Search results for "bonds"
showing 10 items of 155 documents
Recent Advances on the Halo- and Cyano-Trifluoromethylation of Alkenes and Alkynes
2021
Incorporation of fluorine into organic molecules is a well-established strategy in the design of advanced materials, agrochemicals, and pharmaceuticals. Among numerous modern synthetic approaches, functionalization of unsaturated bonds with simultaneous addition of trifluoromethyl group along with other substituents is currently one of the most attractive methods undergoing wide-ranging development. In this review article, we discuss the most significant contributions made in this area during the last decade (2012−2021). The reactions reviewed in this work include chloro-, bromo-, iodo-, fluoro- and cyano-trifluoromethylation of alkenes and alkynes.
Scenario modeling for the management of international bond portfolios
1998
We address the problem of portfolio management in the international bond markets. Interest rate risk in the local market, exchange rate volatility across markets, and decisions for hedging currency risk are integral parts of this problem. The paper develops a stochastic programming optimization model for integrating these decisions in a common framework. Monte Carlo simulation procedures, calibrated using historical observations of volatility and correlation data, generate jointly scenarios of interest and exchange rates. The decision maker's risk tolerance is incorporated through a utility function, and additional views on market outlook can also be incorporated in the form of user specifi…
29Si Hyperfine structure of the E’_alfa center in amorphous silicon dioxide
2006
We report a study by electron paramagnetic resonance on the E0 point defect in amorphous silicon dioxide (a-SiO2). Our experiments were performed on -ray irradiated oxygen-deficient materials and pointed out that the 29Si hyperfine structure of the E0 consists of a pair of lines split by 49 mT. On the basis of the experimental results, a microscopic model is proposed for the E0 center, consisting of a hole trapped in an oxygen vacancy with the unpaired electron sp3 orbital pointing away from the vacancy in a back-projected configuration and interacting with an extra oxygen atom of the a-SiO2 matrix.
Characterization of E'delta and triplet point defects in oxygen-deficient amorphous silicon dioxide
2005
We report an experimental study by electron paramagnetic resonance (EPR) of gamma ray irradiation induced point defects in oxygen deficient amorphous SiO2 materials. We have found that three intrinsic (E'gamma, E'delta and triplet) and one extrinsic ([AlO4]0) paramagnetic centers are induced. All the paramagnetic defects but E'gamma center are found to reach a concentration limit value for doses above 10^3 kGy, suggesting a generation process from precursors. Isochronal thermal treatments of a sample irradiated at 10^3 kGy have shown that for T>500 K the concentrations of E'gamma and E'delta centers increase concomitantly to the decrease of [AlO4]0. This occurrence speaks for an hole tra…
Crystal structures of allyltriphenyl-phosphonium halogenocuprates(I)
2013
Alternating-current electrochemical synthesis is used to obtain for the first time halogenocuprates of an allyl derivative of phosphonium of the composition (CH2=CHCH2(C6H5)3P)CuX2 (X = Br (I), Cl (II)). Compound I crystallizes in the space group P21, a = 9.6341(3) A, b = 12.4167(4) A, c = 9.9618(4) A, β = 117.484(5)°, Z = 2. Compound II crystallizes in the space group P21/n, a = 9.9725(5) A, b = 15.4586(8) A, c = 13.7557(5) A, β = 90.429(4)°, Z = 4. In the structures of I and II quasilinear CuX 2 − anions are held by C-H…X hydrogen bonds inside a framework formed by the stacking of phenyl groups from CH2=CHCH2(C6P5)3P+ cations. Allyl groups are not involved in coordination with copper(I) a…
Intrinsic fluorescence in non-aromatic peptide structures is induced by collective vibrations, charge reorganisation and short hydrogen bonds, as sho…
2020
Abstract Disentangling the origin of the optical activity of non-aromatic proteins is challenging due to their size and thus their high computational requisites. Here we show, in a much smaller model system, that the single amino acid glutamine undergoes a chemical transformation leading to an unreported glutamine-like structure which has a similar broad absorption spectrum reported previously for non-aromatic proteins. We further show computationally that the optical activity of the glutamine-like structure is directly coupled to short-hydrogen bonds, but also displays charge and vibrational fluctuations, the latter of which are also present in less optically active structures such as in L…
Very strong −N–X+⋯−O–N+ halogen bonds
2016
A new (-)N-X(+)(-)O-N(+) paradigm for halogen bonding is established by using an oxygen atom as an unusual halogen bond acceptor. The strategy yielded extremely strong halogen bonded complexes with very high association constants characterized in either CDCl3 or acetone-d6 solution by (1)H NMR titrations and in the solid-state by single crystal X-ray analysis. The obtained halogen bond interactions, RXB, in the solid-state are found to be in the order of strong hydrogen bonds, viz. RXB ≈ RHB.
Self-assembly of 2,8,14,20-tetraisobutyl-5,11,17,23-tetrahydroxyresorc[4]arene
1999
We report herein the observation of a hexameric structure of a hydroxyresorc[4]arene in the solid state, enclosing a large interior space. This artificial molecular container is stabilized only by hydrogen bonds. The tendency to form aggregates in solution is demonstrated mainly by means of ESI-MS methods.
Substituent Effects on the [N-I-N](+) Halogen Bond
2016
We have investigated the influence of electron density on the three-center [N-I-N](+) halogen bond. A series of [bis(pyri din e) io dine](+) and [1,2-bis ( (pyridin e-2-71 ethynyl)b e nze n e)io dine](+) BF4- complexes substituted with electron withdrawing and donating functionalities in the para-position of their pyridine nitrogen were synthesized and studied by spectroscopic and computational methods. The systematic change of electron density of the pyridine nitrogens upon alteration of the para-substituent (NO2, CF3, H, F, Me, OMe, NMe2) was confirmed by N-15 NMR and by computation of the natural atomic population and the pi electron population of the nitrogen atoms. Formation of the [N-…
Creation of glass-characteristic point defects in crystalline SiO2 by 2.5 MeV electrons and by fast neutrons
2019
The support from M -ERANET project “MyND” is acknowledged. K.K. was partially supported by the Collaborative Research Project of Laboratory for Materials and Structures, Tokyo Institute of Technology . Visiting researcher support from Ecole Polytechnique, Palaiseau is appreciated. Mr. Olivier Cavani is thanked for the expert help with irradiations.