Fogmartensen3600

Developing cost-effective and controllable technologies beyond traditional overall N2 electrocatalysis is critical for the large-scale production of NH3 through electrochemical N2 reduction reaction (NRR) under ambient conditions. Herein, the aqueous rechargeable Zn-N2 battery, assembled by coupling the bifunctional cobalt phosphate nanocrystals-loaded heteroatoms-doped carbon nanosheets (CoPi/NPCS) as cathode electrocatalyst and the commercial Zn plate as anode with KOH electrolyte, was fabricated for the sustainable reduction of N2 to NH3 and power generation during discharge process. Benefiting from the desirable active components of cobalt phosphate nanocrystals and the synergistic effect between nanocrystals and carbon substrates, the CoPi/NPCS catalyst exhibits the enhanced NRR and oxygen evolution reaction (OER) performance in alkaline electrolyte. And the cobalt phosphates are confirmed as active components through the associative pathway toward NRR. When measured in the flow battery configuration with gas diffusion electrode by flowing N2 during discharge, this CoPi/NPCS-catalyzed Zn-N2 battery enables the high N2-to-NH3 yield rate of 14.7 μg h-1 mgcat.-1 and Faradaic efficiency of 16.35% at 0.6 V vs Zn2+/Zn, which can be able to maintain stable in discharge processes during cycling tests. Moreover, the impressive power output of the peak power density of 0.49 mW cm-2 and the energy density of 147.6 mWh gzn-1 are still achieved by this Zn-N2 battery, which are both higher than those of previously reported Zn-N2 batteries. This work not only provides the guideline for the rational design of robust and active bifunctional NRR-OER catalysts but also develops a reasonable and promising technology for efficient electrochemical N2-to-NH3 and power generation.Plant diseases result in 20-40% of agricultural loss every year worldwide. Timely detection of plant diseases can effectively prevent the development and spread of diseases and ensure the agricultural yield. High-throughput and rapid methods are in great demand. This review investigates the advanced application of Raman spectroscopy (RS) and surface-enhanced Raman spectroscopy (SERS) in the detection of plant diseases. The determination of bacterial diseases and stress-induced diseases, fungal diseases, viral diseases, pests in beans, and mycotoxins related to plant diseases using RS and SERS are discussed in detail. selleck Then, biomarkers for RS and SERS detection are analyzed with regard to plant disease diagnosis. Finally, the advantages and challenges are further illustrated. Additionally, potential alternatives are proposed for the challenges. The review is expected to provide a reference and guidance for the use of RS and SERS in plant disease diagnostics.On the basis of an undeveloped asymmetrical pyridylcarboxylate ligand, 2-(2-carboxypyridin-4-yl)terephthalic acid (H3CPTA), an indium pyridylcarboxylate framework, [(Me)2NH2]1.5[In1.5(CPTA)2]·5.5NMF·6H2O (1), is synthesized under solvent thermal conditions. 1 displays a 3D anionic framework with a large void space, which contains open square channels with a cross section of 14.6 Å and a pore surface decorated with carboxylic oxygen atoms. Depending on the anionic skeleton and high water stability, 1 exhibits high adsorption selectivity and capacity for cationic dyes in aqueous solution. Furthermore, the luminescence performance illustrates that 1 has selectivity and sensitivity to nitenpyram with good recyclability.Spin-Coupled Generalized Valence Bond (SCGVB) theory provides the foundation for a comprehensive theory of the electronic structure of molecules. SCGVB theory offers a compelling orbital description of the electronic structure of molecules as well as an efficient and effective zero-order wave function for calculations striving for quantitative predictions of molecular structures, energetics, and other properties. The orbitals in the SCGVB wave function are usually semilocalized, and for most molecules, they can be interpreted using concepts familiar to all chemists (hybrid orbitals, localized bond pairs, lone pairs, etc.). SCGVB theory also provides new perspectives on the nature of the bonds in molecules such as C2, Be2 and SF4/SF6. SCGVB theory contributes unparalleled insights into the underlying cause of the first-row anomaly in inorganic chemistry as well as the electronic structure of organic molecules and the electronic mechanisms of organic reactions. The SCGVB wave function accounts for nondynamical correlation effects and, thus, corrects the most serious deficiency in molecular orbital (RHF) wave functions. Dynamical correlation effects, which are critical for quantitative predictions, can be taken into account using the SCGVB wave function as the zero-order wave function for multireference configuration interaction or coupled cluster calculations.Six silyl cobalt(III) hydrides 1-6 with [PSiP] pincer ligands having different substituents at the P and Si atoms ([(2-Ph2PC6H4)2MeSiCo(H)(Cl)(PMe3)] (1), [(2-Ph2PC6H4)2HSiCo(H)(Cl)(PMe3)] (2), [(2-Ph2PC6H4)2PhSiCo(H)(Cl)(PMe3)] (3), [(2- i Pr2PC6H4)2HSiCo(H)(Cl)(PMe3)] (4), [(2- i Pr2PC6H4)2MeSiCo(H)(Cl)(PMe3)] (5), and [(2- i Pr2PC6H4)2PhSiCo(H)(Cl)(PMe3)] (6)) were synthesized through the reactions of the ligands (L1-L6) with CoCl(PMe3)3 via Si-H bond cleavage. Compounds 1-6 have catalytic activity for alkene hydrosilylation, and among them, complex 3 is the best catalyst with excellent anti-Markovnikov regioselectivity. A silyl dihydrido cobalt(III) complex 7 from the reaction of 3 with Ph2SiH2 was isolated, and its catalytic activity is equivalent to that of complex 3. Complex 7 and its derivatives 10-12 could also be obtained through the reactions of complexes 3, 1, 4, and 5 with NaBHEt3. The molecular structure of 7 was indirectly verified by the structures of 10-12. To our delight, the addition of pyridine N-oxide reversed the selectivity of the reaction, from anti-Markovnikov to Markovnikov addition. At the same time, the reaction temperature was reduced from 70 to 30 °C on the premise of high yield and excellent selectivity. However, this catalytic system is only applicable to aromatic alkenes. On the basis of the experimental information, two reaction mechanisms are proposed. The molecular structures of cobalt(III) complexes 3-6 and 10-12 were determined by single crystal X-ray diffraction analysis.Single-particle electrochemical collision has gained great achievements in fundamental research, but it is challenging to use in practice on account of its low collision frequency and the interference of the complex matrix in actual samples. Here, magnetic separation and DNA walker amplification were integrated to build a robust and sensitive single-particle electrochemical biosensor. Magnetic nanobeads (MBs) can specifically capture and separate targets from complex samples, which not only ensures the anti-interference capability of this method but also avoids the aggregation of platinum nanoparticles (Pt NPs) caused by numerous coexisting substances. A low amount of targets can lead to the release of more Pt NPs and the generation of more collision current transients, realizing cyclic amplification. Compared with simple hybridization, a DNA walker can improve the collision frequency by about 3-fold, greatly enhancing detection sensitivity, and a relationship between collision frequency and target concentration is used to realize quantification. The biosensor realized an ultrasensitive detection of 4.86 fM human immunodeficiency virus DNA (HIV-DNA), which is 1-4 orders of magnitude lower than that of traditional methods. The successful HIV-DNA detection in complex systems (serum and urine) demonstrated a great promising application in real samples and in the development of new single-entity biosensors.Development of bioinspired nanomachines with an efficient propulsion and cargo-towing has attracted much attention in the last years due to their potential biosensing, diagnostics, and therapeutics applications. In this context, self-propelled synthetic nanomotors are promising carriers for intelligent and controlled release of therapeutic payloads. However, the implementation of this technology in real biomedical applications is still facing several challenges. Herein, we report the design, synthesis, and characterization of innovative multifunctional gated platinum-mesoporous silica nanomotors constituted of a propelling element (platinum nanodendrite face), a drug-loaded nanocontainer (mesoporous silica nanoparticle face), and a disulfide-containing oligo(ethylene glycol) chain (S-S-PEG) as a gating system. These Janus-type nanomotors present an ultrafast self-propelled motion due to the catalytic decomposition of low concentrations of hydrogen peroxide. Likewise, nanomotors exhibit a directional movement, which drives the engines toward biological targets, THP-1 cancer cells, as demonstrated using a microchip device that mimics penetration from capillary to postcapillary vessels. This fast and directional displacement facilitates the rapid cellular internalization and the on-demand specific release of a cytotoxic drug into the cytosol, due to the reduction of the disulfide bonds of the capping ensemble by intracellular glutathione levels. In the microchip device and in the absence of fuel, nanomotors are neither able to move directionally nor reach cancer cells and deliver their cargo, revealing that the fuel is required to get into inaccessible areas and to enhance nanoparticle internalization and drug release. Our proposed nanosystem shows many of the suitable characteristics for ideal biomedical destined nanomotors, such as rapid autonomous motion, versatility, and stimuli-responsive controlled drug release.

The genetic landscape of intestinal (INT) and pancreatobiliary (PB) type ampullary cancer (AC) has been evolving with distinct as well as overlapping molecular profiles.

We performed whole-exome sequencing in 37 cases of AC to identify the targetable molecular profiles of INT and PB tumors. Paired tumor-normal sequencing was performed on the HiSeq 2500 Illumina platform.

There were 22 INT, 13 PB, and two cases of mixed differentiation of AC that exhibited a total of 1,263 somatic variants in 112 genes (2-257 variants/case) with 183 somatic deleterious variants. INT showed variations in 78 genes (1-31/case), while PB showed variations in 51 genes (1-29/case). Targetable mutations involving one or more major pathways were found in 86.5% of all ACs. Mutations in APC, CTNNB1, SMAD4, KMT2, EPHA, ERBB, and Notch genes were more frequent in INT tumors, while chromatin remodeling complex mutations were frequent in PB tumors. In the major signaling pathways, the phosphoinositide 3-kinase (PI3)/AKT and RAS/mitogen-activated protein kinase (MAPK) pathways were significantly mutated in 70% of cases (82% INT, 46% PB, p = .023), with PI3/AKT mutation being more frequent in INT and RAS/MAPK in PB tumors. Tumor mutation burden was low in both differentiation types, with 1.6/Mb in INT and 0.8/Mb in PB types (p =.217).

The exome data suggest that INT types are genetically more unstable than PB and involve mutations in tumor suppressors, oncogenes, transcription factors, and chromatin remodeling genes. The spectra of the genetic profiles of INT and PB types suggested primary targeting of PI3/AKT in INT and RAS/RAF and PI3/AKT pathways in PB carcinomas.

The exome data suggest that INT types are genetically more unstable than PB and involve mutations in tumor suppressors, oncogenes, transcription factors, and chromatin remodeling genes. The spectra of the genetic profiles of INT and PB types suggested primary targeting of PI3/AKT in INT and RAS/RAF and PI3/AKT pathways in PB carcinomas.