Search results for "SHIFT"

Prediction of the carbon-13 NMR chemical shifts of polysubstituted benzenes with homogeneous substituents

1991

A new incremental scheme for the calculation of the 13C NMR chemical shifts in polysubstituted benzenes with homogeneous substituents was derived and applied to spectral prediction for C6XnH6−n where XCH3, C2H5, i-C3H7, CF3, F, Cl, Br, COOH. Owing to the use of only two-particle increments the procedure is simple enough to be carried out on hand calculators, and gives complete agreement with experimental values within a few tenths of a ppm in all cases compared (76 compounds). The 13C NMR chemical shift was predicted for hexaethylbenzene with a good fit to the experiment value, and also for 20 unmeasured compounds. The present scheme can be used as an algorithm in structure-searching progra…

New Carbaalanes − (AlMe)8(CCH2Me)5(C≡C−Me) and the THF Adduct (AlMe)8(CCH2Me)5H·2THF

2001

The hydroalumination of Me2Al−C≡C−Me with a large excess of Me2AlH afforded the arachno-carbaalane (AlMe)8(CCH2Me)5H (4) by the release of AlMe3. 4 is almost insoluble in noncoordinating solvents and could not be purified by recrystallization. On an attempt to recrystallize 4 from a THF solution, the adduct (AlMe)8(CCH2Me)5H·2THF (5) was isolated as the first stable ether adduct of a carbaalane. Crystal structure determination revealed a cube of eight aluminium atoms, five faces of which are bridged by C−CH2Me groups. The sixth face is µ2-bridged by a hydrogen atom, and two opposite aluminium atoms of this face are coordinated by one THF ligand each. When the excess of dimethylaluminium hyd…

NMR crystallography of 2-Acylamino-6-[1H]pyridones: solid state NMR, GIPAW computational, and single crystal X-ray diffraction studies

2011

Abstract 2-Acylamino-6-[1H]-pyridones [acyl = RCO, where R = methyl (1), ethyl (2), iso-propyl (3), tert-butyl (4), and 1-adamantyl (5)] have been synthesized and characterized by NMR spectroscopy. From three congeners, 2, 3 and 5, also single crystal X-ray structures have been solved. For these derivatives GIPAW calculations acts as a “bridge” between solid-state NMR data and calculated chemical shifts based on X-ray determined geometry. In crystals all three compounds exist as pyridone tautomers possessing similar six-membered ring structure stabilized by intramolecular C O⋯HN hydrogen bond. Theoretical GIPAW calculated and experimental 13C and 15N CPMAS NMR shifts are in excellent agreem…

15N NMR: Substituent effect analysis inpara-andmeta-substituted phenylhydrazines

1994

15N NMR spectra of phenylhydrazine and of 14 para- and meta-substituted phenylhydrazines were measured at natural isotope abundance in DMSO-d6 solution. The substituent present exerts a larger influence on the chemical shift of the nitrogen atom directly bound to the aromatic ring (N-1) than on the second one (N-2), which shows an attenuated and inverted trend. The chemical shifts of N-1 and N-2 give a good cross correlation in both series of compounds if p-NO2 and m-F derivatives are excluded from the correlations of para- and meta-substituted phenylhydrazines, respectively. Moreover, N-1 SCS values show good linear correlations with Hammett substituent constants, with SCSs of directly bou…

Differential disease resistance response in the barley necrotic mutant nec1

2010

Abstract Background Although ion fluxes are considered to be an integral part of signal transduction during responses to pathogens, only a few ion channels are known to participate in the plant response to infection. CNGC4 is a disease resistance-related cyclic nucleotide-gated ion channel. Arabidopsis thaliana CNGC4 mutants hlm1 and dnd2 display an impaired hypersensitive response (HR), retarded growth, a constitutively active salicylic acid (SA)-mediated pathogenesis-related response and elevated resistance against bacterial pathogens. Barley CNGC4 shares 67% aa identity with AtCNGC4. The barley mutant nec1 comprising of a frame-shift mutation of CNGC4 displays a necrotic phenotype and co…

Salvador Beltran, F., Herrando, S., Estreder, V., Ferreres, D., Adell, M. A., i Ruiz-Soler, M. (2011). A language shift simulation based on cellular …

2016

Toward a holistic understanding of pastoralism

2021

Pastoralism is globally significant in social, environmental, and economic terms. However, it experiences crises rooted in misconceptions and poor interdisciplinary understanding, while being largely overlooked in international sustainability forums and agendas. Here, we propose a transdisciplinary research approach to understand pastoralist transitions using (1) social, economic, and environmental dimensions, (2) diverse geographic contexts and scales to capture emerging properties, allowing for cross-system comparisons, and (3) timescales from the distant past to the present. We provide specific guidelines to develop indicators for this approach, within a social-ecological resilience anal…

In situ formation of pyronin dyes for fluorescence protease sensing

2017

International audience; We report a reaction-based strategy for the fluorogenic detection of protease activity. Based on the "covalent-assembly" probe design principle recently put forward by the Yang group for detection of Sarin related threats (J. Am. Chem. Soc., 2014, 136, 6594-6597), we have designed two unusual nonfluorescent caged precursors (mixed bis-aryl ethers) which are readily converted into a fluorescent unsymmetrical pyronin dye through a domino cyclisation-aromatisation reaction triggered by penicillin G acylase (PGA) or leucine aminopeptidase (LAP). Fluorescence-based in vitro assays and HPLCfluorescence/- MS analyses support the claimed activation mechanism whose the furthe…

Multi-subject fMRI analysis via combined independent component analysis and shift-invariant canonical polyadic decomposition

2014

Canonical polyadic decomposition (CPD) may face a local optimal problem when analyzing multi-subject fMRI data with inter-subject variability. Beckmann and Smith proposed a tensor PICA approach that incorporated an independence constraint to the spatial modality by combining CPD with ICA, and alleviated the problem of inter-subject spatial map (SM) variability.This study extends tensor PICA to incorporate additional inter-subject time course (TC) variability and to connect CPD and ICA in a new way. Assuming multiple subjects share common TCs but with different time delays, we accommodate subject-dependent TC delays into the CP model based on the idea of shift-invariant CP (SCP). We use ICA …

The evolution of transmission mode

2017

This article reviews research on the evolutionary mechanisms leading to different transmission modes. Such modes are often under genetic control of the host or the pathogen, and often in conflict with each other via trade-offs. Transmission modes may vary among pathogen strains and among host populations. Evolutionary changes in transmission mode have been inferred through experimental and phylogenetic studies, including changes in transmission associated with host shifts and with evolution of the unusually complex life cycles of many parasites. Understanding the forces that determine the evolution of particular transmission modes presents a fascinating medley of problems for which there is…