ZIF‐Induced d‐Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction

The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst–H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d‐band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 μg mg_cat^?1 h^?1 under ambient conditions. The strategy lowers electrocatalyst d‐band position to weaken H adsorption and concurrently creates electron‐deficient sites to kinetically drive NRR by promoting catalyst–N₂ interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44‐fold compared to without ZIF (ca. 1 %). The Pt/Au‐N_ZIF interaction is key to enable strong N₂ adsorption over H atom.     

Cs2PtI6 Halide Perovskite is Stable to Air,Moisture, and Extreme pH: Application to Photoelectrochemical Solar Water Oxidation

Halide perovskites show incredible photovoltaic power conversion efficiency coupled with several hundreds of hours of device stability. However, their stability is poor in aqueous electrolyte media. Reported here is a vacancy ordered halide perovskite, Cs₂PtI₆, which shows extraordinary stability under ambient conditions (1 year), in aqueous media of extreme acidic (pH 1), basic (pH 13), and under electrochemical reduction conditions. It was employed as an electrocatalyst and photoanode for hydrogen production and water oxidation, respectively. The catalyst remains intact for at least 100 cycles of electrochemical cycling and six hours of hydrogen production at pH 1. Cs₂PtI₆ was employed as a photoanode for PEC water oxidation, and the material displayed a photocurrent of 0.8 mA cm⁻² at 1.23 V (vs. RHE) under simulated AM1.5G sunlight. Using constant voltage measurement, Cs₂PtI₆ exhibited over 12 hours of PEC stability without loss of performance.     

Syntheses and structures of asymmetric Bis(silyl) niobocene hydrides

This paper deals with the preparation and structural investigation of asymmetric bis(silyl) niobocene hydrides, Cp2Nb(SiHMe2)(H)(SiXMe2) (2; X = F (a), Cl (b), Br (c), I (d)) and Cp2Nb(SiXMe2)(H)(SiYMe2) (X,Y= F-I; X not equal Y). Complexes 2a-d were prepared by selective electrophilic activation of the Si-H bond in Cp2Nb(SiHMe2)2(H). The Cp2Nb(SiXMe2)(H)(SiYMe2) complexes were prepared by electrophilic activation of the Si-H bond in 2a-d and, in some cases, by electrophilic exchange of the X halides in Cp2Nb(SiXMe2)2(H) (1) for other halides, Y. The structures of complexes 2b and 2c have been studied by X-ray and neutron diffraction (ND). The ND results unequivocally established that the hydride ligand in 2c is shifted toward the SiBrMe2 ligand and that in 2b is positioned symmetrically between two nonequivalent silyl groups, with the H...SiClMe2 distance being shorter because of the shorter Nb-SiClMe2 bond length. Analysis of the X-ray structures of complexes 2a-d and complexes Cp2Nb(SiXMe2)(H)(SiYMe2) shows that the largest structural distortions are observed for the silyl groups substituted by heavy halogen atoms. These trends are rationalized in terms of stronger interligand hypervalent interactions (IHI) Nb-H...Si-X for heavy atoms X from Group 7.     

Cyclometallated iridium and platinum complexes with noninnocent ligands

The electronic properties of the cyclometalated (CwedgeN) complexes of iridium and platinum metals with a catechol ligand have been studied experimentally and computationally. The synthesis and characterization of (p-tolylpyridine)Ir(3,5-di-tert-butylcatechol) (abbreviated Ir-sq) and (2,4-diflorophenylpyridine)Pt(3,5-di-tert-butylcatechol) (abbreviated Pt-sq) are reported along with their structural, spectral, and electrochemical properties. Reaction of the 3,5-di-tert-butylcatechol (DTBCat) ligand with the prepared cyclometalated metal complex was carried out in air in the presence of a base. The resulting complexes are air stable and are paramagnetic with the unpaired electron residing mainly on the catechol ligand. The bond lengths obtained from X-ray structure analysis and the theoretical results suggest the semiquinone form of the catechol ligand. Low-energy, intense (approximately 10(3) M-1 cm-1) transitions are observed in the visible to near-infrared region (600-700 nm) of the absorption spectra of the metal complexes. Electrochemically, the complexes exhibit a reversible reduction of the semiquinone form to the catechol form of the ligand and an irreversible oxidation to the unstable quinone form of the ligand. The noninnocent catechol ligand plays a significant role in the electronic properties of the metal complexes. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations on the two open-shell molecules provide the ground-state and excited-state energies of the molecular orbitals involved in the observed low-energy transitions. The spin density in the two complexes resides mainly on the catechol ligand. The intense transition arises from excitation of the beta electron from a HOMO-n (n = 1 or 2 here) to the LUMO, rather than from the excitation of the unpaired alpha electron.     

Extending Petri net to reduce control strategies of railway interlocking system

In our previous articles we gave step by step refinement process towards the development of safety properties of moving block interlocking system (MBRIS). The refinement process started from abstraction to fuzzy based safety properties using Z and then fuzzy multi agent specification language. However, one dimensional control of train passing through a switch and level crossing were not discussed. This paper reduces the existing two dimensional controls along the switch and level crossing to one dimensional for shifting it to a train only. For example, in the existing model the train movement along components switches and level crossings depends on both the train and components control. Whereas, in one dimensional control train is the only authority to control a switch and level crossing required for its desired operation. For this reduction, concurrent and mobile agent concepts are required. Therefore, we integrate mobile agent concepts with Petri nets to develop the mobile Petri net (MPN) a new class of PNs. This supports both mobility and concurrency. Further, we prove that the collection of different MPNs in a connected network is a PN. This proof allowed us to use the properties of PN to verify the system. Finally, we use MPN to model the safety properties of MBRIS along the switch and level crossing. This provides one dimensional control to a train along a switch and level crossing which increases the safety of the railway interlocking system. Moreover, we use reachability graph (RG) to verify the switch and level crossing models.     

Near-field subsurface detection using metamaterial inspired probes

Recently, it was shown that single negative media can significantly enhance the sensitivity of near-field probes. Inspired by this recent finding, a new near-field probe is proposed for noninvasive subsurface detection. The new probe uses a single split ring resonator (SRR) instead of a periodic arrangement of SRRs for negative material realization. Experimental tests were conducted to detect the presence of cracks on aluminum plates, the presence of small aluminum blocks located behind a layer of ground chicken (lossy medium), and the presence of a small aluminum block submerged in sodium chloride solution (lossy medium) with a salinity of 1%. Preliminary results show that the proposed near-field probe enables detection of electrically small targets buried in lossy media.     

内窥镜中Walter B流体的蠕动流

研究内窥镜中Walter B流体的蠕动流,在圆柱坐标系中建立问题的模型,目的是研究内窥镜对Walter B流体蠕动流的影响.以delta为摄动参数,使用正规的摄动法求出解析解.利用数值积分,求得压力增量和摩擦力的近似解析解.用图形给出了Walter B流体所显现参数的影响.     

Stereoselective vinylation of aryl N-(2-pyridylsulfonyl) aldimines with 1-alkenyl-1,1-heterobimetallic reagents

Vinylation of aryl N-(2-pyridylsulfonyl) aldimines with versatile 1-alkenyl-1,1-borozinc heterobimetallic reagents is disclosed. In situ hydroboration of air-stable B(pin)-alkynes followed by chemoselective transmetalation with dimethylzinc and addition to aldimines provides B(pin)-substituted allylic amines in 53-93% yield in a one-pot procedure. The addition step can be followed by either B-C bond oxidation to provide α-amino ketones (71-98% yield) or Suzuki cross-coupling to furnish trisubstituted 2-arylated (E)-allylic amines (51-73% yield).     

Green Synthesis of Silver Nanoparticles Using Euphorbia wallichii Leaf Extract: Its Antibacterial Action against Citrus Canker Causal Agent and Antioxidant Potential

Biologically synthesized silver nanoparticles are emerging as attractive alternatives to chemical pesticides due to the ease of their synthesis, safety and antimicrobial activities in lower possible concentrations. In the present study, we have synthesized silver nanoparticles (AgNPs) using the aqueous extract of the medicinal plant Euphorbia wallichii and tested them against the plant pathogenic bacterium Xanthomonas axonopodis, the causative agent of citrus canker, via an in vitro experiment. The synthesized silver nanoparticles were characterized by techniques such as UV-Vis spectroscopy, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction analysis and transmission electron microscopy. Moreover, the plant species were investigated for phenolics, flavonoids and antioxidant activity. The antioxidant potential of the extract was determined against a DPPH radical. The extract was also evaluated for phenolic compounds using the HPLC technique. The results confirmed the synthesis of centered cubic, spherical-shaped and crystalline nanoparticles by employing standard characterization techniques. A qualitative and quantitative phytochemical analysis revealed the presence of phenolics (41.52 mg GAE/g), flavonoids (14.2 mg QE/g) and other metabolites of medicinal importance. Different concentrations (1000 µg/mL to 15.62 µg/mL—2 fold dilutions) of AgNPs and plant extract (PE) alone, and both in combination (AgNPs-PE), exhibited a differential inhibition of X. axanopodis in a high throughput antibacterial assay. Overall, AgNPs-PE was superior in terms of displaying significant antibacterial activity, followed by AgNPs alone. An appreciable antioxidant potential was recorded as well. The observed antibacterial and antioxidant potential may be attributed to eight phenolic compounds identified in the extract. The Euphorbia wallichii leaf-extract-induced synthesized AgNPs exhibited strong antibacterial activity against X. axanopodis, which could be exploited as effective alternative preparations against citrus canker in planta in a controlled environment. In addition, as a good source of phenolic compounds, the plant could be further exploited for potent antioxidants.     

Extraction and Fractionation of Prokinetic Phytochemicals from Chrozophora tinctoria and Their Bioactivities

Chrozophora tinctoria is an annual plant of the family Euphorbiaceae, traditionally used as a laxative, a cathartic and an emetic. A methanolic extract of Chrozophora tinctoria (MEC) whole plant and an n-butanol fraction of Chrozophora tinctoria (NBFC) were analyzed by gas chromatography–mass spectrometry (GC-MS) to detect the phytochemicals. MEC and NBFC were tested for in vitro anti acetylcholinesterase (AChE) potential. The effect of both samples on intestinal propulsive movement and spasmolytic activity in the gastrointestinal tract (GIT) was also studied. About twelve compounds in MEC and three compounds in NBFC were tentatively identified through GC-MS. Some of them are compounds with known therapeutic activity, such as toluene; imipramine; undecane; 14-methyl-pentadecanoic acid methyl ester; and hexadecanoic acid. Both NBFC and MEC samples were checked for acute toxicity and were found to be highly toxic in a dose-dependent manner, causing diarrhea and emesis at 1 g/kg concentration in pigeons, with the highest lethargy and mortality above 3 g/kg. Both the samples of Chrozophora tinctoria revealed significant (p ≤ 0.01) laxative activity against metronidazole (7 mg/kg) and loperamide hydrochloride (4 mg/kg)-induced constipation. NBFC (81.18 ± 2.5%) and MEC (68.28 ± 2.4%) significantly increased charcoal meal intestinal transit compared to distal water (41.15 ± 4.3%). NBFC exhibited a significant relaxant effect (EC₅₀ = 3.40 ± 0.20 mg/mL) in spontaneous rabbit jejunum as compared to MEC (EC₅₀ = 4.34 ± 0.68 mg/kg). Similarly, the impact of NBFC on KCl-induced contraction was more significant than that of MEC (EC₅₀ values of 7.22 ± 0.06 mg/mL and 7.47 ± 0.57 mg/mL, respectively). The present study scientifically validates the folk use of Chrozophora tinctoria in the management of gastrointestinal diseases such as constipation. Further work is needed to isolate the phytochemicals that act as diarrheal agents in Chrozophora tinctoria.