Origin and stabilization of axial chirality in the construction of naphthyl-C2-indoles: a DFT study

2020 ◽  
Vol 7 (20) ◽  
pp. 3166-3173
Author(s):  
Qianqian Deng ◽  
Yang Wang ◽  
Shi-Jun Li ◽  
Ling-Bo Qu ◽  
Yu Lan ◽  
...  

A novel method for predicting the stabilization of axial chirality in the construction of naphthyl-C2-indoles has been suggested for the first time.

1994 ◽  
Vol 59 (1) ◽  
pp. 1-74 ◽  
Author(s):  
Pavel Kočovský

This review summarizes the main topics of our research and covers the period of the last 15 years. The prime interest is focused on various ways of controlling the regio- and stereoselectivity of selected organic reactions, in particular electrophilic additions, cleavage of cyclopropane rings, and allylic substitutions by means of neighboring groups and/or transition and non-transition metals. In the first part, the factors governing the course of electrophilic additions are assessed, culminating in the formulation of selection rules for the reactivity of cyclohexene systems, and in a concise synthesis of the natural cardioactive drug, strophanthidin. These studies also contribute to a better understanding of the mechanisms of electrophilic additions. The second part describes recent developments in the stereo- and regiocontrolled cleavage of cyclopropane rings by non-transition metals (Tl and Hg), and the reactivity and transmetalation (with Pd) of the primary products. This methodology has resulted in novel routes to unique polycyclic structures, and will have synthetic applications in the near future. Evidence for the stereospecific "corner" cleavage of the cyclopropane ring has been provided for the first time for Tl and later for Hg. The third part deals with transition metal-catalyzed allylic substitution. Evidence for a new "syn" mechanism for the formation of the intermediate (π-allyl)palladium complex has been provided, which runs counter to the generally accepted "anti" mechanism. A novel method for a Pd-catalyzed allylic oxidation has been developed and employed in the synthesis of natural sesquiterpenes. The increasing importance of transition and non-transition metals for synthetic organic chemistry is demonstrated by their unique reactivity in a number of the papers included in this review.


2019 ◽  
Vol 15 (S356) ◽  
pp. 225-225
Author(s):  
Dalya Baron

AbstractIn this talk I will show that multi-wavelength observations can provide novel constraints on the properties of ionized gas outflows in AGN. I will present evidence that the infrared emission in active galaxies includes a contribution from dust which is mixed with the outflow and is heated by the AGN. We detect this infrared component in thousands of AGN for the first time, and use it to constrain the outflow location. By combining this with optical emission lines, we constrain the mass outflow rates and energetics in a sample of 234 type II AGN, the largest such sample to date. The key ingredient of our new outflow measurements is a novel method to estimate the electron density using the ionization parameter and location of the flow. The inferred electron densities, ∼104.5 cm−3, are two orders of magnitude larger than found in most other cases of ionized outflows. We argue that the discrepancy is due to the fact that the commonly-used [SII]-based method underestimates the true density by a large factor. As a result, the inferred mass outflow rates and kinetic coupling efficiencies are 1–2 orders of magnitude lower than previous estimates, and 3–4 orders of magnitude lower than the typical requirement in hydrodynamic cosmological simulations. These results have significant implications for the relative importance of ionized outflows feedback in this population.


2019 ◽  
Vol 23 ◽  
pp. 201-212
Author(s):  
Shivkumari Panda ◽  
Dibakar Behera ◽  
Tapan Kumar Bastia

This chapter presents the preparation and characterization of some unique properties of nanocomposites by dispersing graphite flakes in commercial unsaturated polyester (UPE) matrix. The composite was prepared by a novel method with the use of solvent swelling technique. Three different specimens of UPE/graphite nanocomposites were fabricated with addition of 1, 2 and 3 wt% of graphite flakes. Except mechanical, viscoelastic and thermo gravimetric properties, transport properties like electrical conductivity, thermal conductivity and water transport properties were studied for the first time. Graphite flakes propose enhanced properties to the composites suggesting homogeneous distribution of the nanofiller in the matrix and strong interaction with the matrix. 2wt% nanofiller loading showed superior essential characteristics and after that the properties reduced may be due to the nucleating tendency of the nanofiller particles. The XRD pattern showed the compatibility of the graphite flakes by introducing a peak around 26.550 in the nanocomposites. SEM Properties are also in agreement with the compatibility. Nanocomposite with 2wt% graphite also showed remarkable enhancement in transport, mechanical, viscoelastic and thermo gravimetric properties. So by introduction of a small quantity of graphite endow the new class of multiphase nanocomposites with inimitable structure and tremendous application.


2021 ◽  
Author(s):  
Robin Smith ◽  
Moshe Gai ◽  
Sarah Stern ◽  
Deran Schweitzer ◽  
Mohammad Ahmed

Abstract Stellar Evolution theory relies on our knowledge of nuclear reactions, with the carbon/oxygen (C/O) ratio, at the end of helium burning, being the single most important input. However, the C/O ratio is still not known with sufficient accuracy, due to large uncertainties in the cross section for the fusion of helium with 12C to form 16O, denoted as the 12C(α,γ)16O reaction. We present initial results at moderately low energies using a novel method, which is significantly different from the experimental efforts of the past four decades. Precise angular distributions of the 12C(α,γ)16O reaction were obtained by measuring the inverse 16O(γ,α)12C reaction with gamma-beams and a Time Projection Chamber detector. These allowed us to measure, for the first time, the interference angle of the l = 1 and 2 partial waves contributing to this reaction (φ12), which agrees with predictions based on the unitarity of the scattering matrix.


2018 ◽  
Vol 20 (24) ◽  
pp. 16770-16776 ◽  
Author(s):  
Siwar Chibani ◽  
Michael Badawi ◽  
Thierry Loiseau ◽  
Christophe Volkringer ◽  
Laurent Cantrel ◽  
...  

The potential use of zeolite and MOF materials for the capture of RuO4 has been investigated for the first time. A hydrated form of HKUST-1 could be a promising sorbent due to its ability to form multiple hydrogen bonds.


2009 ◽  
Vol 92 (3) ◽  
pp. 730-733 ◽  
Author(s):  
Thomas Erk ◽  
Hannah Bergmann ◽  
Elke Richling

Abstract Organic acids play an important role in the flavor and taste of plant-derived foods. Quinic acid (QA) is one of the major acids. In the past, several methods like HPLC/UV, GC, and capillary electrophoresis were used for identification and quantification of QA. For the first time, a novel, sensitive, and selective method for the quantification of QA in food using stable isotope dilution analysis with HPLC/MS/MS has been established. Uniformly labeled 13C-QA was used as a standard to reduce sample preparations and to overcome matrix and ionization effects. The method was used to determine the QA content of red wines, instant coffees, and cloudy apple juices. QA contents of instant coffees were 64.4 and 63.6 g/kg powder. The concentrations in red wines were 24.0 and 25.1 mg/L, and 1493.3 and 1705.2 mg/L in cloudy apple juices.


2015 ◽  
Vol 7 (19) ◽  
pp. 8227-8234 ◽  
Author(s):  
Xiu-Ju Li ◽  
Qi-Feng Fu ◽  
Qi-Hui Zhang ◽  
Xue-Mei Jiang ◽  
Feng-Qing Yang ◽  
...  

A novel method for the preparation of permanent coating columns with a high phase ratio based on the multiple properties of PDA and LBL self-assembly of polydopamine/gold nanoparticles/thiols has been developed for the first time.


Energies ◽  
2018 ◽  
Vol 12 (1) ◽  
pp. 28 ◽  
Author(s):  
Arkaitz Rabanal ◽  
Alain Ulazia ◽  
Gabriel Ibarra-Berastegi ◽  
Jon Sáenz ◽  
Unai Elosegui

A novel multi-criteria methodology for the identification of defective anemometers is shown in this paper with a benchmarking approach: it is called MIDAS: multi-technique identification of defective anemometers. The identification of wrong wind data as provided by malfunctioning devices is very important, because the actual power curve of a wind turbine is conditioned by the quality of its anemometer measurements. Here, we present a novel method applied for the first time to anemometers’ data based on the kernel probability density function and the recent reanalysis ERA5. This estimation improves classical unidimensional methods such as the Kolmogorov–Smirnov test, and the use of the global ERA5’s wind data as the first benchmarking reference establishes a general method that can be used anywhere. Therefore, adopting ERA5 as the reference, this method is applied bi-dimensionally for the zonal and meridional components of wind, thus checking both components at the same time. This technique allows the identification of defective anemometers, as well as clear identification of the group of anemometers that works properly. After that, other verification techniques were used versus the faultless anemometers (Taylor diagrams, running correlation and R M S E , and principal component analysis), and coherent results were obtained for all statistical techniques with respect to the multidimensional method. The developed methodology combines the use of this set of techniques and was able to identify the defective anemometers in a wind farm with 10 anemometers located in Northern Europe in a terrain with forests and woodlands. Nevertheless, this methodology is general-purpose and not site-dependent, and in the future, its performance will be studied in other types of terrain and wind farms.


Synlett ◽  
2020 ◽  
Vol 31 (09) ◽  
pp. 856-860
Author(s):  
Laurent El Kaïm ◽  
Mansour Dolé Kerim ◽  
Pakoupati Boyode ◽  
Julian Garrec

We report for the first time a metal-free addition of boronic acids to silylnitronates to afford oxime derivatives through aryl transfer on the carbon nitrogen double bond. A reaction mechanism has been proposed in relation with a DFT study on the key aryl transfer. This arylation process is effective for cycloalkenyl nitro derivatives leading to oximes that may be oxidatively converted into 3-arylisoxazole derivatives.


2013 ◽  
Vol 31 (15_suppl) ◽  
pp. 4100-4100
Author(s):  
Dominique Werner ◽  
Achim Battmann ◽  
Kristina Steinmetz ◽  
Tobin Jones ◽  
Michele Martinez ◽  
...  

4100 Background: Amplification and/or protein overexpression of HER2 in gastric cancer is a prerequisite to establish an adequate treatment strategy. The European standard defined HER2 positivity by IHC as first evaluation assay followed by ISH in 2+ cases. Gastric tumors are heterogeneous and separate evaluations lead to uncertainties and in localizing distinct clones and are time consuming. The aim of this study was to evaluate the feasibility of gene-protein platform in comparison to single staining methods. Methods: IHC plus SISH and gene-protein platform (IHC/SISH, protein/gene) method for HER2 were performed in randomly collected 100 cases of gastric carcinoma. Results of IHC and SISH were compared with IHC/SISH staining. Rüschoff criteria were applied. Tumors were HER2 positive when expression 3+ or 2+ plus gene amplification (EU-Norm) was found. In Second definition (US-Norm), tumors showing HER2 expression 3+ or amplification were considered HER2 positive. Results: 96 of 100 samples were eligible. Amplification was observed in 14.6% and 15.6% by SISH and IHC/SISH. 71.9% by IHC vs. 75.0% by IHC/SISH had no expression (0) and 10.4% (IHC vs. IHC/SISH) had weak (1+) HER2 expression. Moderate expression (2+) and overexpression (3+) were observed in IHC 6.3%/11.5% and IHC/SISH 6.3%/8.3%, respectively. There were high concordances in IHC assessment of cases with score 0 (94.8%; κ=0.87) and 3+ (96.9%; κ=0.83) and moderate concordances in 1+/2+ cases (89.6%; κ= 0.44 vs. 93.8%; κ=0.47). Rate of HER2 positivity was similar in standard or novel method. In EU Definition 14.6% vs. 10.4% (p=0.52) were positive, respectively, with very good concordance (95.8%; κ=0.81).Concordance between HER2 positivity in standard or novel method was very good (99.0%; κ=0.96) in US definition with no significant differences (17.7% vs. 16.7%; p=1). Conclusions: Gene-protein platform has been tested for first time in gastric carcinoma. Results showed that this novel platform can be a feasible alternative to single methods. Discrepancies in cases with weak or moderate HER2 expression can be a result of observer variability.


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