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Unveiling the contributions of electroosmotic flow (EOF) in the electrokinetic transport through structurally-defined nanoscale pores and channels is challenging but fundamentally significant because of the broad relevance of charge transport in energy conversion, desalination and analyte mixing, micro and nano-fluidics, single entity analysis, capillary electrophoresis etc. This report establishes a universal method to diagnose and deconvolute EOF in the nanoscale transport processes through current-potential measurements and analysis without simulation. By solving Poisson, Nernst-Planck (PNP) with and without Navier-Stokes (NS) equations, the impacts of EOF on the time-dependent ion transport through asymmetric nanopores are unequivocally revealed. A sigmoidal shape in the I-V curves indicate the EOF impacts which further deviate from the well-known non-linear rectified transport features. Two conductance signatures, an absolute change in conductance and a 'normalized' one relative to ion migration, are proions.Ferrous nitrosyl FeNO7 species is an intermediate common to the catalytic cycles of Cd1NiR and CcNiR, two heme-based nitrite reductases (NiR), and its reactivity varies dramatically in these enzymes. [https://www.selleckchem.com/products/pf-04691502.html check details] The former reduces NO2- to NO in the denitrification pathway while the latter reduces NO2- to NH4+ in a dissimilatory nitrite reduction. With very similar electron transfer partners and heme based active sites, the origin of this difference in reactivity has remained unexplained. Differences in the structure of the heme d 1 (Cd1NiR), which bears electron-withdrawing groups and has saturated pyrroles, relative to heme c (CcNiR) are often invoked to explain these reactivities. A series of iron porphyrinoids, designed to model the electron-withdrawing peripheral substitution as well as the saturation present in heme d 1 in Cd1NiR, and their NO adducts were synthesized and their properties were investigated. The data clearly show that the presence of electron-withdrawing groups (EWGs) and saturated pyrroles together in a synthetic porphyrinoid (FeDEsC) weakens the Fe-NO bond in FeNO7 adducts along with decreasing the bond dissociation free energies (BDFENH) of the FeHNO8 species. The EWG raises the E° of the FeNO7/8 process, making the electron transfer (ET) facile, but decreases the pKa of FeNO8 species, making protonation (PT) difficult, while saturation has the opposite effect. The weakening of the Fe-NO bonding biases the FeNO7 species of FeDEsC for NO dissociation, as in Cd1NiR, which is otherwise set-up for a proton-coupled electron transfer (PCET) to form an FeHNO8 species eventually leading to its further reduction to NH4+.A new method for the direct synthesis of primary and secondary amides from carboxylic acids is described using Mg(NO3)2·6H2O or imidazole as a low-cost and readily available catalyst, and urea as a stable, and easy to manipulate nitrogen source. This methodology is particularly useful for the direct synthesis of primary and methyl amides avoiding the use of ammonia and methylamine gas which can be tedious to manipulate. Furthermore, the transformation does not require the employment of coupling or activating agents which are commonly required.Indium phosphide quantum dots (InP QDs) are nontoxic nanomaterials with potential applications in photocatalytic and optoelectronic fields. Post-synthetic treatments of InP QDs are known to be essential for improving their photoluminescence quantum efficiencies (PLQEs) and device performances, but the mechanisms remain poorly understood. Herein, by applying ultrafast transient absorption and photoluminescence spectroscopies, we systematically investigate the dynamics of photogenerated carriers in InP QDs and how they are affected by two common passivation methods HF treatment and the growth of a heterostructure shell (ZnS in this study). The HF treatment is found to improve the PLQE up to 16-20% by removing an intrinsic fast hole trapping channel (τh,non = 3.4 ± 1 ns) in the untreated InP QDs while having little effect on the band-edge electron decay dynamics (τe = 26-32 ns). The growth of the ZnS shell, on the other hand, is shown to improve the PLQE up to 35-40% by passivating both electron and hole traps in InP QDs, resulting in both a long-lived band-edge electron (τe &gt; 120 ns) and slower hole trapping lifetime (τh,non &gt; 45 ns). Furthermore, both the untreated and the HF-treated InP QDs have short biexciton lifetimes (τxx ∼ 1.2 ± 0.2 ps). The growth of an ultra-thin ZnS shell (∼0.2 nm), on the other hand, can significantly extend the biexciton lifetime of InP QDs to 20 ± 2 ps, making it a passivation scheme that can improve both the single and multiple exciton lifetimes. Based on these results, we discuss the possible trap-assisted Auger processes in InP QDs, highlighting the particular importance of trap passivation for reducing the Auger recombination loss in InP QDs.Methods for direct functionalization of C-H bonds mediated by N-oxyl radicals constitute a powerful tool in modern organic synthesis. While several N-oxyl radicals have been developed to date, the lack of structural diversity for these species has hampered further progress in this field. Here we designed a novel class of N-oxyl radicals based on N-hydroxybenzimidazole, and applied them to the direct C-H functionalization reactions. The flexibly modifiable features of these structures enabled facile tuning of their catalytic performance. Moreover, with these organoradicals, we have developed a metal-free approach for the synthesis of acyl fluorides via direct C-H fluorination of aldehydes under mild conditions.Hydrogenation of aromatic rings promoted by earth-abundant metal composites under mild conditions is an attractive and challenging subject in the long term. In this work, a simple active site creation and stabilization strategy was employed to obtain a Cu+-containing ternary mixed oxide catalyst. Simply by pre-treatment of the ternary metal oxide precursor under a H2 atmosphere, a Cu+-derived heterogeneous catalyst was obtained and denoted as Cu1Co5Ce5O x . The catalyst showed (1) high Cu+ species content, (2) a uniform distribution of Cu+ doped into the lattices of CoO x and CeO2, (3) formation of CoO x /CuO x and CeO2/CuO x interfaces, and (4) a mesoporous structure. These unique properties of Cu1Co5Ce5O x endow it with pretty high hydrogenation activity for aromatic rings under mild conditions (100 °C with 5 bar H2), which is much higher than that of the corresponding binary counterparts and even exceeds the performance of commercial noble metal catalysts (e.g. Pd/C). The synergetic effect plays a crucial role in the catalytic procedure with CeO2 functioning as a hydrogen dissociation and transfer medium, Cu+ hydrogenating the benzene ring and CoO x stabilizing the unstable Cu+ species.