Craneobrien0448

The rate limiting step was found to be consistent with a four-centered activation of the C-H bond, in agreement with previous calculations. The product branching was modeled as a competition between dissociation of an insertion intermediate directly after the rate-limiting transition state, and traversing a transition state corresponding to a methyl migration leading to a Mg-CH3OH+ complex, though only if this transition state is stabilized significantly relative to the dissociated MgOH+ + CH3 product channel. An alternative, non-statistical mechanism is discussed, whereby a post-transition state bifurcation in the potential surface could allow the reaction to proceed directly from the four-centered TS to the Mg-CH3OH+ complex thereby allowing a more robust competition between the product channels.The "shuttle effect" of long-chain polysulfides and the low conductivity of elemental sulfur lead to the inferior cycling stability of lithium-sulfur batteries and imped their practical applications. Herein, Co3O4 nanoflakes with uniform macro pores distribution were synthesized via facile oil bath and calcination methods. Coupled with super P and coated on common polypropylene separators, they were expected to hinder the migration of lithium polysulfides (LiPSs) and accelerate the redox kinetics of polysulfides. Coin cells assembled with the Co3O4-super P interlayer exhibited a capacity of 760 mA h g-1 at 1 C, maintained 598 mA h g-1 after 350 cycles, and the decay rate of discharge capacity was only about 0.062% per cycle. Such high performance can be attributed to the synergistic effects between polar Co3O4 and conductive super P. The facile fabrication method and high performance make the Co3O4-super P interlayer a feasible material to apply in lithium-sulfur batteries.A facile synthetic method for the preparation of allyl sulfoxides by S-allylation of sulfinate esters proceeds through sulfonium intermediates without [3,3]-sigmatropic rearrangement and further Pummerer-type reactions of the resulting allyl sulfoxides. On the basis of the plausible reaction mechanism involving sulfonium salt intermediates, S-alkynylation and S-arylation were also accomplished.Fe-Based catalysts play crucial roles in Fischer-Tropsch synthesis (FTS). Herein, we for the first time demonstrate a facile sol-gel approach using natural magnetite and citric acid to fabricate porous Fe@C nanohybrids as FTS catalysts. Excellent FTS activity and stability were revealed and attributed to the formation of an Fe3C active phase and a core-shell structure. This flexible synthesis strategy clearly highlights the promising application of such materials in FTS.The quadruple perovskite oxides RCu3Fe4O12 (R rare-earth metals) exhibit large latent-heat capacities (25 J g-1 at maximum) with variable transition temperatures between 254 and 368 K, whereas their transition entropies are almost completely retained. This finding proposes an effective way to design robust thermal-energy-storage materials with various operating temperatures.A photoactivatable fluorogenic tetrazine-rhodaphenothiazine probe was synthesized and studied in light-assisted, bioorthogonal labeling schemes. Experimental results revealed that the bioorthogonally conjugated probe efficiently sensitizes 1O2 generation upon illumination with green or orange light and undergoes self-oxidation leading to an intensely fluorescent sulfoxide product. An added value of the present probe is that it is also suitable for STED super-resolution microscopy using a 660 nm depletion laser.Isotope-selective rotational spectroscopy allows to calculate molecular structures independent of assumptions or theoretical predictions. Here, we present the first de novo structure determination based on mass-correlated rotational Raman spectroscopy, analyzing the carbon atom positions of butadiene. Mass correlation allowed us to analyze signals of rare 13C isotopologues at natural abundance, without interference from the main isotopologue signals. Fitted rotational constants and structural parameters confirm literature data from rovibrational spectroscopy of synthetic isotopologues and electron diffraction experiments.Effects of non-linear coupling between the system and the bath vibrational modes on the system internal conversion dynamics are investigated using the Dirac-Frenkel variational approach with a newly defined sD2 ansatz. It explicitly accounts for the entangled system electron-vibrational states, while the bath quantum harmonic oscillator states are expanded in a superposition of quantum coherent states. Using a non-adiabatically coupled three-level model, we show that efficient irreversible internal conversion due to quadratic vibrational-bath coupling occurs when the initially populated system vibrational levels are in resonance with the vibrational levels of a lower energy electronic state, also, a non-Gaussian bath wavepacket representation is required. The quadratic system-bath couplings result in broadened and asymmetrically squeezed bath quantum harmonic oscillator wavepackets in the coordinate-momentum phase space.Disruptions to circadian rhythm have been associated with an increased risk of nonalcoholic fatty liver disease (NAFLD). DHA has been found to affect both circadian rhythm and lipid metabolism. In this study, the relationship between DHA substitution and improvements in lipid metabolism and circadian clock regulation was studied. Male C57BL/6 mice were fed a control, a high fat or a DHA substituted diet for 12 weeks. Biochemical analysis and H&E staining showed that the high-fat diet (HFD) could induce NAFLD, and DHA substitution (AOH) could attenuate NAFLD. The qPCR results showed that the expressions of core clock genes Clock and Bmal1 were significantly higher at zeitgeber (ZT) 0 (700 am) than those at ZT12 (700 pm) in the control group, while this difference in day and night disappeared in the HFD group, but was observed in the AOH group. Western blotting results indicated that the expressions of rhythm output molecules (RORα and REV-ERBα) and their downstream protein INSIG2 all showed the corresponding circadian changes. SREBP-regulated proteins were significantly increased in the HFD group at both ZT0 and ZT12, but decreased in the AOH group accompanied by the corresponding changes in the protein expressions of HMGCR, LXR, CYP7A1 and CYP27A1. Altogether, HFD can decrease or disrupt circadian rhythm fluctuation by up-regulating the expression of core circadian rhythm genes Clock and Bmal1 at ZT12, and induce metabolic abnormalities through the INSIG2-SREBP pathway regulated by RORα and REV-ERBα. DHA substitution seems to restore circadian rhythm similar to the normal circadian rhythm of "night-high, day-low" through the metabolic pathway regulated by rhythmic nuclear receptors, improving the lipid metabolism rhythm and reducing liver fat.Thermochemical air separation via cyclic redox reactions of oxide-based oxygen sorbents has the potential to achieve high energy efficiency. Although a number of promising sorbents have been investigated, further improvements in sorbent performance through a fundamental understanding of the structure-performance relationships are highly desirable. In this study, we systematically investigated the effects of A and B site dopants on the oxygen uptake/release properties (i.e., vacancy formation energy, reduction enthalpy, oxygen release temperature, and oxygen capacity) of the SrFeO3 family of perovskites as oxygen sorbents. A monotonic correlation between DFT calculated oxygen vacancy formation energy and oxygen release temperature demonstrates the effectiveness of DFT for guiding sorbent selection. Combining vacancy formation energy with stability analysis, dopants such as Ba and Mn have been identified for tuning the redox property of SrFeO3 sorbents, and increasing the oxygen capacity for temperature and pressure swings when compared to undoped SrFeO3. The Mn doped sample proved to be highly stable, with less than a 3% decrease in capacity over 1000 cycles. Although the dynamic nature of the redox process makes it difficult to use a single vacancy formation energy as the descriptor, a systematic approach was developed to correlate the oxygen storage capacities with the sorbents' compositional properties and vacancy formation energies. The combination of DFT calculations with experimental studies from this study provides a potentially effective strategy for developing improved sorbents for thermochemical air separation.The reactions between Ni+(2D) and O3, O2, N2, CO2 and H2O were studied at 294 K using the pulsed laser ablation at 532 nm of a nickel metal target in a fast flow tube, with mass spectrometric detection of Ni+ and NiO+. The rate coefficient for the reaction of Ni+ with O3 is k(294 K) = (9.7 ± 2.1) × 10-10 cm3 molecule-1 s-1; the reaction proceeds at the ion-permanent dipole enhanced Langevin capture rate with a predicted T-0.16 dependence. selleckchem Electronic structure theory calculations were combined with Rice-Ramsperger-Kassel-Markus theory to extrapolate the measured recombination rate coefficients to the temperature and pressure conditions of planetary upper atmospheres. The following low-pressure limiting rate coefficients were obtained for T = 120-400 K and He bath gas (in cm6 molecule-2 s-1, uncertainty ±σ at 180 K) log10(k, Ni+ + N2) = -27.5009 + 1.0667log10(T) - 0.74741(log10(T))2, σ = 29%; log10(k, Ni+ + O2) = -27.8098 + 1.3065log10(T) - 0.81136(log10(T))2, σ = 32%; log10(k, Ni+ + CO2) = -29.805 + 4.2282log10(T) - 1.4303(log10(T))2, σ = 28%; log10(k, Ni+ + H2O) = -24.318 + 0.20448log10(T) - 0.66676(log10(T))2, σ = 28%). Other rate coefficients measured (at 294 K, in cm3 molecule-1 s-1) were k(NiO+ + O) = (1.7 ± 1.2) × 10-10; k(NiO+ + CO) = (7.4 ± 1.3) × 10-11; k(NiO+ + O3) = (2.7 ± 1.0) × 10-10 with (29 ± 21)% forming Ni+ as opposed to NiO2+; k(NiO2+ + O3) = (2.9 ± 1.4) × 10-10, with (16 ± 9)% forming NiO+ as opposed to ONiO2+; and k(Ni+·N2 + O) = (7 ± 4) × 10-12. The chemistry of Ni+ and NiO+ in the upper atmospheres of Earth and Mars is then discussed.Borohydride (BH4-)-containing coordination polymers converted CO2 into HCO2- or [BH3(OCHO)]-, whose reaction routes were affected by the electronegativity of metal ions and the coordination mode of BH4-. The reactions were investigated using thermal gravimetric analysis under CO2 gas flow, infrared spectroscopy, and NMR experiments.Antisense oligonucleotides are now entering the clinic for hard-to-treat diseases. New chemical modifications are urgently required to enhance their drug-like properties. We combine amide coupling with standard oligonucleotide synthesis to assemble backbone chimera gapmers that trigger an efficient RNase H response while improving serum life time and cellular uptake.The emergence of viral nanotechnology over the preceding two decades has created a number of intellectually captivating possible translational applications; however, the in vitro fate of the viral nanoparticles in cells remains an open question. Herein, we investigate the stability and lifetime of virus-like particle (VLP) Qβ-a representative and popular VLP for several applications-following cellular uptake. By exploiting the available functional handles on the viral surface, we have orthogonally installed the known FRET pair, FITC and Rhodamine B, to gain insight of the particle's behavior in vitro. Based on these data, we believe VLPs undergo aggregation in addition to the anticipated proteolysis within a few hours of cellular uptake.