Molecular polarisability. Aromatic isothiocyanates

Cheng, C. L.; Fèvre, R. J. W. Le; Ritchie, G. L. D.

doi:10.1039/j29710000435

Cited by 12 publications

(13 citation statements)

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“…Hydrogen peroxide (30% v/v) was used as the main component of the etching solution. In the etching reaction, hydrogen peroxide is used as the oxidant, and the electric potential difference between H 2 O 2 /H 2 O (E ϴ = 1.776 V) and AuBr 4 − /Au (E ϴ = 0.854 V) [39] ensures its occurrence of the following reaction [40]:…”

Section: Real-time Oxidation Process Of Single Particles In Capillarymentioning

confidence: 99%

Direct observation of single plasmonic metal nanoparticle reaction in microcolumn with chromatic‐aberration‐free LASER light‐sheet scattering imaging

et al. 2019

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Direct observation and characterization of individual noble metal nanoparticles (MNPs) and their chemical reactions have attracted much attention owing to their unique physical and chemical properties and extensive applications. To achieve high‐throughput information‐rich evaluation of MNPs, it would be advantageous to combine highly efficient microcolumn separation technology with on‐column high resolution plasmonic imaging technique. Here, with a chromatic aberration‐suppressed supercontinuum laser light‐sheet scattering imaging system and colorimetric detection, we monitored oxidation process of single gold nanorods inside a capillary under gravity driven flow, and observed heterogenous reaction intermediates and pathways for different MNP surface modifications. The results suggest that molecular interactions and bindings with MNPs have a significant impact on their reaction kinetics. This high‐throughput on‐line single particle detection technique could be potentially applied to chemical and biochemical reaction studies of other MNPs.

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Section: Real-time Oxidation Process Of Single Particles In Capillarymentioning

confidence: 99%

Direct observation of single plasmonic metal nanoparticle reaction in microcolumn with chromatic‐aberration‐free LASER light‐sheet scattering imaging

et al. 2019

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“…These quantities were substituted in Eqs. (9) and (14) instead of E V 2 . In so doing, we used data from papers cited in Table 2 on the concentration coefficients a, b, g, and d and on the molar refractions of these compounds.…”

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confidence: 96%

“…Thus, it is possible to considerably simplify a procedure for determining the dipole moments and Kerr constants in solutions, at least for those classes of compounds for which an additive scheme for calculating molar volumes will be constructed. It should be noted that, when using transformed formulas (9) and (14), it is unnecessary to replace E V 2 by V ad . If it is difficult to determine the densities in the same solvent as that used for determining the dielectric permittivities e 12 and Kerr constants B 12 of solution, because of a low solubility of the solute, E V 2 can be determined in another solvent.…”

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confidence: 99%

“…If such a scheme will give sufficiently accurate results for various classes of compounds, it will substantially reduce the experimental time required to determine the dipole moments of molecules in solutions from their polarization E P 2 [4], and also the Kerr constants E ( m K 2 ) [5]. In this case, it will be necessary to replace the molar volume E V 2 in formulas (9) and (14) by the additively calculated molar volume V ad . This replacement will make it unnecessary to measure the solution densities when determining the dipole moments and Kerr constants, the more so as measuring densities is one of the most labor-consuming steps of the corresponding experiments [4].…”

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confidence: 99%

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Molecular Polarizability of Organic Compounds and Their Complexes: XLVIII. Molar Volumes of Benzene Derivatives in Solutions at Infinite Dilution, Their Additivity, and Correlation with the Dipole Moments and Kerr Constants

et al. 2005

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Extrapolation formulas were derived for determination of the molar volume of a solute at infinite dilution. This quantity is stable to solvent replacement and additive with respect to increments of substituents in polysubstituted benzenes. The molar polarization and molar Kerr constant of a solute can be expressed through the molar volumes of the solute at infinite dilution and of the solvent. Replacement of the molar volume in the calculation formulas by the quantity calculated by the additive scheme considerably reduces the experimental time required for determining the dipole moments and Kerr constants of compounds in solution.Partial molar volumes of components are the simplest but important characteristics of liquid solutions, furnishing information on their properties [2]. Of particular interest is the molar volume of a solute extrapolated to infinite dilution, at which the solute molecules do not interact with each other and interact only with the solvent. Division of this quantity by the Avogadro number gives the molecular volume, i.e., the volume of the cavity occupied by a particle in the dynamic structure of the solvent. The molecular volume allows certain conclusions on the features of the solvation shell [2, 3] and, as will be shown in the subsequent papers, on the solute steric structure.The molar volumes of molecules and ions at infinite dilution were determined in numerous papers, but the lack of convenient extrapolation formulas decreasing the random experimental errors apparently complicates the calculations. At the same time, extrapolation formulas have been well developed for determining such partial quantities at infinite dilution as polarization [4] and Kerr constant [5].In this context, our goal was to derive extrapolation formulas for determining the molar volume of a solute at infinite dilution and to reveal correlations of this quantity with the molar polarization and molar Kerr ÄÄÄÄÄÄÄÄÄÄÄÄ 1 For communication XLVII, see [1].constant of the solute. It was also interesting to find whether such molar volume is additive with respect to substituents in molecules, like, e.g., molar refraction, dipole moment, or polarizability tensor. The positive answer we obtained is demonstrated with a wide range of mono-and polysubstituted benzene derivatives.The solution molar volume V 12 is additive with respect to the molar volumes of the solvent V 1 and solute V 2 in accordance with their mole fractions 1 3 x and x:where V 12 = M 12 /r 12 ; M 12 is the mean molar weight of the solution, M 12 = M 1 (1 -x) + M 2 x, M 1 and M 2 are the molar weights of the solvent and solute, respectively; r 12 is the solution density; V 1 = M 1 /r 1 is the solvent molar volume; and r 1 is the solvent density. From formula (1), the molar volume V 2 extrapolated to the infinite dilution, E V 2 , can be expressed by formula (2):Apparently, the limit in formula (2) can be replaced by the derivative in the point x = 0 [formula (3)]:

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“…First, as the isothiocyanate group is considerably more polar than the azido and isocyanate groups (dipole moments of C 6 H 5 N 3 , C 6 H 5 N=C=O, and C 6 H 5 N=C=S: 1.82, 2.43, 2.69 D, respectively), [14] it is possible that the isothiocyanate simply serves as a strongly electron-withdrawing group and promotes S N 2 glycosylation, as has been proposed [15] for the oxazolidinone system. Alternatively, consistent with current models for the through-space stabilization of glycosyl oxocarbenium ions, [16] it is possible that a transient intermediate sialyl oxocarbenium ion preferentially adopts the 5 H 4 conformation 15, which benefits from stabilization by the pseudoaxial 4-Oacetate and the isothiocyanate groups, with the latter providing significant steric shielding to the b-face (Scheme 3).…”

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confidence: 99%

The Isothiocyanato Moiety: An Ideal Protecting Group for the Stereoselective Synthesis of Sialic Acid Glycosides and Subsequent Diversification

Mandhapati¹,

Rajender²,

Shaw³

et al. 2014

Angewandte Chemie

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The preparation of a crystalline, peracetyl adamantanyl thiosialoside donor protected by an isothiocyanate group is described. On activation at −78 °C in the presence of typical carbohydrate acceptors, this donor gives high yields of the corresponding sialosides with exquisite α‐selectivity. The high selectivity extends to the 4‐O‐benzyl‐protected 3‐OH acceptors, which are typically less reactive and selective than galactose 3,4‐diols. Treatment of the α‐sialosides with tris(trimethylsilyl)silane or allyltris(trimethylsilyl)silane results in replacement of the C5N5 bond by a CH or a CC bond. The reaction of the isothiocyanate‐protected sialosides with thioacids generates amides, while reaction with an amine gives a thiourea, which can be converted into a guanidine. The very high α‐selectivities observed with the new donor and the rich chemistry of the isothiocyante function considerably extend the scope for optimization at the sialoside 5‐position.

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Molecular polarisability. Aromatic isothiocyanates

Cited by 12 publications

References 0 publications

Direct observation of single plasmonic metal nanoparticle reaction in microcolumn with chromatic‐aberration‐free LASER light‐sheet scattering imaging

Direct observation of single plasmonic metal nanoparticle reaction in microcolumn with chromatic‐aberration‐free LASER light‐sheet scattering imaging

Molecular Polarizability of Organic Compounds and Their Complexes: XLVIII. Molar Volumes of Benzene Derivatives in Solutions at Infinite Dilution, Their Additivity, and Correlation with the Dipole Moments and Kerr Constants

The Isothiocyanato Moiety: An Ideal Protecting Group for the Stereoselective Synthesis of Sialic Acid Glycosides and Subsequent Diversification

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