The effectiveness of solvents as hydrogen bond donors

Taft and Kamlet's -scale of solvent hydrogen bond donation ability is reexamined with regard to its correlations with three widely used polarity scales: Dimroth and Reichardt's E _T (30), Kosower's Z and Mayer's A _N , as well as with the _m values of the solvents when present as monomeric solutes. The correlation with E _T serves to extend the solvent -scale according to the expression:

Extraction and micro-determination of manganese(II) with oxine and aliquat 336

A sensitive and selective method has been developed for the micro-determination of Mn(II) by the selective extraction of the yellow Mn(II)-8-hydroxyquinolinate complex with a liquid ion-exchanger, Aliquat 336, from basic medium. The molar absorptivity of the complex is 2.2 x 10(4)1.mole(-1).cm(-1) at 420 nm and the colour system obeys Beer's law in the range 0.1-3.5 ppm Mn(II) in the final solution. The composition and stability of the complex are discussed. Potential interferents have been examined and the method is applied to analysis of standard steel and bronze samples.     

Hole doping and superconductivity characteristics of the s=1, 2 and 3 members of the (Cu,Mo)-12s2 homologous series of layered copper oxides

Superconductivity characteristics have been systematically evaluated for a two-CuO₂-plane copper oxide system, (Cu,Mo)-12s2, upon increasing the number of fluorite-structured layers, s, between the two CuO₂ planes. Essentially single-phase samples of (Cu_0.75Mo_0.25)Sr₂YCu₂O_7+δ (s=1), (Cu_0.75Mo_0.25)Sr₂(Ce_0.45Y_0.55)₂Cu₂O_9+δ (s=2) and (Cu_0.75Mo_0.25)Sr₂(Ce_0.67Y_0.33)₃Cu₂O_11+δ (s=3) were synthesized through a conventional solid-state route in air. To make the samples superconductive an additional high-pressure oxygenation (HPO) treatment was required. Such treatment (carried out at 5 GPa and 500 °C in the presence of 75 mol% Ag₂O₂ as an oxygen source to maximize the T_c) compressed the crystal lattice for the three members of the (Cu_0.75Mo_0.25)-12s2 series equally, i.e., by 0.01 Å for the a parameter and by 0.07 Å for the c parameter per formula unit. From both Cu L-edge and O K-edge XANES spectra the s=1 sample was found to possess the highest overall hole-doping level among the HPO samples. Accordingly it exhibited the best superconductivity characteristics. With increasing s, both the T_c (s=1: 88 K, s=2: 61 K, s=3: 53 K) and H_irr values got depressed, being well explained by the trend of decreasing CuO₂-plane hole concentration with increasing s as revealed from O K-edge XANES spectra for the same samples. Hence, the present results do not suggest any significant (negative) impact on the superconductivity characteristics from the gradually thickened fluorite-structured block itself.     

An evaluation of acid digestion methods for amniotic fluid phospholipids

Five methods of acid digestion of amniotic fluid phospholipids for inorganic phosphate release were evaluated at a temperature of 225 °C and a heating time of 30 min. The methods used the following digestants: (A (perchloric acid), B (perchloric acid containing molybdate), C (sulfuric acid, 30% hydrogen peroxide, 5% urea), D (sulfuric-perchloric acids), and E (sulfuric-perchloric acids with vanadium pentoxide). After digestion and dilution with water, a hydrogen ion concentration of about 2.5 mol/ liter was obtained that permitted the use of stannous chloride-hydrazine sulfate as the reducing agent for phosphate color development. Recoveries of the different amniotic fluid phospholipids and aqueous phosphate standards were quantitative for all methods. A comparative study with amniotic fluids showed similar results for all methods. Since all methods were found to be equivalent under the specified conditions described, the choice was dependent upon the user's preference.     

Functional monomers and polymers. LXI. Photochemical reactions on the synthetic polymers containing thymine bases

Photodimerization of N-2-isobutyloxyethyl thymine (T-M), bis[2-(5-methyl-1-primidinyl)-ethyl] glutarate (T-T), poly(N-2-methacryloyloxyethyl thymine) (polyMAOT), and poly(N-2-acryloyloxyethyl thymine) (poly AOT) was studied in dimethylformamide solution. The rate of intramolecular photodimerization of polyMAOT and polyAOT was 5.7 and 7.2 times faster, respectively, than that of T-T. In T-M, however, intermolecular photodimerization did not occur under the reaction condition used. Quenching studies with isoprene suggest that the photodimerization of T-T occurs predominantly in an excited triplet state, whereas that of polyMAOT and polyAOT occur in singlet and triplet states. It was concluded that the photodimers of T-T, polyMAOT, and polyAOT are two syn-fused cyclobutane-type dimers (cis-syn and trans-syn). Quantum efficiencies of thymine base disappearance were determined by ultraviolet (UV) analysis to be 0.0012 for T-T, 0.0084 for polyMAOT, and 0.010 for polyAOT.     

Probing organic layers on the TiO2(110) surface

In this work, we use first principles simulations to provide features of the dynamic scanning force microscopy imaging of adsorbed organic layers on insulating surfaces. We consider monolayers of formic (HCOOH) and acetic (CH(3)COOH) acid and a mixed layer of acetic and trifluoroacetic acids (CF(3)COOH) on the TiO(2)(110) surface and study their interaction with a silicon dangling bond tip. The results demonstrate that the silicon tip interacts more strongly with the substrate and the COO(-) group than the adsorbed acid headgroups, and, therefore, molecules would appear dark in images. The pattern of contrast and apparent height of molecules is determined by the repulsion between the tip and the molecular headgroups and by significant deformation of the monolayer and individual molecules. The height of the molecule on the surface and the size of the headgroup play a large role in determining access of the tip to the substrate and, hence, the contrast in images. Direct imaging of the molecules themselves could be obtained by providing a functionalized tip with attraction to the molecular headgroups, for example, a positive potential tip.     

The allyloxycarbonyl group for alcohol protection: quantitative removal or transformation into allyl protecting group via π-allyl complexes of palladium

In the presence of Pd catalysts and under mild, essentially nonbasic conditions, the allyloxycarbonyl derivatives of alcohols may be either converted into the corresponding allyl ethers or hydrogenolysed (Bu₃SnH) back to the starting alcohol.     

H-bonds of imidazole crystals. II. Determination of the magnitudes of the various anharmonic couplings of vs modes

In this article results given in a previous paper (part I), concerning the spectra of NH and ND species recorded with a polarization parallel to the c axis are analyzed, the necessary corrections on the raw data performed, v_s bands and their first moments are then compared with corresponding quantities predicted from a simple theory which describes quantitatively the anharmonic interactions of a single H-bond with a low frequency vibration of the same H-bond and with binary combinations of modes (Fermi resonances). This allows us to determine the magnitudes of the various anharmonic interactions involved. It appears that the low frequency vibration which modulates v_s is a bending mode of the H-bond (NH ↑ … N), a finding somewhat unexpected, as this low frequency vibration is usually thought to be the stretching vibration v_σ of the H-bond

     

Abnormal protein spots revealed by two-dimensional electrophoresis in mycoplasma-infected human fibroblasts

Six new protein spots were detected by two-dimensional electrophoresis in cultured human fibroblasts infected with mycoplasma. No changes were observed in other protein spots present in normal and pathological cells. After treatment with an antimycoplasma drug for a week, the new spots disappeared and the cells became negative for mycoplasma stain.     

A simple technique to measure regional cerebral blood flow during intravascular balloon clamping

A case of giant internal carotid ophthalmic aneurysm was presented. In order to clarify whether the patient could tolerate carotid occlusion, a balloon clamping test was performed. before surgery. The cerebral blood flow was measured using early imaging by single photon emission computed tomography (SPECT) with N-isopropyl-(iodine-123)-p-iodoamphetamine (123I-IMP). When the balloon clamping test was performed the tracer was injected, and scanning was performed 35 minutes after removing the catheter. This tracer enabled a "memory of blood flow" during temporary ischemia to determine the character of quick diffusion and slow wash out, that could not be performed by other methods of cerebral blood flow measurement. SPECT with 123I-IMP can simplify the measurement of cerebral blood flow during the balloon clamping test.