Detailed Structural Characterization of Sphingolipids via 193 nm Ultraviolet Photodissociation and Ultra High Resolution Tandem Mass Spectrometry

Sphingolipids serve not only as components of cellular membranes but also as bioactive mediators of numerous cellular functions. As the biological activities of these lipids are dependent on their structures, and due to the limitations of conventional ion activation methods employed during tandem mass spectrometry (MS/MS), there is a recognized need for the development of improved structure-specific methods for their comprehensive identification and characterization. Here, positive-ionization mode 193 nm ultraviolet photodissociation (UVPD)-MS/MS has been implemented for the detailed structural characterization of lipid species from a range of sphingolipid classes introduced to the mass spectrometer via electrospray ionization as their lithiated or protonated adducts. These include sphingosine d18:1(4E), dihydrosphingosine (sphinganine) d18:0, sphingadiene d18:2(4E,11Z), the isomeric sphingolipids ceramide d18:1(4E)/18:0 and dihydroceramide d18:0/18:1(9Z), ceramide-1-phosphate d18:1(4Z)/16:0, sphingomyelin d18:1(4E)/18:1(9Z) the glycosphingolipids galactosyl ceramide d18:1(4E)/24:1(15Z) and lactosyl ceramide d18:1(4E)/24:0, and several endogenous lipids present within a porcine brain total lipid extract. In addition to the product ions formed by higher energy collision dissociation (HCD), UVPD is shown to yield a series of novel structurally diagnostic product ions resulting from cleavage of both sphingosine carbon–carbon and acyl chain carbon–carbon double bonds for direct localization of site(s) of unsaturation, as well as via diagnostic cleavages of the sphingosine backbone and N–C amide bond linkages. With activation timescales and dissociation efficiencies similar to those found in conventional MS/MS strategies, this approach is therefore a promising new tool in the arsenal of ion activation techniques toward providing complete structural elucidation in automated, high-throughput lipid analysis workflows.

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Stability enhancement of nanofibrillated cellulose in electrolytes through grafting of 2-acrylamido-2-methylpropane sulfonic acid

This study aimed to improve the stability of nanofibrillated cellulose (NFC) in an electrolyte containing system, which was achieved by the grafting of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) via the ceric ammonium nitrate-induced polymerization process. The results indicated that upon grafting the salt resistance and thermal stability of NFC were significantly improved. Moreover, the stability of the modified NFC increased with the AMPS loading. Compared to the control (the original NFC), the poly-AMPS/NFC (357.5 mg/g AMPS) exhibited much improved stability in a 400 mmol/L NaCl solution, and its viscosity was 350 mPa s. The thermogravimetric analysis results showed that the initial decomposition temperature of the modified NFC increased from 265 to 330 °C. Transmission electron microscopy (TEM) observations showed that the main morphologic features of NFC were not altered, suggesting that the grafting reaction occurred on the fiber surface. The modified NFC can have promising industrial applications, such as oil recovery.     

Synthesis of TiO<Subscript>2</Subscript> nanotubes using different alkaline media and their applications in photocatalysis and DSSCs

TiO₂ nanotubes (TNTs) were successfully synthesized from different alkaline media (i.e., NaOH and KOH) by using a microwave hydrothermal process. The effects of different alkaline media on the formation of TiO₂ nanotubes and their physicochemical properties were investigated. The phases of different TiO₂ nanostructures were studied by using X-ray diffraction patterns. Morphologies of the nanostructures were observed with a transmission electron microscope. The optical properties of the nanostructures were evaluated through the absorption behavior using UV–Vis diffuse reflectance spectroscopy. The photocatalytic activities of the TiO₂ nanostructures were evaluated by the degradation of methylene blue aqueous dye solution under the simulated solar light irradiation. Similarly, the photovoltaic efficiencies of the prepared samples were investigated by making photo-anode layers in the Dye Sensitized Solar Cells (DSSCs). The results revealed that in comparison to the single layered TiO₂ nanostructures in the DSSC, creation of a double layer structure significantly enhanced the efficiency of DSSC.     

Fingerprint and multicomponent quantitative analysis for the quality evaluation of Sibiraea angustata leaves by HPLC-DAD and HPLC-ESI-MS/MS combined with chemometrics

Sibiraea angustata leaves, known as a traditional Tibetan medicine, have been specially used in the treatment of indigestion and obesity. In the study, a simple and sensitive high-performance liquid chromatography (HPLC) method with a diode array detector (DAD) was established to solve the problem of lacking quality standard of S. angustata leaves, including the fingerprint analysis and quantification of six characteristic components. The analytical method was validated for linearity, repeatability, stability, recovery, and specificity. Seventeen raw samples and 1 processed sample of S. angustata leaves were collected from different locations of China to establish the fingerprint. The chemometric methods, including similarity analysis (SA), principal component analysis (PCA), and hierarchical clustering analysis (HCA), were applied to distinguish the 18 batches of S. angustata samples. The results successfully sorted these samples into five clusters and kept in line with each other. According to the result of the fingerprint analysis, 21 peaks were extracted to be the common peaks and most of them were identified by mass spectrometry (MS) with electron-spray ionization (ESI) in the negative mode. Meanwhile, the loading plot of PCA further indicated that the peaks of neochlorogenic acid, chlorogenic acid, ferulic acid, rutin, hyperin, and isoquercitrin played a greater role in the discrimination among the 21 peaks. So the six components mentioned above were investigated as index constituents to evaluate the quality of S. angustata leaves from different locations. The study demonstrated that the developed new method was a beneficial approach for authentication and quality evaluation of S. angustata leaves.     

Fixed point approach for weakly asymptotic stability of fractional differential inclusions involving impulsive effects

We prove the global solvability and weakly asymptotic stability for a semilinear fractional differential inclusion subject to impulsive effects by analyzing behavior of its solutions on the half-line. Our analysis is based on a fixed point principle for condensing multi-valued maps, which is employed for solution operator acting on the space of piecewise continuous functions. The obtained results will be applied to a lattice fractional differential system.     

Value sharing problems for differential and difference polynomials of meromorphic functions in a non-Archimedean field

In this paper we discuss the uniqueness problem for differential and difference polynomials of the form (f ^nm (z)f ^nd (qz + c))^(k) for meromorphic functions in a non-Archimedean field.     

Estimating the height of a tsunami wave propagating over a parabolic bottom in the ray approximation

In this paper, the kinematics of tsunami wave rays and wavefronts propagating over an uneven bottom is considered. Formulas to determine the wave height along a ray tube are obtained. An exact analytical solution for the trajectory of a wave ray over a parabolic bottom is derived. In the wave-ray approximation, this solution makes it possible to analytically determine the heights of tsunami waves over an area with a sloping bottom. The distribution of wave-height maxima over an area with a parabolic bottom is compared with that obtained by numerical computation with a shallow-water model.     

Variational Bayes With Intractable Likelihood

Variational Bayes (VB) is rapidly becoming a popular tool for Bayesian inference in statistical modeling. However, the existing VB algorithms are restricted to cases where the likelihood is tractable, which precludes their use in many interesting situations such as in state--space models and in approximate Bayesian computation (ABC), where application of VB methods was previously impossible. This article extends the scope of application of VB to cases where the likelihood is intractable, but can be estimated unbiasedly. The proposed VB method therefore makes it possible to carry out Bayesian inference in many statistical applications, including state--space models and ABC. The method is generic in the sense that it can be applied to almost all statistical models without requiring too much model-based derivation, which is a drawback of many existing VB algorithms. We also show how the proposed method can be used to obtain highly accurate VB approximations of marginal posterior distributions. Supplementary material for this article is available online.     

Phase-Selective Syntheses of Cobalt Telluride Nanofleeces for Efficient Oxygen Evolution Catalysts

Cobalt-based nanomaterials have been intensively explored as promising noble-metal-free oxygen evolution reaction (OER) electrocatalysts. Herein, we report phase-selective syntheses of novel hierarchical CoTe₂ and CoTe nanofleeces for efficient OER catalysts. The CoTe₂ nanofleeces exhibited excellent electrocatalytic activity and stablity for OER in alkaline media. The CoTe₂ catalyst exhibited superior OER activity compared to the CoTe catalyst, which is comparable to the state-of-the-art RuO₂ catalyst. Density functional theory calculations showed that the binding strength and lateral interaction of the reaction intermediates on CoTe₂ and CoTe are essential for determining the overpotential required under different conditions. This study provides valuable insights for the rational design of noble-metal-free OER catalysts with high performance and low cost by use of Co-based chalcogenides.     

Application of holomorphic invariants in reproducing kernel

We use holomorphic invariants to calculate the Bergman kernel for generalized quasi-homogeneous Reinhardt-Hartogs domains. In addition, we present a complete orthonormal basis for the Bergman space on bounded Reinhardt-Hartogs domains.