Mcfaddenspence1743

The enthalpies for the Pt substitution reactions, i.e., Pt + OAnOn+ → PtAnOn+ + O, are calculated to range from about 14-62 kcal/mol, and the Pt-AnOn+ bond dissociation enthalpies range from about 78-149 kcal/mol for the ground electronic states. For the PtAnO+ species, the LSSs were all predicted to be the ground state, whereas the PtAnO2+ molecules all favored the HSSs. The prediction for PtUO2+ is consistent with previous theoretical findings. The natural bond orbital analyses indicate a triple bond between An and O, with a double to quadruple bond between the An and Pt.The reshaping of metal nanocrystals on substrates is usually realized by pulsed laser irradiation or ion-beam milling with complex procedures. In this work, we demonstrate a simple method for reshaping immobilized Au nanoplates through plasma treatment. Au nanoplates can be reshaped gradually with nearly periodic right pyramid arrays formed on the surface of the nanoplates. The gaseous environment in the plasma-treatment system plays a significant role in the reshaping process with only nitrogen-containing environments leading to reshaping. Siponimod The reshaping phenomenon is facet-dependent, with right pyramids formed only on the exposed 111 facets of the Au nanoplates. The morphological change of the Au nanoplates induced by the plasma treatment leads to large plasmon peak redshifts. The reshaped Au nanoplates possess slightly higher refractive index sensitivities and largely increased surface-enhanced Raman scattering intensities compared to the flat, untreated nanoplates. Our results offer insights for studying the interaction mechanism between plasma and the different facets of noble metal nanocrystals and an approach for reshaping light-interacting noble metal nanocrystals.We present the SHARC/COBRAMM approach to enable easy and efficient excited-state dynamics simulations at different levels of electronic structure theory in the presence of complex environments using a quantum mechanics/molecular mechanics (QM/MM) setup. SHARC is a trajectory surface-hoping method that can incorporate the simultaneous effects of nonadiabatic and spin-orbit couplings in the excited-state dynamics of molecular systems. COBRAMM allows ground- and excited-state QM/MM calculations using a subtractive scheme, with electrostatic embedding and a hydrogen link-atom approach. The combination of both free and open-source program packages provides a modular and extensive framework to model nonadiabatic processes after light irradiation from the atomistic scale to the nano-scale. As an example, the relaxation of acrolein from S1 to T1 in solution is provided.Sensitive, accurate, and nondestructive probing of endogenous messenger RNA (mRNA) in living cells places extremely high demands on nanocarriers and probes and is still a challenge. In the present study, we describe a target-triggered self-assembled DNA tree for amplified analysis of mRNA in intact living cells. The probes assembled into a DNA tree are transported into cells by exosomes, which is beneficial for reducing cell damage and realizing nondestructive analysis. The probes are l-configured single-stranded DNAs (LDNAs) that can resist the degradation of exonuclease and endonuclease, thus laying the foundation for accurate analysis. Under the induction of the target mRNA, the probes in the cells assemble into a small plantlet and eventually grow into a tree after a few rounds of self-cycling, achieving the exponential amplification of fluorescence signals. Compared with the signal amplification based on one-dimensional DNA trunk self-assembly, the three-dimensional DNA tree shows an excellent sensitivity both ex situ and in situ. In this way, favorable sensitivity, accuracy, and nondestructive analysis are integrated into one system. This DNA tree expands the analysis platform for analyzing more biomarkers on a genetic level in an intracellular, nondestructive, and hypersensitive manner and holds great potential in clinical diagnostic and research applications.Sulfur is a prospective material for next-generation batteries with high theoretical capacity, but its drawbacks hinder its commercialization. To overcome the low conductivity of natural sulfur and the shuttle effect of lithium polysulfide, the study proposes a novel sulfur film coated with three-dimensional nitrogen and cobalt-codoped polyhedral carbon wrapped on a multiwalled carbon nanotube sponge (3D-S@NCoCPC sponge) composite as a high-performance cathode material for rechargeable lithium-sulfur batteries. The interconnected conductive carbon network with abundant pores provides more room for the homogeneous distribution of sulfur within the composite and creates a favorable pathway for electrolyte permeability and lithium-ion diffusion. Moreover, the strong interaction between cobalt and lithium polysulfides leads to efficient suppression of the shuttle effect. In addition, the homogeneous distribution of sulfur and cobalt within the composite enhances electronic transfer for the conversion reaction of sulfur. As expected, the cathode with a high sulfur content of 77.5 wt % in the composite achieved a high initial discharge capacity of 1192 mA h g-1 and high Coulombic efficiency of 99.98% after 100 cycles at 100 mA g-1 current density. Stable performance was achieved with 92.9% capacity retention after 200 cycles at 1000 mA/g current density.Physical-assisted chemical modification is effective to reduce the allergenicity of α-lactalbumin (ALA). However, there are few in-depth studies on the allergenicity changes of physical-assisted chemical-modified ALA during digestion. The effect of gastroduodenal digestion on the allergenicity changes of ALA treated by sonication-assisted glycation was assessed. Digestion of both ALA and its glycated forms generated peptide fractions, and intact undigested glycated ALA in the hydrolysates still covalently bound to d-galactose. High-resolution mass spectrometry revealed that a higher glycation degree was discovered in sonication-preprocessed ALA compared to native ALA. Enzyme-linked immunosorbent assay and basophil degranulation showed that sonication-assisted glycation could significantly reduce ALA allergenicity. The allergenicity of both gastric and gastroduodenal hydrolysates was further increased, and the hydrolysates of sonication-assisted glycated ALA showed the lowest allergenicity. The reason could be the shielding effect of the linear epitope found to be caused by a higher glycation degree; although linear epitopes were exposed, d-galactose covalently bound to intact undigested glycated ALA in the hydrolysates retained its masking role.