Measurement of time histories of stable intermediates during first stage ignition of n-heptane and its two isomers in a shock tube

We report the first shock tube measurements of formaldehyde (CH₂O) during the first stage ignition of n-heptane, 2-methylhexane and 3,3-dimethylpentane, in highly diluted fuel/oxygen mixtures in the pressure range of 7–10 atm and temperature range of 700–880 K. Combined time histories of all carbonyl (–C = O) species, CO and fuel were also measured simultaneously in an effort to study the impact of fuel structure on the concentration and the rate of evolution of first stage ignition products. Of the three isomers studied in this work, n-heptane was found to be the fastest, while 3,3-dimethylpentane was found to be the slowest. The differences in the time scale of formation, and plateau concentration of the intermediates between the isomers across the entire range of test conditions suggests a strong dependency of the measured time histories to fuel structure. These species therefore act as markers of the Negative Temperature Coefficient (NTC) behavior of fuels and can be used as targets for developing semi-empirical, hybrid chemistry models of complex, multi-component petroleum derived gasoline and jet fuels. The time histories reported in this work should prove very useful in the refinement of detailed kinetic models of n-heptane, and development of rate rules for branched alkane isomers.     

On the chemical synthesis of titanium nanoparticles from ionic liquids

Abstract  

We report on attempts towards the synthesis of titanium nanoparticles using a wet chemical approach in imidazolium-based ionic liquids (ILs) under reducing conditions. Transmission electron microscopy finds nanoparticles in all cases. UV/Vis spectroscopy confirms the nanoparticulate nature of the precipitate, as in all cases an absorption band between ca. 280 and 300 nm is visible. IR spectroscopy shows that even after extensive washing and drying, some IL remains adsorbed on the nanoparticles. Raman spectroscopy suggests the formation of anatase nanoparticles, but X-ray diffraction reveals that, possibly, amorphous titania forms or that the nanoparticles are so small that a clear structure assignment is not possible. The report thus shows that (possibly amorphous) titanium oxides even form under reducing conditions and that the chemical synthesis of titanium nanoparticles in ILs remains elusive.     

Generation of 520 mW pulsed blue light by frequency doubling of an all-fiberized 978 nm Yb-doped fiber laser source

Pulsed blue light at 489 nm has been generated by second-harmonic-generation of a nanosecond pulsed master-oscillator power amplifier system based on a short Yb(3+) doped single-mode fiber amplifier at 978 nm and an external-cavity diode laser as seed source. The Yb(3+)-doped fiber was core-pumped by a W type Nd(3+) doped double-clad fiber laser operating on the transition near 930 nm ((4)F(3/2)→(4)I(9/2)). 520 mW of average power was generated at 489 nm using a periodically poled MgO:LiNbO(3), corresponding to a conversion efficiency of 34%.     

A sliced inverse regression approach for data stream

In this article, we focus on data arriving sequentially by blocks in a stream. A semiparametric regression model involving a common effective dimension reduction (EDR) direction \(\beta \) is assumed in each block. Our goal is to estimate this direction at each arrival of a new block. A simple direct approach consists of pooling all the observed blocks and estimating the EDR direction by the sliced inverse regression (SIR) method. But in practice, some disadvantages appear such as the storage of the blocks and the running time for large sample sizes. To overcome these drawbacks, we propose an adaptive SIR estimator of \(\beta \) based on the optimization of a quality measure. The corresponding approach is faster both in terms of computational complexity and running time, and provides data storage benefits. The consistency of our estimator is established and its asymptotic distribution is given. An extension to multiple indices model is proposed. A graphical tool is also provided in order to detect changes in the underlying model, i.e., drift in the EDR direction or aberrant blocks in the data stream. A simulation study illustrates the numerical behavior of our estimator. Finally, an application to real data concerning the estimation of physical properties of the Mars surface is presented.     

Frontier estimation with local polynomials and high power-transformed data

We present a new method for estimating the frontier of a sample. The estimator is based on a local polynomial regression on the power-transformed data. We assume that the exponent of the transformation goes to infinity while the bandwidth goes to zero. We give conditions on these two parameters for obtaining almost complete convergence. The asymptotic conditional bias and variance of the estimator are provided and its good performance is illustrated for some finite sample situations.     

Quantitative Proteomic Analysis of Optimal Cutting Temperature (OCT) Embedded Core-Needle Biopsy of Lung Cancer

With recent advances in understanding the genomic underpinnings and oncogenic drivers of pathogenesis in different subtypes, it is increasingly clear that proper pretreatment diagnostics are essential for the choice of appropriate treatment options for non-small cell lung cancer (NSCLC). Tumor tissue preservation in optimal cutting temperature (OCT) compound is commonly used in the surgical suite. However, proteins recovered from OCT-embedded specimens pose a challenge for LC-MS/MS experiments, due to the large amounts of polymers present in OCT. Here we present a simple workflow for whole proteome analysis of OCT-embedded NSCLC tissue samples, which involves a simple trichloroacetic acid precipitation step. Comparisons of protein recovery between frozen versus OCT-embedded tissue showed excellent consistency with more than 9200 proteins identified. Using an isobaric labeling strategy, we quantified more than 5400 proteins in tumor versus normal OCT-embedded core needle biopsy samples. Gene ontology analysis indicated that a number of proliferative as well as squamous cell carcinoma (SqCC) marker proteins were overexpressed in the tumor, consistent with the patient’s pathology based diagnosis of “poorly differentiated SqCC”. Among the most downregulated proteins in the tumor sample, we noted a number of proteins with potential immunomodulatory functions. Finally, interrogation of the aberrantly expressed proteins using a candidate approach and cross-referencing with publicly available databases led to the identification of potential druggable targets in DNA replication and DNA damage repair pathways. We conclude that our approach allows LC-MS/MS proteomic analyses on OCT-embedded lung cancer specimens, opening the way to bring powerful proteomics into the clinic.

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Graphical Abstract ?

     

Unsteadiness of Flow Separation and End-Effects Regime in a Thrust-Optimized Contour Rocket Nozzle

Turbulent flow separation in over-expanded rocket nozzles is investigated experimentally in a sub-scale model nozzle fed with cold air and having a thrust-optimized contour. Depending upon the pressure ratio either a free shock separation (FSS) or a restricted shock separation (RSS) is observed with a significant hysteresis between these two flow regimes. It is shown that the RSS configuration may involve several separated regions. Analysis of wall pressure fluctuations give quantitative information on the fluctuating pressure field directly connected with the occurrence of significant side loads. Direct measurements of the evolution of the side loads with respect to the pressure ratio show the occurrence of three distinct peaks which are explained by the wall pressure fluctuations measurements.     

Sensitivity improvement of 1H-15N cross-polarization at high MAS frequency applied to NMR structural characterization of organic solids

(15)N CP/MAS solid state NMR should be a method of choice to obtain essential structural information on organic materials containing nitrogen atoms. However, the technique is generally not selected for the characterization of non-labelled chemical compounds, which represents the most common situation encountered by chemists. Actually, due to the poor sensitivity of (15)N the method is time-consuming and a very fine calibration is often a prerequisite to reach a sufficient signal/noise. The main drawback comes from the weakness of (15)N-(1)H dipolar couplings which leads to a splitting of the static Hartman Hahn condition into very narrow sideband conditions under MAS. Practically, it is more difficult to obtain a high enough CP transfer level on (15)N for the entire spectrum than on other more conventional nuclei like (13)C. An experimental investigation of the CP efficiency using the ramp and adiabatic CP transfer experiments is here proposed. Preliminary adjustments of experimental settings were first made on an (15)N-labeled substituted heterocyclic model system, and then applied to several other organic compounds. Particular attention was paid to the detection of non-protonated nitrogen atoms with a significant chemical shift anisotropy, which represented the least favourable case. It was experimentally demonstrated that, for these atoms, the adiabatic passage provided a much higher transfer level than the more conventional ramp sequence leading to an enhancement factor of up to 3.5 at a MAS frequency of 30 kHz. The resulting sensitivity rendered possible the detection of non-protonated nitrogen atoms at natural abundance with 2.5-mm rotors at 9.4 T.     

On-chip multi-electrochemical sensor array platform for simultaneous screening of nitric oxide and peroxynitrite

In this work we report on the design, microfabrication and analytical performances of a new electrochemical sensor array (ESA) which allows for the first time the simultaneous amperometric detection of nitric oxide (NO) and peroxynitrite (ONOO(-)), two biologically relevant molecules. The on-chip device includes individually addressable sets of gold ultramicroelectrodes (UMEs) of 50 μm diameter, Ag/AgCl reference electrode and gold counter electrode. The electrodes are separated into two groups; each has one reference electrode, one counter electrode and 110 UMEs specifically tailored to detect a specific analyte. The ESA is incorporated on a custom interface with a cell culture well and spring contact pins that can be easily interconnected to an external multichannel potentiostat. Each UME of the network dedicated to the detection of NO is electrochemically modified by electrodepositing thin layers of poly(eugenol) and poly(phenol). The detection of NO is performed amperometrically at 0.8 V vs. Ag/AgCl in phosphate buffer solution (PBS, pH = 7.4) and other buffers adapted to biological cell culture, using a NO-donor. The network of UMEs dedicated to the detection of ONOO(-) is used without further chemical modification of the surface and the uncoated gold electrodes operate at -0.1 V vs. Ag/AgCl to detect the reduction of ONOOH in PBS. The selectivity issue of both sensors against major biologically relevant interfering analytes is examined. Simultaneous detection of NO and ONOO(-) in PBS is also achieved.     

<Superscript>1</Superscript>H NMR signal at 2.10 ppm in the spectrum of KMnO<Subscript>4</Subscript>-bleached heparin sodium: identification of the chemical origin using an NMR-only approach

The recently revised European Pharmacopeia and US Pharmacopeia heparin sodium monographs include nuclear magnetic resonance (NMR) tests on both identity and purity. In KMnO₄-bleached heparin, an unidentified NMR signal is present at 2.10 ppm at a level of 15–20% of the mean of signal height of the major glucosamine (GlcNAc/GlcNS,6S) anomeric proton signal at 5.42 ppm and of the major iduronic acid (IdoA2S) anomeric proton signal at 5.21 ppm. According to the new monographs, no unidentified signals greater than 4% should be detected at that position. Thus, the material did not meet the acceptance criterion. The signal at 2.10 ppm has been present at the same level in all released MSD KMnO₄-bleached heparin sodium batches analyzed over the past 10 years. The signal is a result of the KMnO₄ bleaching. No (oversulfated) chondroitin sulfate or dermatan sulfate was detected in this material. A comprehensive NMR study using long-range heteronuclear 2D techniques identifies this signal at 2.10 ppm as originating from the acetyl methyl group of (6-sulfated) 2-N-acetyl-2-deoxy-glucono-1,5-lactone. This modified monosaccharide is formed by the KMnO₄ oxidation of the reducing end of a terminal N-acetylglucosamine.