Reaction mechanism of aerobic oxidation of alcohols conducted on activated-carbon-supported cobalt oxide catalysts

Catalytic performances and the reaction mechanism of Co(3)O(4)/AC (AC=activated carbon) for aerobic oxidation of alcohols carried out in the liquid phase were investigated. Co(3)O(4)/AC shows a high activity for aerobic oxidation of benzyl alcohol, comparable to noble metal catalysts (e.g., Au/AC) even in the absence of additives or promoters (e.g., NaOH). Changing preparation conditions, such as treatment temperature and/or time, can affect the catalytic performances of Co(3)O(4)/AC, due to decomposition of surface groups of the carbon support. Careful studies show that low alcohol conversions are obtained with either Co(3)O(4) or AC alone, which indicates that the high conversion observed over the Co(3)O(4)/AC is due to a synergistic effect between Co(3)O(4) and AC. Parallel experiments using a high-surface-area covalent triazine framework or oxygen-inert carbon nitride as support for the Co(3)O(4) catalyst also show lower conversions, which suggest that the ability of AC (in Co(3)O(4)/AC) to activate molecular oxygen is essential for the reaction. FTIR and XPS spectra taken from catalysts before and after the reaction confirm that oxygen activation proceeds mainly on the carbon support. As a result, it can be assumed that the alcohol dehydrogenation step proceeds on the metal oxide, whereas the oxygen activation step occurs mainly on the carbon support.     

Network growth with preferential attachment for high indegree and low outdegree

We study the growth of a directed transportation network, such as a food web, in which links carry resources. We propose a growth process in which new nodes (or species) preferentially attach to existing nodes with high indegree (in food-web language, number of prey) and low outdegree (or number of predators). This scheme, which we call inverse preferential attachment, is intended to maximize the amount of resources available to each new node. We show that the outdegree (predator) distribution decays at least exponentially fast for large outdegree and is continuously tunable between an exponential distribution and a delta function. The indegree (prey) distribution is poissonian in the large-network limit.     

Time-resolved x-ray microscopy of spin-torque-induced magnetic vortex gyration

Time-resolved x-ray microscopy is used to image the influence of alternating high-density currents on the magnetization dynamics of ferromagnetic vortices. Spin-torque-induced vortex gyration is observed in micrometer-sized permalloy squares. The phases of the gyration in structures with different chirality are compared to an analytical model and micromagnetic simulations, considering both alternating spin-polarized currents and the current's Oersted field. In our case the driving force due to spin-transfer torque is about 70% of the total excitation while the remainder originates from the current's Oersted field. This finding has implications to magnetic storage devices using spin-torque driven magnetization switching and domain-wall motion.     

The significance of anti-neuronal antibodies for acute psychiatric disorders: a retrospective case–controlled study

Background

The clinical significance of anti-neuronal antibodies in patients with psychiatric disorders, but without encephalitis, remains unknown. In patients admitted to acute psychiatric inpatient care we aimed to identify clinical features distinguishing anti-neuronal antibody positive patients from matched controls.

Results

Patients who were serum-positive to N-methyl d-aspartate receptor (NMDAR) (n?=?21), contactin-associated protein 2 (CASPR2) (n?=?14) and/or glutamic acid decarboxylase 65 (GAD65) (n?=?9) antibodies (cases) were age and sex matched (1:2) with serum-negative patients from the same cohort (controls). The prevalence and severity of psychiatric symptoms frequently encountered in NMDAR, CASPR2 and GAD65 antibody associated disorders were compared in cases and controls. NMDAR, CASPR2 and GAD65 antibody positive patients did not differ in their clinical presentation from matched serum negative controls.

Conclusion

In this cohort, patients with and without NMDAR, CASPR2 and GAD65 antibodies admitted to acute psychiatric inpatient care had similar psychiatric phenotypes. This does not exclude their clinical relevance in subgroups of patients, and studies further investigating the clinical significance of anti-neuronal antibodies in patients with psychiatric symptomatology are needed.

     

Testing Fluorescence Lifetime Standards using Two-Photon Excitation and Time-Domain Instrumentation: Fluorescein,Quinine Sulfate and Green Fluorescent Protein

It is essential for everyone working with experimental science to be certain that their instruments produce reliable results, and for fluorescence lifetime experiments, information about fluorescence lifetime standards is crucial. A large part of the literature on lifetime standards dates back to the 1970s and 1980s, and the use of newer and faster measuring devices may deem these results unreliable. We have tested the three commonly used fluorophores fluorescein, quinine sulfate and green fluorescent protein for their suitability to serve as lifetime standards, especially to be used with two-photon excitation measurements in the time-domain. We measured absorption and emission spectra for the fluorophores to determine optimal wavelengths to use for excitation and detector settings. Fluorescence lifetimes were measured for different concentrations, ranging from 10^??3 ??10^??5 M, as well as for various solvents. Fluorescein was soluble in both ethanol, methanol and sulfuric acid, while quinine sulfate was only soluble in sulfuric acid. Green fluorescent protein was prepared in a commercial Tris-HCl, EDTA solution, and all three fluorophores produced stable lifetime results with low uncertainties. No siginificant variation with concentration was measured for any of the fluorophores, and all showed single-exponential decays. All lifetime measurements were carried out using two-photon excitation and lifetime data was obtained in the time-domain using time-correlated single-photon counting.     

Novel low‐loss waveguide delay lines using Vernier ring resonators for on‐chip multi‐λ microwave photonic signal processors

In this paper, novel photonic delay lines (DLs) using Vernier/non‐identical ring resonators (VRRs) are proposed and demonstrated, which are capable of simultaneous generation of multiple different delays at different wavelengths (frequencies). The simple device architectures and full reconfigurability allow the DLs to be integrated with other functional building blocks in photonic integrated circuits to realize on‐chip, complex multi‐λ microwave photonic signal processors with reduced system complexity. To prove the concept, DLs using VRRs in cascaded and coupled configurations have been fabricated in TriPleX^TM waveguide technology, which enables a very low delay‐induced loss of approximately 0.18 dB/100 ps. The fabricated DLs demonstrated simultaneous generation of four incremental delays, where a maximum incremental step of 550 ps and a corresponding top delay of 1650 ps were measured for a bandwidth up to 1 GHz. To our knowledge, this is the first report on VRRs for delay generation functionalities.     

Crystalline Anions Based on Classical N-Heterocyclic Carbenes

Herein, the first stable anions K[SIPr^Bp] ( 4 a-K ) and K[IPr^Bp] ( 4 b-K ) (SIPr^Bp=BpC{N(Dipp)CH₂}₂, IPr^Bp=BpC{N(Dipp)CH}₂; Bp=4-PhC₆H₄; Dipp=2,6-iPr₂C₆H₃) derived from classical N-heterocyclic carbenes (NHCs) (i.e. SIPr and IPr) have been isolated as violet crystalline solids. 4 a-K and 4 b-K are prepared by KC₈ reduction of the neutral radicals [SIPr^Bp] ( 3 a ) and [IPr^Bp] ( 3 b ), respectively. The radicals 3 a and 3 b as well as [Me-IPr^Bp] 3 c (Me-IPr^Bp=BpC{N(Dipp)CMe}₂) are accessible as crystalline solids on treatment of the respective 1,3-imidazoli(ni)um bromides (SIPr^Bp)Br ( 2 a ), (IPr^Bp)Br ( 2 b ), and (Me−IPr^Bp)Br ( 2 c ) with KC₈. The cyclic voltammograms of 2 a–2 c exhibit two one-electron reversible redox processes in −0.5 to −2.5 V region that correspond to the radicals 3 a–3 c and the anions ( 4 a–4 c )⁻. Computational calculations suggest a closed-shell singlet ground state for ( 4 a–4 c )⁻ with the singlet-triplet energy gap of 17–24 kcal mol⁻¹.     

Boron-Centered Lewis Superacid through Redox-Active Ligands: Application in C−F and S−F Bond Activation

A series of redox-responsive ferrocenyl-substituted boranes and boronic esters were synthesized. Oxidation of the ferrocenyl ligand to the ferrocenium resulted in a drastic increase in the Lewis acidity beyond the strength of SbF₅, which was investigated experimentally and computationally. The resulting highly Lewis acidic boron compounds were used for catalytic C−F and S−F bond activation.