Lynggaardkamp3718
In the atmosphere, water in all phases is ubiquitous and plays important roles in catalyzing atmospheric chemical reactions, participating in cluster formation and affecting the composition of aerosol particles. Direct measurements of water-containing clusters are limited because water is likely to evaporate before detection, and therefore, theoretical tools are needed to study hydration in the atmosphere. We have studied thermodynamics and population dynamics of the hydration of different atmospherically relevant base monomers as well as sulfuric acid-base pairs. The hydration ability of a base seems to follow in the order of gas-phase base strength whereas hydration ability of acid-base pairs, and thus clusters, is related to the number of hydrogen binding sites. Proton transfer reactions at water-air interfaces are important in many environmental and biological systems, but a deeper understanding of their mechanisms remain elusive. By studying thermodynamics of proton transfer reactions in clusters containing up to 20 water molecules and a base molecule, we found that that the ability of a base to accept a proton in a water cluster is related to the aqueous-phase basicity. We also studied the second deprotonation reaction of a sulfuric acid in hydrated acid-base clusters and found that sulfate formation is most favorable in the presence of dimethylamine. Molecular properties related to the proton transfer ability in water clusters are discussed.Supramolecular luminescent frameworks with conjugated architectures exhibits interesting photophysical properties with phenomenal chemical and thermal stability. This has instigated global researchers towards its extensive application in toxic analyte detection and the formulation of anti-counterfeit materials. In correlation with this present scenario, luminescent metal-organic frameworks (LMOFs), possessing tailorable structural and functional properties and exceptional physicochemical features, have been categorized as emerging 'smart materials'. Interestingly, LMOFs have assisted in the rapid development of an effectual sensing platform and swift fabrication of anti-counterfeit materials on desirable substrates with the aid of 'Inkjet Printing', which is a viable, low-cost, and high-resolution technology. Inkjet printing is an excellent material deposition technique in the modern era owing to its easy settling over flexible substrates, simplistic emergence of large area image patterns with improved throughput, minimal cost, explicit resolution, and least waste generation. The present review provides state-of-the-art progress on LMOFs based (i) luminescent security ink fabrication with static and dynamic multinodal luminescent materials and (ii) sensory device formulation for the easy and instantaneous recognition of hazardous analytes through the 'Inkjet Printing' technology. This techno-chemical integration will be certainly beneficial to prevent the growth of counterfeit materials and monitor the bioaccumulation of hazardous analytes in our ecological system.The energy storage behavior of the Li3V2(PO4)3 cathode in zinc batteries is evaluated. The dissolution or decomposition into vanadium oxide in aqueous electrolytes is revealed. Using the optimal combination of water and acetonitrile solvents in electrolyte, those processes are effectively prevented without sacrificing the Zn2+ de/insertion kinetics. Further investigation demonstrates a water induced phase transformation into a VOPO4 type structure, which is still a polyanion material and preserves the high voltage. It delivers 128 mA h g-1 capacity at 1C with 1.45 V discharge voltage, and 87 mA h g-1 capacity is retained at 10C. A stable cycling is obtained for 1000 cycles.Correction for 'Assembly of fluorinated chromanones via enantioselective tandem reaction' by Mengxue Lu et al., Chem. Commun., 2021, 57, 4722-4725, DOI 10.1039/D1CC01187A.Cyclocurcumin is a natural compound extracted from turmeric and showing, in addition to antiinfective, antibacterial, and intinflammatory capabilities, solvent-dependent phtoswitching ability. The solvent-dependent photochemistry of cyclocurcumin has been rationalized on the basis of a competition between π-π* and n-π* states. Recently we have reported the synthesis of a biomimetic analogue showing enhanced photochemical properties and in particular presenting photoswitching capacity in various media. In the present contribution we rely on the use of molecular modeling and simulation, incuding density functional and wavefunction based methods to explore the excited states potential energy surface landscape. We see that the addition of a carbon-carbon double bond to the core of the natural compounds favors the population of the π-π* state, whatever the choice of the solvent, and hence leads to photoisomerisation, with fluorescence reduced to only a minor channel, rationalizing the experimental observations. In addition, the two photon absorption cross section is also strongly increased compared to the parent compound, paving the way to the use in biologically oriented applications.In an effort to synthesize cyclometalated iridium complexes containing a tridentate C^N^C ligand, transmetallation of [Hg(HC^N^C)Cl] (1) (H2C^N^C = 2,6-bis(4-tert-butylphenyl)pyridine) with various organoiridium starting materials has been studied. The treatment of 1 with [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) in acetonitrile at room temperature afforded a hexanuclear Ir4Hg2 complex, [Cl(κ2C,N-HC^N^C)(cod)IrHgIr(cod)Cl2]2 (2), which features Ir-Hg-Ir and Ir-Cl-Ir bridges. Refluxing 2 with sodium acetate in tetrahydrofuran (thf) resulted in cyclometalation of the bidentate HC^N^C ligand and formation of trinuclear [(C^N^C)(cod)IrHgIr(cod)Cl2] (3). On the other hand, refluxing [Ir(cod)Cl]2 with 1 and sodium acetate in thf yielded [Ir(C^N^C)(cod)(HgCl)] (4). Chlorination of 4 with PhICl2 gave [Ir(C^N^C)(cod)Cl]·HgCl2 (5·HgCl2) that reacted with tricyclohexylphosphine to yield Hg-free [Ir(C^N^C)(cod)Cl] (5). Chloride abstraction of 5 with silver(i) triflate (AgOTf) gave [Ir(C^N^C)(cod)(H2O)](OTf) (6) that can ca voltammetry. Reaction of [Ir(PPh3)3Cl] with 1 and sodium acetate in refluxing thf led to isolation of the previously reported compound [Ir(κ2P,C-C6H4PPh2)2(PPh3)Cl] (10). The crystal structures of 2-5, 8, 8', 9 and 10 have been determined.Developing low-cost electrocatalysts for the nitrate reduction reaction (NO3RR) with superior performance is of great significance for wastewater treatment. Herein, we synthesized bimetal Cu/Fe nanoparticles encased in N-doped carbon nanofibers (Cu/Fe@NCNFs) through simple electrospinning followed by a pyrolysis reduction strategy. Metallic copper is beneficial for reducing nitrate to nitrite, and the existence of Fe is conducive to convert nitrate and nitrite into nitrogen. Additionally, the nitrogen-doped carbon nanofibers also facilitate the adsorption of nitrate, and the continuous and complete fiber structure enhances the stability of the catalyst and prevents the corrosion of the active sites. Therefore, the synergetic effect of bimetal Cu/Fe and N-doped carbon fiber plays a key role in promoting the efficiency of nitrate reduction. The obtained Cu/Fe@NCNF catalyst exhibits a satisfactory nitrate conversion efficiency of 76%, removal capacity of 5686 mg N g-1 Cu/Fe and nitrogen selectivity of 94%.Designing non-noble-metal electrocatalysts with excellent performance and economic benefits toward the hydrogen evolution reaction (HER) is extremely crucial for future energy development. In particular, the rational cationic-doped strategy can effectively tailor the electronic structure of the catalysts and improve the free energy of the adsorbed intermediate, thus enhancing HER performance. Herein we reported Zn-doped Ni3S2 nanosheet arrays supported on Ni foam (Zn-Ni3S2/NF) that were synthesized by a two-step hydrothermal process for improving HER catalysis under alkaline conditions. Remarkably, the obtained Zn-Ni3S2/NF displays excellent HER catalytic performance with an overpotential of 78 mV to reach a current density of 10 mA cm-2 and dramatic long-term stability for 18 h in 1 M KOH. In addition, the results based on the density functional theory calculations reveal that Zn dopants can modulate the electronic structure of Ni3S2 and optimize the hydrogen adsorption free energy (ΔGH*). Thus cationic-doping engineering provides an efficient method to enhance the intrinsic activities of transition-metal sulfides, which may contribute to the development of nonprecious electrocatalysts for HER.In recent years, transition-metal-catalyzed tandem cyclization reactions of alkynes, especially those involving a metal carbene intermediate, have received worthwhile interest, as this type of reaction does not require the use of risky and potentially explosive diazo compounds as starting materials for carbene generation. A significant and general strategy for the stereospecific synthesis of 5-membered cycles is Nazarov cyclization based on the 4π-conrotatory electrocyclization of a conjugated pentadienyl cation to afford a cyclopentenyl cation. In this review, we introduce an overview of recent advances in the transition-metal-catalyzed Nazarov cyclization of alkynes via a metal carbene intermediate, and categorize these reactions according to the structure of the metal carbene. Our aim is to accelerate advancements in this enchanting area of research.The behavior of an enediyne photoswitch is modulated with halogen bonding, coordinative bonding and hydrogen bonding. Through NMR and computational studies we demonstrate that the relative strength of the secondary bonding directly influences the rate of photoisomerization and the photostationary state.Handling and manipulation of particle-encapsulating droplets (PED) have profound applications in biochemical assays. Herein we report encapsulation of microparticles in aqueous ferrofluid droplets in a primary continuous phase (CP) and sorting of PED from empty droplets (ED) at the interface of the CP in coflow with a second continuous phase using a magnetic field. We find that the encapsulation process results in a size contrast between the PED and ED that depends on the flow regime - squeezing, dripping, or jetting - which in turn is governed by the ratio of the discrete phase to the continuous phase capillary number, Car. The difference between the volume fractions of ferrofluid in the PED and ED, ΔαPED, is utilized for sorting, and is found to depend on the ratio of the capillary numbers, Car. The difference ΔαPED is found to be maximum in the jetting regime, suggesting that the jetting regime is most suitable for encapsulation and sorting. The sorting criterion is represented in terms of a parameter ξ, which is a function of the ratios of the magnetic force to the interfacial force experienced by the PED and ED. Our study revealed that sorting is possible for ξ 0.25. The maximum sorting efficiency of our system is found to be ∼95% at a throughput of ∼100 drops per s.Hydrosilylation of C[double bond, length as m-dash]C double and C[triple bond, length as m-dash]C triple bonds is one of the most widely used processes in organosilicon chemistry, mostly catalyzed by Pt-based complexes. We report here the synthesis of an air-stable dicationic Zn2+-based complex in a hemilabile tris(2-methyl-6-pyridylmethyl) phosphine (TmPPh) ligand, 12+[B(C6F5)4]2. When heated, 12+[B(C6F5)4]2 activates Si-H bonds reversibly via ligand/metal cooperation between Lewis acidic Zn2+ and Lewis basic N centers in a frustrated Lewis pair (FLP) type fashion. https://www.selleckchem.com/products/gsk2795039.html Consequently, 12+[B(C6F5)4]2 was found to be an effective catalyst for hydrosilylation reactions of C[double bond, length as m-dash]C double and C[triple bond, length as m-dash]C triple bonds. Remarkably, these hydrosilylation reactions can be loaded under aerobic conditions, as well as, in some cases, work under neat conditions. The mechanism of the activation of the Si-H bond and the hydrosilylation reaction is proposed based on experiments and density functional theory (DFT) calculations.
