicrobials to block pathogen entry. However, whether and how pathogens tolerate ROS stress remains elusive. Here, we report the chromatin remodeling in Verticillium dahliae, a soil-borne pathogenic fungus that causes vascular wilts of a wide range of plants, facilitates the DNA damage repair in response to plant ROS stress. We identified VdDpb4, encoding a histone-fold protein of the ISW2 chromatin remodeling complex in V. dahliae, is a virulence gene. The reduced virulence in wild type Arabidopsis plants arising from VdDpb4 deletion was impaired in the rbohd mutant plants that did not produce ROS. Further characterization of VdDpb4 and its interacting protein, VdIsw2, an ATP-dependent chromatin-remodeling factor, we show that while the depletion of VdIsw2 led to the decondensing of chromatin, the depletion of VdDpb4 resulted in a more compact chromatin structure and affected the VdIsw2-dependent transcriptional effect on gene expression, including genes involved in DNA damage repair. A knockout mutant of either VdDpb4 or VdIsw2 reduced the efficiency of DNA repair in the presence of DNA-damaging agents and virulence during plant infection. Together, our data demonstrate that VdDpb4 and VdIsw2 play roles in maintaining chromatin structure for positioning nucleosomes and transcription regulation, including genes involved in DNA repair in response to ROS stress during development and plant infection.

The convergence characteristics of China's carbon intensity: Evidence from a dynamic spatial panel approach.

In recent years, China's CO2 emissions have surged as the country's economy has expanded rapidly. Faced with mounting international and domestic pressures, China has made great efforts to curb CO2 emissions. To formulate targeted regional reduction plans, the features and characters of provincial carbon intensity should be carefully evaluated. In this study, the existence of convergence in China's carbon intensity and possible technological factors that may influence the convergence, are carefully investigated by building a united framework and employing dynamic spatial panel approach. The estimation results verify that there is significant spatial correlation in China's provincial carbon intensity. There is also evidence that the three different types of convergence (i.e., stochastic convergence, σ-convergence and ß-convergence) exist during the sample period of 2000-2016. Moreover, among the technological factors of conditional ß-convergence, indigenous innovation activity is most critical. Not all foreign innovations stem from the inflow of foreign direct investment and trade exert a positive effect on carbon intensity reduction. Besides, it is estimated that the spatial spillovers effects from neighboring provinces are important to carbon intensity.

[Instantaneous chaometry applied in heart rate study].

Instantaneous chaometry was defined on uniformity theory constructed by the present authors. The sample data, sinus heart rate data and arrhythmia heart rate data from MIT-BIH were analyzed with instantaneous chaometry (ICM); the situation not being distinguished with HRV can be differentiated with ICM. The normal sinus rhythm was found to be of three evident characteristics: (1) instant returning to zero, (2) stability-stable characteristic of ICM on the initial position, (3) interval of mean: 2-7, variance: 1.5-5. The third characteristic shows that the variability of ICM is necessary. The studies on arrhythmia database showed that arrhythmia cases exhibited no returning to zero, nonstability of ICM on the initial position, too small mean or standard deviation, respectively. Evidently, the arithmetic of ICM is simple; ICM can be easily applied in clinical and pathologic analyses.

Presynaptic alpha-7 nicotinic acetylcholine receptors modulate excitatory synaptic transmission in hippocampal neurons.

The effects of presynaptic nicotinic acetylcholine receptors (nAChRs) on excitatory synaptic transmission in CA1 pyramidal neurons of the rat hippocampus were examined by blind whole-cell patch clamp recording from hippocampal slice preparations. Local application of the nAChRs agonist dimethylphenyl-piperazinium iodide (DMPP) did not induce a postsynaptic current response in CA1 pyramidal cells. However, DMPP enhanced the frequency and amplitude of spontaneous excitatory postsynaptic current (sEPSC) in these cells in a dose-dependent manner. This enhancement was blocked by the selective nicotinic alpha-7 receptor antagonist alpha-bungarotoxin, but not by the antagonist mecamylamine, hexamethonium or dihydro-beta-erythroidine. The frequency of miniature excitatory postsynaptic current (mEPSC) in CA1 pyramidal neurons was also increased by application of DMPP, indicating a presynaptic site of action of the agonist. Taken together, these results suggest that activation of presynaptic nAChRs in CA1 pyramidal neurons, which contain alpha-7 subunits, potentiates presynaptic glutamate release and consequently modulate excitatory synaptic transmission in the hippocampus.

Effects of the Superoxide Anionic Radicals to the Cultured Cerebral Cortex Neuron of Newborn Rat.

The effect of the superoxide anionic radicals to the cultured cerebral cortex neuron of newborn rat was investigated by using xanthine oxidase/xanthine. The results are as follows. The growth of neuron was inhibited ATPase activity decreased to 4.223 &mgr;mol/(mg.min(-1))(Pr) total cellular carbonyl increased to 295.40 &mgr;mol/g wet weight lipid peroxides(LPO) increased to 4.87 nmol/g(Pr) membrane lipid fluidity decreased (P value 0.398) in nuclear DNA, thesingle strand breaks(SSB) increased in the single cell gel assay(SCG), DNA migration was 7.35 mm ݣ subcellular structures of the neuron changed (mitochondria were swelling, etc.) and SOD gene expression of the neuron increased (the SOD activity and the SOD content increased, SOD mRNA content increased). These suggest that the superoxide anionic radicals could damage proteins, nucleic acids, lipids and subcellular structures in neurons.