Ab initio calculations on SF2 and its low-lying cationic states: anharmonic Franck-Condon simulation of the UV photoelectron spectrum of SF2

Geometry optimization calculations were carried out on the (approximate)X(1)A(1) state of SF2 and the (approximate)X(2)B(1), (approximate)A(2)A(1), (approximate)B(2)B(2), (approximate)C(2)B(2), (approximate)D(2)A(1), and (approximate)E(2)A(2) states of SF2(+) employing the restricted-spin coupled-cluster single-double plus perturbative triple excitation [RCCSD(T)] method and basis sets of up to the augmented correlation-consistent polarized quintuple-zeta [aug-cc-pV(5+d)Z] quality. Effects of core electron (S 2s(2)2p(6) and F 1s(2) electrons) correlation and basis set extension to the complete basis set limit on the computed minimum-energy geometries and relative electronic energies (adiabatic and vertical ionization energies) were investigated. RCCSD(T) potential energy functions (PEFs) were calculated for the (approximate)X(1)A(1) state of SF2 and the low-lying states of SF2(+) listed above employing the aug-cc-pV(5+d)Z and aug-cc-pV5Z basis sets for S and F, respectively. Anharmonic vibrational wave functions of these neutral and cationic states of SF2, and Franck-Condon (FC) factors of the lowest four one-electron allowed neutral photoionizations were computed employing the RCCSD(T) PEFs. Calculated FC factors with allowance for Duschinsky rotation and anharmonicity were used to simulate the first four photoelectron bands of SF2. The agreement between the simulated and observed first bands in the He I photoelectron spectrum reported by de Leeuw et al. [Chem. Phys. 34, 287 (1978)] is excellent. Our calculations largely support assignments made by de Leeuw et al. on the higher ionization energy bands of SF2.     

Direct measurement of Criegee intermediate (CH2OO) reactions with acetone, acetaldehyde, and hexafluoroacetone

Criegee biradicals, i.e., carbonyl oxides, are critical intermediates in ozonolysis and have been implicated in autoignition chemistry and other hydrocarbon oxidation systems, but until recently the direct measurement of their gas-phase kinetics has not been feasible. Indirect determinations of Criegee intermediate kinetics often rely on the introduction of a scavenger molecule into an ozonolysis system and analysis of the effects of the scavenger on yields of products associated with Criegee intermediate reactions. Carbonyl species, in particular hexafluoroacetone (CF(3)COCF(3)), have often been used as scavengers. In this work, the reactions of the simplest Criegee intermediate, CH(2)OO (formaldehyde oxide), with three carbonyl species have been measured by laser photolysis/tunable synchrotron photoionization mass spectrometry. Diiodomethane photolysis produces CH(2)I radicals, which react with O(2) to yield CH(2)OO + I. The formaldehyde oxide is reacted with a large excess of a carbonyl reactant and both the disappearance of CH(2)OO and the formation of reaction products are monitored. The rate coefficient for CH(2)OO + hexafluoroacetone is k(1) = (3.0 ± 0.3) × 10(-11) cm(3) molecule(-1) s(-1), supporting the use of hexafluoroacetone as a Criegee-intermediate scavenger. The reactions with acetaldehyde, k(2) = (9.5 ± 0.7) × 10(-13) cm(3) molecule(-1) s(-1), and with acetone, k(3) = (2.3 ± 0.3) × 10(-13) cm(3) molecule(-1) s(-1), are substantially slower. Secondary ozonides and products of ozonide isomerization are observed from the reactions of CH(2)OO with acetone and hexafluoroacetone. Their photoionization spectra are interpreted with the aid of quantum-chemical and Franck-Condon-factor calculations. No secondary ozonide was observable in the reaction of CH(2)OO with acetaldehyde, but acetic acid was identified as a product under the conditions used (4 Torr and 293 K).     

Physical and electrical properties of band-engineered SiO2/(TiO2) x (SiO2)1−x stacks for nonvolatile memory applications

In our study, the physical properties of (TiO₂) _x (SiO₂)_1?x , including band-gap, band-offset, and thermal stability and the electrical properties of band-engineered SiO₂/(TiO₂) _x (SiO₂)_1?x tunnel barrier stacks, including the tunneling current and charge-trapping characteristics for applications to nonvolatile memory devices were investigated. It was observed that the band-gap and band-offset of (TiO₂) _x (SiO₂)_1?x can be controlled by adjustment in the composition of the (TiO₂) _x (SiO₂)_1?x films. Ti-silicate film with TiO₂:SiO₂ cycle ratio of 1:5 was maintained in an amorphous phase, even after annealing at 950 °C. The tunneling current of the band-engineered SiO₂/(TiO₂) _x (SiO₂)_1?x stacked tunnel barrier was larger than that of a single SiO₂ barrier under a higher external bias, while the tunneling current of a SiO₂/(TiO₂) _x (SiO₂)_1?x stacked tunnel barrier under a lower external bias was smaller. Charge-trapping tests showed that the voltage shift for SiO₂/(TiO₂) _x (SiO₂)_1?x is slightly larger than that for single SiO₂.     

Indocyanine green encapsulated nanogels for hyaluronidase activatable and selective near infrared imaging of tumors and lymph nodes

Indocyanine green (ICG) encapsulated hyaluronic acid (HA) nanogels were first studied for highly selective detection of specific cancers and lymph nodes via hyaluronidase sensitive switch-on of near infrared fluorescence as a long-lasting and stimuli-responsive imaging probe.     

Characteristic profiles of the inclusion complex of omeprazole/peracylated-β-cyclodextrin formed in supercritical carbon dioxide

Inclusion properties of the drug omeprazole (OMP) with peracetylated-beta-cyclodextrin (PAc-β-CD) prepared by green method, following supercritical carbon-dioxide (scCO₂), were characterized through thermal (TGA and DSC), crystalline (XRD), NMR spectroscopic and dissolution studies. Comparison amongst PAc-β-CD, OMP, physical binary mixture (equimolar ratio of OMP: PAc-β-CD) and the solid inclusion complex (OMP/PAc-β-CD) revealed scCO₂ as a successful technique for inclusion complex formation as well, identified characteristics performances of PAc-β-CD/OMP interactions. For instance, absence of characteristic DSC or XRD peaks of either chemical in the complex was quite noticeable with the shift of proton peaks in ¹H NMR spectra. The formed inclusion complex also showed an important dissolution performance of OMP for controlled release applications partly due to the hydrophobic nature of PAc-β-CD.     

Study on Reduction of Energy Consumption in Pulsed Corona Discharge Process for NOx Removal

We investigated the reduction of electrical energy consumption in thepulsed corona discharge process for the removal of nitrogenoxides. Hydrocarbon chemical additives used in the laboratory-scaleexperiment are responsible for the enhancement of the NO conversionthrough the chain reactions of free radicals, such as, R, RCO, RO,and others. Electrical energy consumption per converted NO moleculehas a minimum value of 17 eV when pentanol is injected. When ethyleneand propylene are injected, 30 and 22 eV of electrical energy consumptionare required for the conversion of a NO molecule, respectively. The ratioof the pulse-forming capacitance (C_e) to the reactor capacitance (C_R)plays an important role in the energy transfer efficiency to thereactor. The maximum energy transfer efficiency of approximately 72%could be obtained by the pulse-forming capacitance, which is 3.4 timeslarger than the reactor capacitance; the maximum NO conversionefficiency was also observed with the same condition.     

High resolution proton magnetic resonance spectroscopy of human brain and liver

Water-suppressed and slice-selective proton spectra of live human brain exhibited several resonances that were tentatively assigned to metabolites such as N-acetylaspartate, glutamate, phosphocreatine and creatine, choline derivatives, and taurine. In the liver spectrum of a healthy volunteer, the major resonance was tentatively assigned to a fatty acyl methylene and the minor resonances to protons in carnitine, taurine, glutamate, and glutamine. In the spectrum of a cancerous liver, resonances in addition to those present in the normal liver were seen. Protein degradation in the liver with cancer was indicated by resonances from urea and from the ring protons in tryptophan, tyrosine, and phenylalanine. Furthermore, increased nucleic acid synthesis was indicated by resonances from nucleotide protons.     

Dioscin-Mediated Autophagy Alleviates MPP+-Induced Neuronal Degeneration: An In Vitro Parkinson’s Disease Model

Autophagy is a cellular homeostatic process by which cells degrade and recycle their malfunctioned contents, and impairment in this process could lead to Parkinson’s disease (PD) pathogenesis. Dioscin, a steroidal saponin, has induced autophagy in several cell lines and animal models. The role of dioscin-mediated autophagy in PD remains to be investigated. Therefore, this study aims to investigate the hypothesis that dioscin-regulated autophagy and autophagy-related (ATG) proteins could protect neuronal cells in PD via reducing apoptosis and enhancing neurogenesis. In this study, the 1-methyl-4-phenylpyridinium ion (MPP⁺) was used to induce neurotoxicity and impair autophagic flux in a human neuroblastoma cell line (SH-SY5Y). The result showed that dioscin pre-treatment counters MPP⁺-mediated autophagic flux impairment and alleviates MPP⁺-induced apoptosis by downregulating activated caspase-3 and BCL2 associated X, apoptosis regulator (Bax) expression while increasing B-cell lymphoma 2 (Bcl-2) expression. In addition, dioscin pre-treatment was found to increase neurotrophic factors and tyrosine hydroxylase expression, suggesting that dioscin could ameliorate MPP⁺-induced degeneration in dopaminergic neurons and benefit the PD model. To conclude, we showed dioscin’s neuroprotective activity in neuronal SH-SY5Y cells might be partly related to its autophagy induction and suppression of the mitochondrial apoptosis pathway.     

Preparation and electrochemical performance of titanium nitride-graphene nanocomposite with high Ti contents and tailored morphology

Titanium nitride (TiN) - graphene (G) nanocomposites are promising for electrochemical charge storage where a high content of Ti species is desired. Herein, we propose an effective method for the preparation of TiN-G nanocomposites with a high concentration of Ti species. These nanocomposites can be successfully achieved through a further deposition of Ti on Ti-graphene oxide (GO) or a thermally exfoliated Ti-GO. Depending on the annealing condition employed (NH₃ and N₂), two types of TiN-G nanocomposites (NH₃ annealing for TiN/G and TiN/G-TE, TE: thermal exfoliation) and a TiO₂-G nanocomposite (N₂ annealing for TiO₂/G-TE) were prepared. These nanocomposites were then investigated for potential application as an electrochemical supercapacitor. Compare with TiO₂/G-TE, the TiN-G nanocomposites both exhibited a higher specific capacitance, although one of these nanocomposites had a lower surface area than TiO₂/G-TE. Among the nanocomposites prepared, TiN/G-TE delivered the best electrochemical performance. The relationship between the physical properties and the capacitive performance of the nanocomposites were systematically evaluated.