Relationships between structure,ionization profile and sensitivity of exogenous anabolic steroids under electrospray ionization and analysis in human urine using liquid chromatography–tandem mass spectrometry

The relationships between the ionization profile, sensitivity, and structures of 64 exogenous anabolic steroids (groups I–IV) was investigated under electrospray ionization (ESI) conditions. The target analytes were ionized as [M + H]⁺ or [M + H–nH₂O]⁺ in the positive mode, and these ions were used as precursor ions for selected reaction monitoring analysis. The collision energy and Q3 ions were optimized based on the sensitivity and selectivity. The limits of detection (LODs) were 0.05–20 ng/mL for the 64 steroids. The LODs for 38 compounds, 14 compounds and 12 compounds were in the range of 0.05–1, 2–5 and 10–20 ng/mL, respectively. Steroids including the conjugated keto‐functional group at C3 showed good proton affinity and stability, and generated the [M + H]⁺ ion as the most abundant precursor ion. In addition, the LODs of steroids using the [M + H]⁺ ion as the precursor ion were mostly distributed at low concentrations. In contrast, steroids containing conjugated/unconjugated hydroxyl functional groups at C3 generated [M + H ? H₂O]⁺ or [M + H ? 2H₂O]⁺ ions, and these steroids showed relatively high LODs owing to poor stability and multiple ion formation. An LC‐MS/MS method based on the present ionization profile was developed and validated for the determination of 78 steroids (groups I–V) in human urine. Copyright © 2015 John Wiley & Sons, Ltd.     

Parameters of Plasma and Way of Etching Silicon in a CF4 + CHF3 + O2 Mixture

Russian Microelectronics - The effect of the CF4/CHF3 ratio in a CF4 + CHF3 + 9% O2 mixture on the parameters of the gaseous phase and kinetics of etching of silicon under the conditions of...     

Studies on the Synthesis of Indothiazinone and Its Derivatives via Direct 3-Acylation of Indole

Indothiazinone is a natural 3-acylindole alkaloid, isolated from a culture of myxobacterial strain. It was found to possess antibacterial activity against yeast and filamentous fungi. Indothiazinone is also structurally related with a mammalian endogenous aryl hydrocarbon receptor ligand, (2-(1′H-indole-3′-carbonyl)thiazol-4-carboxylic acid methyl ester (ITE). In this article, the synthesis of indothiazinone has been disclosed for the first time. Key feature includes direct and selective 3-acylation of indole in the presence of Lewis acid. In addition, an efficient preparation of N-substituted indothiazinone derivatives has been demonstrated.     

EDA-78: A Novel Error Detection Algorithm for Lempel-Ziv-78 Compressed Data

Wireless Personal Communications - This paper presents an error detection algorithm for Lempel-Ziv-78 (LZ78) compressed data. LZ78 data compression involves dictionary coding and aims to compress...     

MAO‐free and extremely active catalytic system for ethylene tetramerization

The original Sasol catalytic system for ethylene tetramerization is composed of a Cr source, a PNP ligand, and MAO (methylaluminoxane). The use of expensive MAO in excess has been a critical concern in commercial operation. Many efforts have been made to replace MAO with non‐coordinating anions (e.g., [B(C₆F₅)₄]^?); however, most of such attempts were unsuccessful. Herein, an extremely active catalytic system that avoids the use of MAO is presented. The successive addition of two equivalent [H(OEt₂)₂]⁺[B(C₆F₅)₄]^? and one equivalent CrCl₃(THF)₃ to (acac)AlEt₂ and subsequent treatment with a PNP ligand [CH₃(CH₂)₁₆]₂C(H)N(PPh₂)₂ ( 1 ) yielded a complex presumably formulated as [ 1 ‐CrAl (acac)Cl₃(THF)]²⁺[B(C₆F₅)₄]^?₂, which exhibited high activity when combined with iBu₃Al (1120 kg/g‐Cr/h; ~4 times that of the original Sasol system composed of Cr (acac)₃, iPrN(PPh₂)₂, and MAO). Via the introduction of bulky trialkylsilyl substituents such as –SiMe₃, –Si(nBu)₃, or –SiMe₂(CH₂)₇CH₃ at the para‐position of phenyl groups in 1 (i.e., by using [CH₃(CH₂)₁₆]₂C(H)N[P(C₆H₄‐p‐SiR₃)₂]₂ instead of 1 ), the activities were dramatically improved, i.e., tripled (2960–3340 kg/g‐Cr/h; more than 10 times that of the original Sasol system). The generation of significantly less PE (<0.2 wt%) even at a high temperature is another advantage achieved by the introduction of bulky trialkylsilyl substituents. NMR studies and DFT calculations suggest that increase of the steric bulkiness on the alkyl‐N and P‐aryl moieties restrict the free rotation around (alkyl)N–P (aryl) bonds, which may cause the generation of more robust active species in higher proportion, leading to extremely high activity along with the generation of a smaller amount of PE.     

Sub‐5 nm Dendrimer Directed Self‐Assembly with Large‐Area Uniform Alignment by Graphoepitaxy

Directed self‐assembly (DSA) using soft materials is an important method for producing periodic nanostructures because it is a simple, cost‐effective process for fabricating high‐resolution patterns. Most of the previously reported DSA methods exploit the self‐assembly of block copolymers, which generates a wide range of nanostructures. In this study, cylinders obtained from supramolecular dendrimer films with a high resolution (<5 nm) exhibit planar ordering over a macroscopic area via guiding topographical templates with a high aspect ratio (>10) and high spatial resolution (≈20 nm) of guiding line patterns. Theoretical and experimental studies reveal that this property is related to geometrical anchoring on the meniscus region and physical surface anchoring on the sidewall. Furthermore, this DSA of dendrimer cylinders is demonstrated by the non‐regular geometry of the patterned template. The macroscopic planar alignment of the dendrimer nanostructure reveals an extremely small feature size (≈4.7 nm) on the wafer scale (>16 cm²). This study is expected to open avenues for the production of a large family of supramolecular dendrimers with different phases and feature dimensions oriented by the DSA approach.     

The role of TDP-43 propagation in neurodegenerative diseases: integrating insights from clinical and experimental studies

TAR DNA-binding protein 43 (TDP-43) is a highly conserved nuclear RNA/DNA-binding protein involved in the regulation of RNA processing. The accumulation of TDP-43 aggregates in the central nervous system is a common feature of many neurodegenerative diseases, such as amyotrophic lateral sclerosis (ALS), frontotemporal dementia (FTD), Alzheimer’s disease (AD), and limbic predominant age-related TDP-43 encephalopathy (LATE). Accumulating evidence suggests that prion-like spreading of aberrant protein aggregates composed of tau, amyloid-β, and α-synuclein is involved in the progression of neurodegenerative diseases such as AD and PD. Similar to those of prion-like proteins, pathological aggregates of TDP-43 can be transferred from cell-to-cell in a seed-dependent and self-templating manner. Here, we review clinical and experimental studies supporting the prion-like spreading of misfolded TDP-43 and discuss the molecular mechanisms underlying the propagation of these pathological aggregated proteins. The idea that misfolded TDP-43 spreads in a prion-like manner between cells may guide novel therapeutic strategies for TDP-43-associated neurodegenerative diseases.Subject terms: Neurodegenerative diseases, Neurodegeneration