Search results for "Solvent"
showing 10 items of 1395 documents
Rotation correlation time as a measure of microviscosity of excited state isomerization reactions of three cyanine dyes in n-alcohol solutions
1994
Abstract Rotation correlation times of three chemically similar cyanine dyes of different sizes in n -alcohol solutions have been recorded at several temperatures by using polarized picosecond spectroscopy. For all three dyes the linear temperature dependencies of τ or on η/ T were observed to be independent of solvent up to viscosities of about 60 cP. The rotational motion of the dyes proceeds at much slower rates than the excited state isomerization in viscous solutions of the same fluidity. Isomerization seems to depend on special solvent-induced changes of the force field of the reactant and clearly proceeds faster, especially for the two larger dyes, than predicted by Kramers' theory a…
Magnetic field-induced alignment of molecular rotor-shaped cyclophanes
2010
Molecular pinwheels consisting of dipolar substituted cyclophanes in solution can function as free microscopic rotors in the presence of a homogeneous static magnetic field B and a circularly polarized electric field E rotating on a plane containing B. Owing to the high magnetic anisotropy of [26](1,2,3,4,5,6)cyclophane and [36](1,2,3,4,5,6)cyclophane biased by strong ring currents, ∼1 in 105 molecules are expected to align with the C6 symmetry axis perpendicular to a magnetic field of 21 T. The magnetic-field-controlled alignment of rotor-shaped cyclophanes is insignificantly affected by nonpolar solvents, for example, toluene.
The reluctant polymorph: investigation into the effect of self-association on the solvent mediated phase transformation and nucleation of theophylline
2015
Little is known concerning the pathway of the crystallization of the thermodynamically stable polymorph of theophylline, form IV. Here we study the reasons why the thermodynamically stable theophylline form IV can be obtained only by slow, solvent mediated phase transformation (SMPT) in specific solvents, and whether the presence of prenucleation aggregates affect the polymorphic outcome. Solution concentration, polymorphic composition and morphology were monitored over time during the transformation from form II to form IV in several solvents. NMR and FTIR spectroscopy were used to detect prenucleation molecular aggregates present in the solutions. It was determined that theophylline self-…
A statistical study of the additivities of substituent effects in the13C NMR chemical shifts of hydroxy- and chloro-substituted benzenes
1980
The 13C NMR spectra of six hydroxybenzenes, all chlorobenzenes, all chlorophenols and eight chlorocatechols are measured and assigned. The additivity of the substituent effects and the usefulness of some corrective parameters are studied with regression analysis. The order of the chemical shifts is most efficiently predicted by the simplest substituent effect model, containing only the direct effects of the substituents, although the 95% confidence limits of the calculated shifts are as high as 5.6 ppm. If the chemical shifts need to be predicted within the measuring errors (approximately 0.05–0.10 ppm, in the present data), the number of necessary corrections is very impractical. The corre…
1H,13C and17O NMR study of aromatic ring-substituted monochloro- and monobromo-(E)-3-phenylpropenals
1991
Trans-Cinnamaldehydes (CAs) or o-, m- and p-X-(E)-3-phenylpropenals; (X = Cl or Br) were synthesized and their 1H, 13C and 17O NMR spectra were measured, assigned and analysed. The long-range benzylic couplings are discussed in terms of the conformational characteristics of the related styrene systems. The 1H, 13C and 17O NMR substituent chemical shifts of the CA derivatives were compared with those of styrene and explained by the π-electron delocalization in the conjugated CCCO bond system of CA.
On the Formation of Droperidol Solvates: Characterization of Structure and Properties
2014
A solvate screening and characterization of the obtained solvates was performed to rationalize and understand the solvate formation of active pharamaceutical ingredient droperidol. The solvate screening revealed that droperidol can form 11 different solvates. The analysis of the crystal structures and molecular properties revealed that droperidol solvate formation is mainly driven by the inability of droperidol molecules to pack efficiently. The obtained droperidol solvates were characterized by X-ray diffraction and thermal analysis. It was found that droperidol forms seven nonstoichiometric isostructural solvates, and the crystal structures were determined for five of these solvates. To b…
Organometallic nucleophiles. Mechanism of halide displacement at saturated carbon by 2-pyridyl and 4-Pyridyl complexes [M(dmtc)(C5H4N-Cn)(L)] (M Pd…
1992
Abstract A mechanistic study is reported of nucleophilic halide substitution by pyridyl complexes [M(dmtc)C 5 H 4 N- C 2 )(L)] (M Pd or Pt; L PMe 3 , PEt 3 or PPh 3 ) and [Pd(dmtc)C 5 H 4 N- C 4 )(L)] (L PMe 3 or PPh 3 ) on organic halides XCH 2 R (X Cl or Br; R CHCH 2 , COMe, Ph, or CN) in various solvents, yielding the pyridylium derivatives [M(dmtc)1-CH 2 R)C 5 H 4 N- C 2 (L)] + and [Pd(dmtc)(1-CH 2 R)(C 5 H 4 N- C 4 (L)] + , respectively. The kinetics obey a second-order rate law: rate k 2 [XCH 2 R][Complex]. A similar rate law is observed for the analogous reactions involving 4-dimethyl-aminopyridine (4-dmapy) as the nucleophile. The effects of solvent and leaving group, a…
Assembly and Separation of Semiconductor Quantum Dot Dimers and Trimers
2011
Repeated precipitation of colloidal semiconductor quantum dots (QD) from a good solvent by adding a poor solvent leads to an increasing number of QD oligomers after redispersion in the good solvent. By using density gradient ultracentrifugation we have been able to separate QD monomer, dimer, and trimer fractions from higher oligomers in such solutions. In the corresponding fractions QD dimers and trimers have been enriched up to 90% and 64%, respectively. Besides directly coupled oligomers, QD dimers and trimers were also assembled by linkage with a rigid terrylene diimide dye (TDI) and separated again by ultracentrifugation. High-resolution transmission electron micrographs show that the …
Anharmonic vibrational frequency calculations for solvated molecules in the B3LYP Kohn–Sham basis set limit
2012
Abstract The solvent dependence of harmonic and anharmonic vibrational wavenumbers of water, formaldehyde and formamide was studied using the B3LYP method. The results obtained with the hierarchy of Jensen's polarization-consistent basis sets were fitted with two-parameter formula toward the B3LYP Kohn–Sham complete basis set (CBS) limit. Anharmonic corrections have been obtained by a second order perturbation treatment (VPT2) and vibrational configuration interaction (VCI) method. The solvent environment was treated according to the self-consistent reaction field polarizable continuum model (SCRF PCM) approach.
Static and dynamic screening effects in the electrostatic self-assembly of nano-particles.
2014
In the description of charge screening in the electrostatic self-assembly of nanoparticles (molecules) embedded into a polar solvent, the static screening effects (a contribution associated with the rapid spatial redistribution of small and highly mobile ions of a solvent) are traditionally treated phenomenologically, using the Yukawa short-range potential for describing the interaction between these particles. However, this model has a limited range of applicability being valid only for infinitely diluted systems and high salt concentrations. During a slow self-assembling process with nanoparticle formation, very dense structural elements (aggregates) are formed, in which the distances bet…