Understanding solvation

The effects of solvents on different chemical phenomena, including reactivity, spectroscopic data, and swelling of biopolymers can be rationalized by use of solvatochromic probes, substances whose UV-vis spectra, absorption, or emission are sensitive to the properties of the medium. Thermo-solvatochromism refers to the effect of temperature on solvatochromism. The study of both phenomena sheds light on the relative importance of the factors that contribute to solvation, namely, properties of the probe, those of the solvent (acidity, basicity, dipolarity/polarizability, and lipophilicity), and the temperature. Solvation in binary solvent mixtures is complex because of ""preferential solvation"" of the probe by some component of the mixture. A recently introduced solvent exchange model is based on the presence in the binary solvent mixture of the organic component (molecular solvent or ionic liquid), S, water, W, and a 1:1 hydrogen-bonded species (S-W). Solvation by the latter is more efficient than by its precursor solvents, due to probe-solvent hydrogen-bonding and hydrophobic interactions; dimethyl sulfoxide (DMSO)-W is an exception. Solvatochromic data are employed in order to explain apparently disconnected phenomena, namely, medium effect on the pH-independent hydrolysis of esters, (1)H NMR data of water-ionic liquid (IL) mixtures, and the swelling of cellulose.

Miscibility and specific interactions in blends of poly(4-vinylphenol) and poly(2-ethoxyethyl methacrylate)

The properties of the hydrogen-bonded polymer blends of poly(4-vinylphenol) and poly(2-ethoxyethyl methacrylate) are presented. Spectroscopic techniques such as C-13 solid-state NMR and FT-IR are used to probe specific interactions of the blends at various compositions. Spectral features from both techniques revealed that site-specific interactions are present, consistent with a significant degree of mixing of the blend components. Changes in chemical shift and line shape of the phenolic carbon and carbonyl resonances in the C-13 CPMAS spectra of the blends as a function of composition are interpreted as resulting from changes in the relative intensities of two closely overlapped signals. A quantitative measure of hydrogen-bonded carbonyl groups using C-13 NMR has been obtained which agreed well with the results from FT-IR analyses. It is also shown that C-13 NMR can be used to measure the fraction of hydroxyl groups associated with carbonyl groups, which was not possible previously using FT-IR due to extensive overlapping of bands in the hydroxyl stretching region. The results of measurements of H-1 T-1 and 1H T-1 rho indicate that PVPh and PEEMA are intimately mixed on a scale less than 2-3 nm.

Comprehensive study of surface chemistry of MCM-41 using Si-29 CP/MAS NMR, FTIR, pyridine-TPD, and TGA

A comprehensive study was conducted on mesoporous MCM-41. Spectroscopic examinations demonstrated that three types of silanol groups, i.e., single, (SiO)(3)Si-OH, hydrogen-bonded, (SiO)(3)Si-OH-OH-Si(SiO)(3), and geminal, (SiO)(2)Si(OH)(2), can be observed. The number of silanol groups/nm(2), alpha(OH), as determined by NMR, varies between 2.5 and 3.0 depending on the template-removal methods. All these silanol groups were found to be the active sites for adsorption of pyridine with desorption energies of 91.4 and 52.2 kJ mol(-1), respectively. However, only free silanol groups (involving single and geminal silanols) are highly accessible to the silylating agent, chlorotrimethylsilane. Silylation can modify both the physical and chemical properties of MCM-41.

1-Ethynyl-2-isopropoxy-3-methoxybenzene

The crystal structure of the title compound, C12H14O2, has been determined at 150 K. Significant intermolecular non-conventional C-H...O interactions involving the terminal acetylinic H atom are observed, which result in a zigzag hydrogen-bonded chain in the b direction.

Adherend thickness effect on the tensile fracture toughness of a structural adhesive using an optical data acquisition method

Adhesive bonding is nowadays a serious candidate to replace methods such as fastening or riveting, because of attractive mechanical properties. As a result, adhesives are being increasingly used in industries such as the automotive, aerospace and construction. Thus, it is highly important to predict the strength of bonded joints to assess the feasibility of joining during the fabrication process of components (e.g. due to complex geometries) or for repairing purposes. This work studies the tensile behaviour of adhesive joints between aluminium adherends considering different values of adherend thickness (h) and the double-cantilever beam (DCB) test. The experimental work consists of the definition of the tensile fracture toughness (GIC) for the different joint configurations. A conventional fracture characterization method was used, together with a J-integral approach, that take into account the plasticity effects occurring in the adhesive layer. An optical measurement method is used for the evaluation of crack tip opening and adherends rotation at the crack tip during the test, supported by a Matlab® sub-routine for the automated extraction of these quantities. As output of this work, a comparative evaluation between bonded systems with different values of adherend thickness is carried out and complete fracture data is provided in tension for the subsequent strength prediction of joints with identical conditions.

Chlorite Dismutase from perchlorate reducing bacteria. A potential biocatalyst to eliminate chlorinated species from polluted water resources and industrial wastes

Magnetospirillum (M.) sp. strain Lusitani, a perchlorate reducing bacteria (PRB), was previously isolated from a wastewater treatment plant and phylogenetic analysis was performed to classify the isolate. The DNA sequence of the genes responsible for perchlorate reduction and chlorite dismutation was determined and a model was designed based on the physiological roles of the proteins involved in the pcr-cld regulon. Chlorite dismutase (Cld) was purified from Magnetospirillum sp. strain Lusitani cells grown in anaerobiosis in the presence of perchlorate. The protein was purified up to electrophoretic grade using HPLC techniques as a 140 kDa homopentamer comprising five ~28 kDa monomers. Steady-state kinetic studies showed that the enzyme follows a Michaelis-Menten model with optimal pH and temperature of 6.0 and 5°C, respectively. The average values for the kinetic constants KM and Vmax were respectively 0.56 mM and 10.2 U, which correspond to a specific activity of 35470 U/mg and a turnover number of 16552 s-1. Cld from M. sp. strain Lusitani is inhibited by the product chloride, but not by dioxygen. Inhibition constants KiC= 460 mM and KiU= 480 mM indicated that sodium chloride is a weak mixed inhibitor of Cld, with a slightly stronger competitive character. The X-ray crystallography structure of M. sp. strain Lusitani Cld was solved at 3.0 Å resolution. In agreement with cofactor content biochemical analysis, the X-ray data showed that each Cld monomer harbors one heme b coordinated by a histidine residue (His188), hydrogen-bonded to a conserved glutamic acid residue (Glu238). The conserved neighboring arginine residue (Arg201) important for substrate positioning, was found in two different conformations in different monomers depending on the presence of the exogenous ligand thiocyanate. UV-Visible and CW-EPR spectroscopies were used to study the effect of redox agents, pH and exogenous ligands on the heme environment.

Nd-, O-, and H-isotopic evidence for complex, closed-system fluid evolution of the peralkaline Ilimaussaq intrusion, South Greenland

Relatively homogeneous oxygen isotope compositions of amphibole, clinopyroxene, and olivine separates (+5.2 to +5.7parts per thousand relative to VSMOW) and neodymium isotope compositions (epsilon(Nd(T)) = -0.9 to -1.8 for primary magmatic minerals and epsilon(Nd(T)) = -0.1 and -0.5 for mineral separates from late-stage pegmatites and hydrothermal veins) from the alkaline to agpaitic llimaussaq intrusion, South Greenland, indicate a closed system evolution of this igneous complex and support a mantle derivation of the magma. In contrast to the homogeneous oxygen and neodymium isotopic data, deltaD values for hand-picked amphibole separates vary between -92 and -232parts per thousand and are among the most deuterium-depleted values known from igneous amphiboles. The calculated fluid phase coexisting with these amphiboles has a homogeneous oxygen isotopic composition within the normal range of magmatic waters, but extremely heterogeneous and low D/H ratios, implying a decoupling of the oxygen- and hydrogen isotope systems. Of the several possibilities that can account for such unusually low deltaD values in amphiboles (e.g., late-stage hydrothermal exchange with meteoric water, extensive magmatic degassing, contamination with organic matter, and/or effects of Fe-content and pressure on amphibole-water fractionation) the most likely explanation for the range in deltaD values is that the amphiboles have been influenced by secondary interaction and reequilibration with D-depleted fluids obtained through late-magmatic oxidation of internally generated CH(4) and/or H(2). This interpretation is consistent with the known occurrence of abundant magmatic CH(4) in the Ilimaussaq rocks and with previous studies on the isotopic compositions of the rocks and fluids. Copyright (C) 2004 Elsevier Ltd.

Influence of pressure and radio frequency power on deposition rate and structural properties of hydrogenated amorphous silicon thin films prepared by plasma deposition

The influence of radio frequency (rf) power and pressure on deposition rate and structural properties of hydrogenated amorphous silicon (a-Si:H) thin films, prepared by rf glow discharge decomposition of silane, have been studied by phase modulated ellipsometry and Fourier transform infrared spectroscopy. It has been found two pressure regions separated by a threshold value around 20 Pa where the deposition rate increases suddenly. This behavior is more marked as rf power rises and reflects the transition between two rf discharges regimes. The best quality films have been obtained at low pressure and at low rf power but with deposition rates below 0.2 nm/s. In the high pressure region, the enhancement of deposition rate as rf power increases first gives rise to a reduction of film density and an increase of content of hydrogen bonded in polyhydride form because of plasma polymerization reactions. Further rise of rf power leads to a decrease of polyhydride bonding and the material density remains unchanged, thus allowing the growth of a-Si:H films at deposition rates above 1 nm/s without any important detriment of material quality. This overcoming of deposition rate limitation has been ascribed to the beneficial effects of ion bombardment on the a-Si:H growing surface by enhancing the surface mobility of adsorbed reactive species and by eliminating hydrogen bonded in polyhydride configurations.

Production of nanometric particles in radio frequency glow discharges in mixtures of silane and methane

The formation of silicon particles in rf glow discharges has attracted attention due to their effect as a contaminant during film deposition or etching. However, silicon and silicon alloy powders produced by plasma¿enhanced chemical vapor deposition (PECVD) are promising new materials for sintering ceramics, for making nanoscale filters, or for supporting catalytic surfaces. Common characteristics of these powders are their high purity and the easy control of their stoichiometry through the composition of the precursor gas mixture. Plasma parameters also influence their structure. Nanometric powders of silicon¿carbon alloys exhibiting microstructural properties such as large hydrogen content and high surface/volume ratio have been produced in a PECVD reactor using mixtures of silane and methane at low pressure (-1 Torr) and low frequency square¿wave modulated rf power (13.56 MHz). The a¿Si1¿xCx:H powders were obtained from different precursor gas mixtures, from R=0.05 to R=9, where R=[SiH4]/([SiH4]+[CH4]). The structure of the a¿Si1¿xCx:H powder was analyzed by several techniques. The particles appeared agglomerated, with a wide size distribution between 5 and 100 nm. The silane/methane gas mixture determined the vibrational features of these powders in the infrared. Silicon-hydrogen groups were present for every gas composition, whereas carbon¿hydrogen and silicon¿carbon bonds appeared in methane¿rich mixtures (R-0.6). The thermal desorption of hydrogen revealed two main evolutions at about 375 and 660¿°C that were ascribed to hydrogen bonded to silicon and carbon, respectively. The estimated hydrogen atom concentration in the sample was about 50%.

Relação entre transferência de carga e as interações intermoleculares em complexos de hidrogênio heterocíclicos

Hydrogen-bonded complexes formed by the interaction of the heterocyclic molecules C2H4O and C2H5N with HF, HCN, HNC and C2H2 have been studied using density functional theory. The hydrogen bond strength has been analyzed through electron density charge transfer from the proton acceptor to the proton donor. The density charge transfer has been estimated using different methods such as Mulliken population analysis, CHELPG, GAPT and AIM. It has been shown that AIM-estimated charge transfer correlates very well with the hydrogen bond energy and the infrared bathochromic effect of the proton donor stretching frequencies.

Um estudo teórico relativo à não-linearidade da ligação de hidrogênio em sistemas heterocíclicos C2H4O-C2H2 e C2H4S-C2H2

B3LYP/6-31G(d,p) calculations were used to determine the optimized geometries of the C2H4O-C2H2 and C2H4S-C2H2 heterocyclic hydrogen-bonded complexes. Results of structural, rotational, electronic and vibrational parameters indicate that the hydrogen bonding is non-linear due to the pi bond of the acetylene interacting with the hydrogen atoms of the methyl groups of the three-membered rings. Moreover, the theoretical investigation showed that the non-linearity is much more intriguing, since there is a structural disjunction on the acetylene within the heterocyclic system.

Um estudo teórico de propriedades moleculares em complexos de hidrogênio trimoleculares C2H4···2HF, C2H2···2HF e C3h6···2HF

We present a theoretical study of molecular properties in C2H4···2HF, C2H2···2HF and C3H6···2HF trimolecular hydrogen-bonded complexes. From B3LYP/6-311++G(d,p) calculations, the most important structural deformations are related to the C=C (C2H4), C≡C (C2H2), C-C (C3H6) and HF bond lengths. According to the Bader's atoms in molecules and CHELPG calculations, it was identified a tertiary interaction between the fluorine atom of the second hydrofluoric acid molecule and hydrogen atoms of the ethylene and acetylene within the C2H4···2HF and C2H2···2HF complexes, respectively. Additionally, the evaluation of the infrared spectrum characterized the new vibrational modes and bathochromic effect of the HF molecules.

Metodologia AGOA: a modelagem de clusters de hidratação no complexo aziridina···ácido fluorídrico

We present a theoretical study of solvent effect on C2H5N···HF hydrogen-bonded complex through the application of the AGOA methodology. By using the TIP4P model to orientate the configuration of water molecules, the hydration clusters generated by AGOA were obtained through the analysis of the molecular electrostatic potential (MEP) of solute (C2H5N···HF). Thereby, it was calculated the hydration energies on positive and negative MEP fields, which are maxima (PEMmax) and minima (PEMmin) when represent the -CH2- methylene groups and hydrofluoric acid, respectively. By taking into account the higher and lower hydration energy values of -370.6 kJ mol-1 and -74.3 kJ mol-1 for PEMmax and PEMmin of the C2H5N···HF, our analysis shows that these results corroborate the open ring reaction of aziridine, in which the preferential attack of water molecules occurs at the methylene groups of this heterocyclic.

Solvation simplified

The effects of solvents on chemical phenomena is complex because there are various solute-solvent interaction mechanisms. Solvatochromism refers to the effects of solvents on the spectra of probes. The study of this phenomenon sheds light on the relative importance of the solvation mechanisms. Solvation in pure solvents is quantitatively analyzed in terms of a multi-parameter equation. In binary solvent mixtures, solvation is analyzed by considering the organic solvent, S, water, W, and a 1:1 hydrogen bonded species (S-W). The applications of solvatochromism to understand distinct chemical phenomena, reactivity and swelling of cellulose, is briefly discussed.

Orientation of Non-Native 2-Monosubstituted and 2,3-Disubstituted 1,4-Naphthoquinones in the A1 binding site of PSI and the effect on the rate of electron transfer : an electron paramagnetic resonance spectroscopy study

The proce-ss ofoxygenic photosynthesis is vital to life on Earth. the central event in photosynthesis is light induced electron transfer that converts light into energy for growth. Ofparticular significance is the membrane bound multisubunit protein known as Photosystem I (PSI). PSI is a reaction centre that is responsible for the transfer of electrons across the membrane to reduce NADP+ to NADPH. The recent publication ofa high resolution X-ray structure of PSI has shown new information about the structure, in particular the electron transfer cofactors, which allows us to study it in more detail. In PSI, the secondary acceptor is crucial for forward electron transfer. In this thesis, the effect of removing the native acceptor phylloquinone and replacing it with a series of structurally related quinones was investigated via transient electron paramagnetic resonance (EPR) experiments. The orientation of non native quinones in the binding site and their ability to function in the electron transfer process was determined. It was found that PSI will readily accept alkyl naphthoquinones and anthraquinone. Q band EPR experiments revealed that the non-native quinones are incorporated into the binding site with the same orientation of the headgroup as in the native system. X band EPR spectra and deuteration experiments indicate that monosubstituted naphthoquinones are bound to the Al site with their side group in the position occupied by the methyl group in native PSI (meta to the hydrogen bonded carbonyl oxygen). X band EPR experiments show that 2, 3- disubstituted methyl naphthoquinones are also incorporated into the Al site in the same orientation as phylloquinone, even with the presence of a halogen- or sulfur-containing side chain in the position normally occupied by the phytyl tail ofphylloquinone. The exception to this is 2-bromo-3-methyl --.- _. -. - -- - - 4 _._ _ _ - _ _ naphthoquinone which has a poorly resolved spectrum, making determination of the orientation difficuh. All of the non-native quinones studied act as efficient electron acceptors. However, forward electron transfer past the quinone could only be demonstrated for anthraquinone, which has a more negative midpoint potential than phylloquinone. In the case of anthraquinone, an increased rate of forward electron transfer compared to native PSI was found. From these results we can conclude that the rate ofelectron transfer from Al to Fx in native PSI lies in the normal region ofthe Marcus Curve.