Resolving Sphingolipid Isomers Using Cryogenic Infrared Spectroscopy

1‐Deoxysphingolipids are a recently described class of sphingolipids that have been shown to be associated with several disease states including diabetic and hereditary neuropathy. The identification and characterization of 1‐deoxysphingolipids and their metabolites is therefore highly important. However, exact structure determination requires a combination of sophisticated analytical techniques due to the presence of various isomers, such as ketone/alkenol isomers, carbon–carbon double‐bond (C=C) isomers and hydroxylation regioisomers. Here we demonstrate that cryogenic gas‐phase infrared (IR) spectroscopy of ionized 1‐deoxysphingolipids enables the identification and differentiation of isomers by their unique spectroscopic fingerprints. In particular, C=C bond positions and stereochemical configurations can be distinguished by specific interactions between the charged amine and the double bond. The results demonstrate the power of gas‐phase IR spectroscopy to overcome the challenge of isomer resolution in conventional mass spectrometry and pave the way for deeper analysis of the lipidome.     

Summary of the IZEST science and aspiration

Over 30 associated laboratories across 13 countries are part of the international program known as IZEST (International center for Zetta-Exawatt Science and Technology), which has been initiated and coordinated by the École Polytechique and the CEA. Together, this collaboration of laboratories are exploring new ways to push laser peak power and intensities beyond the present horizon with the aim to perform Laser-Based High Energy Physics.     

Biotransformation-mediated synthesis of (1S)-1-(2,6-dichloro-3-fluorophenyl)ethanol in enantiomerically pure form

An efficient four-step biotransformation-mediated synthesis of (1S)-1-(2,6-dichloro-3-fluorophenyl)ethanol in enantiomerically pure form is described. This compound is a key intermediate required for the preparation of PF-2341066, a potent inhibitor of c-Met/ALK that is currently in clinical development. The described synthesis was used to manufacture 6 kg of the title compound and can also be employed to produce the corresponding (1R)-enantiomer.     

Thermal performance of a carbon fiber composite material heat sink in an FC-72 thermosyphon

This study analyzes the use of a carbon fiber epoxy heat sink for evaporator surface enhancement in a FC-72 thermosyphon. The pin-fin heat sink features 945 small-cross-section (1.27 mm by 0.965 mm) fins fabricated with an integral base plate. These fins have a high thermal conductivity (500 W/m K) along the length of the fin. The influence of heat load, thermosyphon fill volume, and condenser operating temperature on the overall thermal performance is examined. The results of this experiment provide significant insight into the possible implementation and potential benefits of carbon-fiber heat sink technology in two-phase flow leading to significant improvements in thermal management strategies for advanced electronics.     

Investigation of Terra Cotta artefacts with terahertz

Terahertz Time Domain Imaging has been used in the last few years for the investigation of cultural heritage. In this article, the authors demonstrate the possibility to apply it for the investigation of clay artifacts. Tomographic images were obtained of a model in reflection, and an Egyptian vessel in transmission.     

On the Development of Titanium κ1-Amidinate Complexes,Commercialized as Keltan ACE™ Technology,Enabling the Production of an Unprecedented Large Variety of EPDM Polymer Structures

ARLANXEO Elastomers has developed and commercialized Keltan ACE™ technology, a class of half-sandwich cyclopentadienyl κ¹-amidinate metal complexes, which are extremely active for the production of first-class ethylene/propylene/diene copolymers (EPDM). In this review, the development and some of the key features of the Keltan ACE™ catalyst system are presented. Many different ACE catalysts have been synthesized over the past years, including bridged and bimetallic catalysts. With Keltan ACE™, a complete range of EPDM products with similar polymer characteristics as their Ziegler–Natta (ZN) counterparts can be produced, including variations containing very high 5-ethylidene-2-norbornene (ENB) contents, controlled long chain branching, very high molecular weight, as well as oil-extended products. Moreover, other EPDM structures can be polymerized. The Keltan ACE™ catalyst technology also allows the production of EPDMs with very high amounts of dicyclopentadiene (DCPD) or 5-vinyl 2-norbornene (VNB) without excessive gelation and reactor fouling, that is, products that cannot or are extremely difficult to obtain via classical ZN catalysis. In a next step, high-VNB-EPDM can be postreactor modified, for example, via metathesis chemistry. In addition, EPDM polymers with a very broad or even bimodal molecular weight distribution can be obtained in a single reactor with certain ACE catalyst structures at particular activator/precatalyst ratios. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2877–2891     

On the stability of a family of finite element methods for hyperbolic problems

We consider a family of tensor product finite element methods for hyperbolic equations in , , which are explicit and generate a continuous approximate solution. The base case (an extension of the box scheme to higher order) is due to Winther, who proved stability and optimal order convergence. By means of a simple counterexample, we show that, for linear approximation with , the corresponding methods are unstable.

     

The Flooding Time in Random Graphs

Based on our analysis of the hopcount of the shortest path between two arbitrary nodes in the class G _p (N) of random graphs, the corresponding flooding time is investigated. The flooding time T _N (p) is the minimum time needed to reach all other nodes from one node. We show that, after scaling, the flooding time T _N (p) converges in distribution to the two-fold convolution ^(2*) of the Gumbel distribution function (z)=exp (–e ^–z ), when the link density p _N satisfies Np _N /(log N)³ if N .     

Analysis of the pi-pi stacking interactions between the aminoglycoside antibiotic kinase APH(3')-IIIa and its nucleotide ligands

A key contact in the active site of an aminoglycoside phosphotransferase enzyme (APH(3')-IIIa) is a pi-pi stacking interaction between Tyr42 and the adenine ring of bound nucleotides. We investigated the prevalence of similar Tyr-adenine contacts and found that many different protein systems employ Tyr residues in the recognition of the adenine ring. The geometry of these stacking interactions suggests that electrostatics play a role in the attraction between these aromatic systems. Kinetic and calorimetric experiments on wild-type and mutant forms of APH(3')-IIIa yielded further experimental evidence of the importance of electrostatics in the adenine binding region and suggested that the stacking interaction contributes approximately 2 kcal/mol of binding energy. This type of information concerning the forces that govern nucleotide binding in APH(3')-IIIa will facilitate inhibitor design strategies that target the nucleotide binding site of APH-type enzymes.     

Synthesis and reactivity of a ferrocene-derived PCP-pincer ligand

The 1,3-bis(diphosphinomethyl)ferrocene 3 readily reacts with [(C2H4)2RhCl]2 to form an equilibrating pair of diastereomers 8a and 8b by C-H insertion into the ferrocene.