Search results for "SOLVENT"
showing 10 items of 1395 documents
Hydration dependent dynamics in sol-gel encapsulated myoglobin.
2008
In this work we study the effect of hydration on the dynamics of a protein in confined geometry, i.e. encapsulated in a porous silica matrix. Using elastic neutron scattering we investigate the temperature dependence of the mean square displacements of non-exchangeable hydrogen atoms of sol-gel encapsulated met-myoglobin. The study is extended to samples at 0.2, 0.3 and 0.5 g water/g protein fractions and comparison is made with met-myoglobin powders at the same average hydration and with a dry powder sample. Elastic data are analysed using a model of dynamical heterogeneity to take into account deviations of elastic intensity from gaussian behaviour in a large momentum transfer range and r…
Photochemical Size Reduction of CdSe and CdSe/ZnS Semiconductor Nanoparticles Assisted by nπ* Aromatic Ketones
2009
A novel effect of n pi* aromatic ketones on the quantum dots optical properties is reported. By controlling experimental conditions such as time of irradiation, presence of air in the media, hydrogen donor capacity of the solvent, and irradiation wavelength, core and core-shell CdSe QDs can be resized as convenient.
Hydrophobic interactions and stacking forces: A convenient model system
1980
Abstract We consider solvent–biomolecule interactions and the role of solvent structural and isotopic alterations on the thermodynamic stability of biomolecular structures. Approaches to this problem range from the study of biomolecular functional stability, to that of the stability of small structural entities suitable of being taken as model systems for (parts of) larger molecules. We shall focus on this latter case and shall consider the dimerization process of small planar molecules (Methylene Blue). These are a convenient model system for the study of interactions responsible e.g. for base stacking in DNA. As an additional advantage, they do not form hydrogen bonds. The experimental st…
Encapsulation of diquats by resorcinarenes: a novel staggered anion–solvent mediated hydrogen bonded capsule
2002
Crystallisation studies of ethyl resorcinarene with diquats 2b and 3a (1,4-dimethyl-1,4-diazoniabicyclo[2.2.2]octane dibromide and 1,4-diazoniabicyclo[2.2.2]octane dichloride, respectively) resulted in hydrogen bonded molecular capsules in which the cations are encapsulated in between the cavities of two resorcinarene molecules and anions are located in the middle of the lower rim ethyl chains.
Tautomerism in pyridazin-3(2H)-one: a theoretical study using implicit/explicit solvation models.
2013
Abstract The tautomeric conversion of pyridazin-3(2H)-one 1 into pyridazin-3-ol 2 has been theoretically studied using density functional theory (DFT) methods at the B3LYP/6-311++G** level. Two mechanisms have been considered for this process: (i) one in which the hydrogen is directly transferred through TS12; and (ii) another one in which a double hydrogen transfer takes place via TS1122 upon formation of the corresponding dimer. The former requires a very high activation energy of 42.64 kcal/mol as a consequence of the strain associated with the formation of the four-membered TS12, while the latter requires a much lower activation energy, 14.66 kcal/mol. Implicit, explicit, and a combinat…
Anharmonicity modeling in hydrogen bonded solvent dimers
2021
Abstract Harmonic and anharmonic frequencies of dimers and mixed dimers of water, methanol and benzene were computed and the results were critically analysed to investigate the anharmonicity of the normal mode vibrations within density functional theory (DFT) with empirically included Grimme correction for dispersion (D3). From several options, the B3LYP-D3/6-31++G* level of theory was selected as a good compromise between accuracy and calculation speed, suitable for future modeling of larger solvent clusters. The obtained raw harmonic and anharmonic second-order perturbation theory of vibrational frequencies (VPT2) were additionally scaled using a two-range procedure (below and above 2000 …
A Bioinspired Dinickel(II) Hydrolase: Solvent Vapor-Induced Hydrolysis of Carboxyesters under Ambient Conditions
2016
From the perspective of synthetic metallohydrolases, a phenoxo-bridged dinickel(II) complex [NiII2(L)(H2O)2(CH3OH)][ClO4]·CH3OH (1) (H3L = 2,6-bis[{{(5-bromo-2-hydroxybenzyl)(N′,N″-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol) has been synthesized and structurally characterized. The presence of a vacant coordination site and a weakly bound water molecule provides the scope for substrate binding to act as a metallohydrolase model. Ethyl acetate vapor diffusion at 298 K to a CH3CN/CH3OH solution of 1 results in the formation of a pentanuclear acetato-bridged complex [NiII5(H2L)2(μ3-OH)2(μ-O2CCH3)4][ClO4]2·CH3CO2C2H5 (2), demonstrating for the first time the metal-coordinated water-promo…
Stereoselective Hydrosilylation of Enals and Enones Catalysed by Palladium Nanoparticles
2011
A highly versatile and efficient hydrosilylation method by palladium nanoparticle catalysis allows the direct and chemoselective synthesis of 1) enolsilanes of high isomeric purity, 2) saturated aldehydes or ketones, or 3) the corresponding saturated acetals from α,β-unsaturated aldehydes or ketones. The choice of the product is determined by simply switching the solvent from THF to mixtures of THF/water or THF/alcohol.
New Internal-Charge-Transfer Second-Order Nonlinear Optical Chromophores Based on the Donor Ferrocenylpyrazole Moiety
2016
A series of new N-arylated ferrocenepyrazole structures, carrying different donor or acceptor substituents in the para position of the aryl ring, has been synthesized by the Chan-Lam cross-coupling reaction. The nonplanar geometric molecular structure of some of these chromophores together with their crystal packing was determined by X-ray diffraction, and the HOMO and LUMO energy levels were evaluated by electrochemical and optical measurements and by density functional theoretical (DFT) calculations. By the investigation of solvent effects and time-dependent DFT (TD-DFT) calculations, the intense electronic absorption band around 270-310 nm was confirmed to be an internal-chargetransfer (…
Purification, crystallization and preliminary X-ray studies of sylvaticin, an elicitin-like protein from Pythium sylvaticum.
2003
Sylvaticin belongs to the elicitin family. These 10 kDa oomycetous proteins induce a hypersensitive response in plants, including necrosis and cell death, but subsequently leading to a non-specific systemic acquired resistance (SAR) against other pathogens. Sylvaticin has been crystallized using PEG 2000 MME as a precipitant agent in the presence of nickel chloride. The crystals belong to space group C2, with unit-cell parameters a = 99.29, b = 25.67, c = 67.45 A, beta = 99.66 degrees. Diffraction data were recorded to 2.1 A resolution at a synchrotron-radiation source.